Reactive Modifiers For Polymers

Reactive Modifiers for Polymers
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Reactive Modifiers
for Polymers
Edited by
S. AL-MALAIKA
Polymer Processing and Performance Group
Department of Chemical Engineering and Applied Chemistry
Aston University
Birmingham
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First edition 1997
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Contents
List of contributors
Preface
1
Free-radical grafting of monomers onto polymers by

reactive extrusion: principles and applications
xi
xiii
1
G.-H. HU, J.-J. FLAT and M. LAMBLA

Introduction
Free-radical grafting: an overall mechanistic view
1.2.1 Overall reaction scheme
1.2.2 Initiator decomposition: halflife, initiator grafting efficiency
and hydrogen-abstracting capacity
1.2.3 Fate of macroradicals: chain scission, branching and
cross-linking and/or grafting
1.3 Melt free-radical grafting: particular features
1.3.1 Temperature effects
1.3.2 Viscosity effects
1.3.3 Heterogeneity effects
1.4 Challenges facing melt free-radical grafting
1.4.1 Grafting versus degradation, cross-linking
and homopolymerisation
1.4.2 Effects of processing parameters
1.4.3 Grafting mechanisms and microstructure of grafts
1.5 Recent advances in melt free-radical grafting
1.5.1 Description of the grafting systems and reactors used
1.5.2 Maleic anhydride (MA) onto polypropylene (PP)
1.5.3 Glycidyl methacrylate (GMA) onto polypropylene (PP)
1.5.4 Mechanisms of melt free-radical grafting
1.6 Concluding remarks
1.1
1.2
Appendix I.A
1.A.1
List of abbreviations
1.A.1.1 Polymers and chemicals
LA. 1.2 Miscellaneous
References
Modification of polypropylene by organic peroxides
1
2
2
4
13
17
17
20
20
21
22
23
25
29
30
32
49
65
77
80
80
80
81
82
84
A.H. HOGT, J. MEIJER and J. JELENIC

2.1
Introduction
2.1.1 Modifications of polyolefins
84
84
CONTENTS
VI
2.1.2 Polypropylene
2.1.3 Organic peroxides
2.2 Background
2.2.1 Radical reactions in polymers
2.2.2 Organic peroxides
2.2.3 Model studies
2.2.4 Summary
2.3 Modifications of PP by organic peroxides
2.3.1 Controlled degradation of PP
2.3.2 Cross-linking of PP
2.3.3 Peroxidation of PP
2.3.4 Grafting of PP with reactive monomers
2.3.5 Reactive blending of PP
2.4 Future trends
Acknowledgements
Appendix 2.A
2.A.l
2.A.1.1 Polymers
2.A.1.2 Peroxides
2.A.1.3 Miscellaneous
References
Blends of polyamides and maleic-anhydridecontaining polymers: interfacial chemistry

and properties
84
85
85
85
86
88
91
92
92
98
102
104
117
122
123
124
124
124
124
125
125
133
M. VAN DUIN and R.J.M. BORGGREVE

3.1
Introduction
3.1.1 (In situ) compatibilization of polymer blends
3.1.2 Blends of polyamides and maleic-anhydridecontaining polymers
3.1.3 Scope ofreview
3.2 Interdependence of chemistry, rheology and morphology-interface
3.2.1 Chemistry in blends of polyamides and maleic-anhydridecontaining polymers
3.2.2 Morphology and rheology of blends of polyamides and
maleic-anhydride-containing polymers
3.3 Relationships between morphology-interface and blend properties
3.3.1 Rubber-toughened polyamides
3.3.2 PolyamidejABS blends
3.3.3 Tough polyamidejpoly(phenylene oxide) blends
3.4 Overall model and future trends
Appendix 3.A
3.A.l
3.A.1.1 Polymers
References
133
133
134
135
137
137
150
154
154
155
156
157
160
160
160
160
160
CONTENTS
Modification of polymer melts by oxazolines

and their use for interfacial coupling reactions
with other functional polymers
Vll
163
N.C. LIU and W.E. BAKER

4.1
4.2
Introduction
Preparation of oxazoline-functionalized polymers
4.2.1 Vinyl oxazoline monomers
4.2.2 Copolymerization
4.2.3 Modification
4.3 Interfacial reactions with other functional polymers
4.3.1 Interfacial reactions
4.3.2 Properties of blends with oxazoline-modified interfaces
4.3.3 The separate roles of interfacial reaction and rubber particle
size in toughening polymers
4.4 Modification of polymer melts by bis-2-oxazolines
4.5 Conclusions
4.6 Future trends
Appendix 4.A
4.A.1 List of abbreviations
References
Moisture cross-linkable silane-modified polyolefins
163
164
164
164
165
167
167
176
187
190
192
192
194
194
195
196
D. MUNTEANU
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
Introduction
Processes for cross-linking polyolefins
5.2.1 Irradiation cross-linking
5.2.2 Peroxide cross-linking
5.2.3 Silane cross-linking
The chemistry of silane cross-linking
5.3.1 Synthesis of silane-modified polyolefins
5.3.2 Cross-linking of silane-modified polyolefins
Silane-grafting processes
5.4.1 Reactive processing equipment
5.4.2 The effects of various parameters on the grafting reaction
5.4.3 The effects of various parameters on the cross-linking process
Silane copolymerisation processes
5.5.1 High-pressure ethylene polymerisation plants
5.5.2 Product differentiation
Structure and general properties of silane cross-linked polyolefins
Applications of silane cross-linked polyolefins
5.7.1 Specific requirements for the use of silane cross-linkable
polyolefins in practice
5.7.2 Wire and cable insulation
5.7.3 Pipes
5.7.4 Mouldings
5.7.5 Adhesion-related applications
5.7.6 Foams
5.7.7 Other applications
Other silane cross-linking approaches
Concluding remarks and future trends
196
197
198
199
201
204
204
207
215
216
219
226
230
230
233
239
241
242
245
247
249
249
250
250
251
256
CONTENTS
Vlll
Appendix S.A
5.A.1
5.A.1.1 Polymers
5.A.1.2 Monomers and chemicals
References
Reactive antioxidants for polymers
s. AL-MALAIKA
6.1 Introduction
6.2 Antioxidants and polymer oxidation: a mechanistic overview
6.2.1 Polymer oxidation
6.2.2 Antioxidant classes and mechanisms of action
6.3 Effect of chemical structure and physical factors on antioxidant
performance
6.3.1 Chemical effects
6.3.2 Physical effects
6.4 Reactive antioxidants and routes to antioxidant permanency
in polymers
6.4.1 Copolymerisation of reactive antioxidants during polymer
manufacture
6.4.2 Chemical grafting of reactive antioxidants post polymer
manufacture
Appendix 6.A
6.A.l
Abbreviations
6.A.1.1 Polymers
References
Synthesis of polyolefin graft and block

copolymers by reactive borane reagents and
applications in polyolefin trends and composites
260
260
260
260
261
261
266
266
267
267
268
273
274
274
276
280
282
298
299
299
299
299
299
303
T.e. CHUNG
7.1 Introduction
7.2 Synthesis of borane-functionalized olefinic polymers
7.2.1 Borane monomers
7.2.2 Direct copolymerization of boranes with olefin monomers
7.2.3 Post-copolymerization of borane reagents with preformed
polymers: hydroboration reaction
7.3 Utilization of borane-functionalized polymers in graft and block
copolymer formation
7.3.1 Autoxidation of alkyl-9-BBN
7.3.2 Free-radical reactions for graft formation
7.3.3 Ring-opening reactions for graft formation
7.3.4 Chain extension via diblock polymer formation
7.4 The use of graft and block copolymers prepared via boranefunctionalized polymer intermediates in the compatibilization
of polymer blends
303
305
305
306
307
308
308
309
314
318
323
CONTENTS
7.4.1 PP/PMMA blends
7.4.2 PP/PCL blends
7.4.3 PP/PC blends
7.5 Conclusions and future trends
Acknowledgement
Appendix 7.A
References
Electron beam radiation graft modification of

preformed polymer architecture
IX
323
325
325
328
328
329
329
329
331
B. SVARFVAR
8.1
8.2
8.3
8.4
8.5
Introduction
Principles of pre-irradiation electron-beam grafting in inert atmosphere
Parameters affecting electron-beam grafting
Different polymer architectures suitable for electron-beam grafting
Applications of electron-beam grafting
8.5.1 Adhesion
8.5.2 Textiles
8.5.3 Supports for catalysts and reagents
8.5.4 Ion-exchange
8.5.5 Separations
8.5.6 Fuel cells
8.5.7 Membrane reactors
8.5.8 Controlled release of drugs
Appendix 8.A
References
Thermoplastic elastomers based on elastomerl

thermoplastic blends dynamically vulcanized
331
332
334
340
340
342
342
342
343
343
344
344
344
344
346
346
346
349
A.Y. CORAN and R.P. PATEL

9.1 Introduction
9.2 The preparation of elastomer/plastic blends by dynamic vulcanization
9.3 Properties of blends prepared by dynamic vulcanization
9.3.1 Polyolefin-based thermoplastic vulcanizates
9.3.2 NBR-nylon thermoplastic elastomer compositions
9.3.3 Other thermoplastic vulcanizates
9.3.4 Characteristics of elastomers and plastics for correlations with
blend properties
9.3.5 The correlation between blend properties and the
characteristics of blend components
9.3.6 Technological compatibilization of NBR/polyolefin blends
by elastomer-plastic graft formation
9.3.7 Blends of thermoplastic vulcanizates based on dissimilar
plastics
349
351
353
353
364
369
374
377
379
384
CONTENTS
9.4 Technological applications
9.4.1 Processing-Fabrication technology
9.4.2 End-use applications
Appendix 9.A
9.A.1
Abbreviations
9.A.l.l Polymers and rubbers
9.A.1.2 Curative systems
9.A.1.3 Other abbreviations
References
Index
386
387
390
392
392
392
392
393
393
395
List of contributors
S. AI-Malaika
Polymer Processing and Performance Group,

Department of Chemical Engineering and Applied
Chemistry, Aston University, Aston Triangle,
Birmingham, B4 7ET, UK
W.E. Baker
Department of Chemistry, Queen's University,

Kingston, Ontario, K7L 3N6, Canada
R.J.M. Borggreve
DSM Research, PO Box 18,6160 MD,

Geleen, The Netherlands
T.e. Chung
Department of Materials Science and Engineering,

Pennsylvania State University, University Park,
P A 16802, USA
A.Y. Coran
University of Akron, Institute of Polymer

Engineering, Sidney L. Olson Research Centre, Akron,
OH 44325-0301, USA
J.-J. Flat*
Laboratoire d'Extrusion Reactive, ECPM Departement Polymeres Institut Charles Sadron,

4 rue Boussingault, 67000 Strasbourg, France
A.H. Hogt
Akzo Nobel Central Research, Zutphenseweg 10, 7418

AJ Deventer, PO Box 10, 7400 AA Deventer,
The Netherlands
G.-H. Hu

J. Jelemc
Akzo Nobel Central Research, Zutphenseweg 10,7418

The Netherlands
M. Lamblat

N.C. Liu
Polymeric Materials Research Institute, Shanghai Jiao

Tong University, Shanghai, 200240, China
*Presently at CERDATO Elf Atochem, 27470 Serguigny, France.

tDeceased 5 January 1997.
xu
CONTRIBUTORS
J. Meijer
Akzo Nobel Central Research, Zutphenseweg 10, 7418

The Netherlands
D. Munteanu
Polymer Research Centre, 25 Garii Street, R-1900

Timisoara, Romania
R.P. Patel*
Advanced Elastomer Systems, 388 South Main Street,

Akron, OH 44311-1059, USA
B. Svarfvar
Materials Research, Department of Polymer

Technology, Abo Akademi University, Artillerigatan
4D, SF -20520 Abo, Finland
M. van Duin
DSM Research, PO Box 18,6160 MD, Geleen, The

Netherlands
*Now retired.
Preface
Chemical modification of polymers by reactive modifiers is no longer an

academic curiosity but a commercial reality that has delivered a diverse
range of speciality materials for niche markets: reactively grafted styrenic
alloys, maleated polyolefins, super-tough nylons, silane modified and
moisture-cured polyolefins, and thermoplastic elastomers, are but few examples of commercial successes.
Although the approach of reactive modification of polymers has been
largely achieved either in solution or in the solid state (through in situ
reactions in polymer melts), it is the latter route that has attracted most
attention in the last two decades owing to its flexibility and cost-effectiveness. This route, referred to as reactive processing, focuses on the use of
suitable reactive modifier(s) and the adoption of conventional polymer
processing machinery, an extruder or a mixer, as a chemical reactor, to
perform in situ targeted reactions for chemical modification of preformed
polymers. This relatively simple, though scientifically highly challenging,
approach to reactive modification offers unique opportunities in exploiting
various reactive modifiers for the purpose of altering and transforming in a
controlled manner the properties of preformed commercial polymers into
new/speciality materials with tailor-made properties and custom-designed
performance for target applications. Such an economically attractive route
constitutes a radical diversion away from the traditional practices of
manufacturing new polymers from monomers which involves massive investments in sophisticated technologies and chemical plants.
This book aims to bring together both theoretical and applied aspects of
the science and technology of chemical modification through the use of
reactive modifiers. Each chapter starts with introductory remarks followed
by a discussion of the underlying chemical principles, some aspects of
contemporary basic and industrial researches and innovative commercial
developments. The nine chapters of the book, which have been written by
experts from industry and academia, are intended to illustrate the wide
scope and the unlimited potential of this exciting and innovative scientific
and technological endeavour.
One of the major problems associated with grafting of reactive modifiers
on polymers is the interference of competing side reactions with the target
grafting reaction. The chemistry of free radical grafting in polymer melts by
reactive processing and the effect of the mechanisms identified on the
xiv
PREFACE
microstructure of the graft and the nature and importance of competing

reactions and grafting efficiency is critically reviewed in chapter 1 by Hu,
Flat and Lambla. These authors discuss also recent advances in the free
radical grafting of polypropylene melt by two of the most industrially
important reactive modifiers, maleic anhydride and glycidyl methacrylate.
The preferred free radical initiators for chemical grafting of reactive
modifiers are the peroxides. Hogt, Meijer and Jelenic (chapter 2) discuss the
chemistry of different commercial organic peroxides and their use as
initiators and reactive modifiers for polyolefins.
Carboxylation reactions involving the functionalization of polymers by
maleic anhydride to promote compatibilization of immiscible polymer
blends is an industrially important process. This area is covered in both
chapters 3 and 4. The interfacial chemistry of coupling reactions between
different maleic anhydride-functionalized polymers and the reactive functionality of polyamides is discussed by Van Duin and Borggreve in chapter
3. The authors evaluate critically the effects of the chemistry involved on the
rheology and morphology of compatibilized blends of polyamides and
maleic anhydride-containing polymers together with an assessment of the
morphology - interface - ultimate property inter-relationship of the blends.
This theme is continued in chapter 4 by Liu and Baker, who examine the
role of functional oxazolines, in different polymers as reactive modifiers for
promoting interfacial reactions with other functional(ized) polymers, and for
preparing compatibilized polymer blends with enhanced properties.
Functionalization of polyolefins by silanes and their subsequent crosslinking by moisture is another important commercial process. Munteanu, in
chapter 5, gives a very detailed discussion of both the grafting of reactive
silanes on polyolefins using post-reactor (melt grafting) and in-reactor
(copolymerization) routes, and the subsequent moisture cross-linking process. The structure and property of silane modified and cross-linked polymers are outlined together with a range of applications for these materials.
Stabilization is a pre-requisite for most hydrocarbon polymers in order
to survive high temperature conversion processes, storage and the aggressive
and extractive conditions of service environment. The different approaches
used to effect efficient chemical grafting of reactive antioxidants on polymers
are discussed in chapter 6 by AI-Malaika.
In chapter 7, Chung reviews recent advances in the chemistry and
application of borane-functionalized polyolefins. Reactive borane reagents
are used to prepare polyolefin block and graft copolymers which are applied
further to the compatibilization of polypropylene-containing blends.
An alternative method to peroxide initiation for chemical grafting of
reactive modifiers on polymers is the use of electron-beam irradiation.
Svarfvar (chapter 8) outlines the principles of this method and discusses at
length its applications.
PREFACE
xv
The final chapter of the book centres on one of the most versatile areas
of polymer modification via dynamic vulcanization. Coran and Patel
(chapter 9) give a detailed account of dynamically modified thermoplastic
elastomers and their properties and highlight present and future technological applications.
I wish to express sincere thanks and appreciation to all the contributing
authors to this work. I am most grateful for their willingness to share their
research findings and for submitting manuscript and proofs on time making
my editorial tasks all the more pleasant. I would like to acknowledge with
gratitude the opportunity that the publishers Chapman and Hall have
provided with special thanks to the editorial staff, and in particular, to
Dr Paul Sayer and David Hemsley, for their professionalism and help.
Special thanks are due to my family for their tolerance and understanding
throughout.
Sahar Al-Malaika
Birmingham, Oct 1996
Free-radical grafting of monomers onto polymers

by reactive extrusion: principles and applications
G.-H. HU, I.-J. FLAT and M. LAMBLAffi
1.1
Introduction
In recent years, increasing activities have been directed towards chemical

modifications of existing polymers in order to obtain functional and/or
engineered new materials [1,2]. Chemical modifications of existing polymers are important for at least two reasons: 1. they can be an inexpensive
and rapid way of obtaining new polymers without having to search for new
monomers1; 2. sometimes they may be the only way to synthesise intended
polymers2. One of the important chemical modification methods is the
free-radical grafting of reactive monomers, which involves reaction of a
polymer with a vinyl-containing monomer or a mixture of monomers
capable of forming grafts onto the polymer backbone. If the grafts are long,
the modified polymer becomes a true graft copolymer, of which the
properties will be very different from those of the original polymer substrate.
When the grafts are short with less than, say, five moieties, most of the
physical and/or mechanical properties of the original polymer substrate will
be retained. However, the chemical properties of the modified polymer may
become quite different, this often being the ultimate objective.
Of all possible chemical modification methods, free-radical grafting is
probably the oldest, widely practised and most inexpensive one. These
advantages are further gained with the use of batch mixers or screw
extruders as chemical reactors, which allow the free-radical grafting reaction
to occur without solvents [3]. As a chemical modification method, freeradical grafting has been used to promote functional and/or mechanical
properties of various types of polymers, but most frequently to promote
those of polyolefins such as polyethylene (PE) and polypropylene (PP). This
is because they possess the most important volume share of the plastics
industry owing to their low cost, versatile properties and growing commercial applications. However, they are limited in various technologically
iFThis chapter is dedicated to the memory of M. Lambla who has sadly died before the
completion of this book.
lIt is virtually impossible to obtain maleic anhydride containing polypropylene starting from
the corresponding monomers. However, it can be easily obtained by free-radical grafting.
2Poly(vinyl alcohol) cannot be synthesised upon polymerisation of its corresponding monomer
vinyl alcohol, for this does not exist. It can be obtained by hydrolysis or alcoholysis of
poly(vinyl acetate).
S. Al-Malaika (ed.), Reactive Modifiers for Polymers

Chapman & Hall 1997
REACTIVE MODIFIERS FOR POLYMERS
important fields because of, for example, their lack of chemical functionalities, low paintability and dyeability, poor adhesion to metal or glass, high
sensitivity to photo- and/or thermal oxidation, low elastic modulus, limited
impact strength and poor compatibility with other polymers including
engineering plastics. As a matter of fact, melt free-radical grafting of
monomers onto polymers has become one of the most important applications of reactive extrusion technology.
A variety of vinyl monomers have been grafted onto a number of polymer
substrates by free-radical chemistry, with much of the effort disclosed in the
patent literature. The state of the art has been the subject of various chapters
[2] and books [4]. Thus, the primary aim of this chapter is to describe the
principles of melt free radical grafting by reactive extrusion rather than
specific gains or applications of modified polymers in terms of chemical,
physicochemical, physical or mechanical properties such as chemical reactivity, thermal stability, adhesion, dye ability, tensile strength and impact
resistance. For the sake of readability, this chapter starts with an overall
mechanistic view to free-radical grafting, followed by a brief description of
some particular features of melt free-radical grafting compared with solution
free-radical grafting. It then addresses challenges facing melt free-radical
grafting. Finally, a considerable space is used to describe some of the recent
advances in this field made in the authors' Reactive Extrusion Laboratory.
1.2 Free-radical grafting: an overall mechanistic view
1.2.1
Overall reaction scheme
A free-radical grafting system usually contains three types of reactants:

polymer, unsaturated molecule, such as vinyl monomer, and free radical
initiator. Irrespective of their nature, a typical free-radical grafting scheme
can be represented by Figure 1.1.
Primary free radicals (R *) are generated by some mechanism of initiator
decomposition (kd) in the presence of monomer (M) and polymer. A
primary free radical thus formed may follow two completely different
reaction pathways, with one leading to undesired homopolymerisation (kp;)
and the other one desired grafting (kH)' When it reacts with a monomer
molecule (k p ;), the undesired homopolymerisation is initiated forming a
monomer radical (RM*). If this monomer radical continues to react with
more monomer molecules (k p ) an oligomer or polymer will be formed. The
grafting of this oligomer or polymer onto the desired polymer backbone
rarely occurs because a propagating monomer radical usually has a limited
hydrogen abstracting capacity unless it is very reactive, such as the vinyl
acetate radical. On the other hand, when the primary free radical undergoes
transfer with the polymer upon abstracting a hydrogen from the polymer
FREE-RADICAL GRAFTING OF MONOMERS ONTO POLYMERS
R'
1
~C~
Ykcl
~C=CH
R'
CH~
R'
R'
R'
1
~C~
~C~
~,
~t~
I.
~C~
R'
1
R'
1
~C~C~
1
MH
R'
1
~C~
MyM
Figure 1.1 Overall scheme of free-radical grafting onto a polymer backbone.
backbone (kH) a macroradical is then formed. As will be discussed later in

detail, this macroradical faces one of the following three important fates, the
probability of which depends on its structure: chain scission (ks ), crosslinking (k c ) and grafting (k gi ). When the macroradical reacts with a monomer molecule, this monomer molecule is then grafted (or fixed) onto the
polymer backbone forming a branched macroradical (kg;). This branched
macroradical may continue to react with more monomer molecules forming
longer grafts (kgp ). It may also undergo transfer with a hydrogen atom of
the same or another polymer backbone forming a new macroradical (kHt).
The macro radical transfer can be an important step for grafting as the newly
formed macroradical is expected to repeat the grafting cycle described
above, yielding more grafts.
Although the above free-radical grafting scheme should be completed
with various termination and transfer processes along with other possible
reactions it clearly shows that free-radical grafting competes against polymerisation. The relative importance of the free-radical grafting with respect
to the polymerisation depends primarily on the two reaction constant ratios:
(kH + kHt)/kpi and kg;/kp. The first ratio, (kH + kHt)/k pi , is considered as the
ratio between the reactivity of the hydrogen atoms of the polymer chain and
that of the monomer towards the primary radicals and macroradicals. It can
also be viewed as the ratio of the fraction of the primary radicals and
macroradicals which abstract hydrogen atoms from the polymer backbone
to that of the primary radicals which react with the monomer. The larger is
(kH + kHt)/k p;, the more macroradicals will be formed from the hydrogen
abstraction by the primary radicals as well as by the macro radical transfer
mechanism and, consequently, the higher the grafting and the less important
the polymerisation should be. The second ratio, kg;/kp, measures the relative
capability of the macroradical to initiate grafting with respect to that of the
propagating monomer radical to initiate homopolymerisation. Obviously,
the higher is kg;/kp, the more monomer molecules will be grafted.
The ratio kH/kgp is also an important parameter in free radical grafting
because it measures the relative importance between the rate of intramolecular and/or intermolecular macroradical transfer and that of monomer
addition to macroradicals. If this ratio is high, the graft length should be
short, and vice versa. In other words, kH/kgp characterises the length of
grafts.
In what follows, the various individual steps involved in the free-radical
grafting are discussed as follows.
1.2.2
Initiator decomposition: halflife, initiator grafting efficiency and

hydrogen-abstracting capacity
Free-radical initiators are sources of free radicals necessary for initiating a

free-radical grafting process. Those used to initiate a grafting reaction can
be organic peroxides and, less commonly, air or ionising radiation. Free
radicals may also be generated by pure thermal or mechanical means. But
under normal grafting conditions in solution or in the melt, free radicals
formed by thermomechanical means under ambient atmosphere are at
concentrations too low to bring about grafting to a desired extent. Therefore, thermomechanically induced formation of free radicals must be considered as a minor source of radicals which must be supplemented by other
sources. The most useful source is, of course, organic peroxides (ROOR')
which are often added in small amounts to the grafting system. An organic
peroxide supplies free radicals by the homolytic cleavage of the labile
oxygen-oxygen bond of the peroxide at appropriate temperatures. Freeradical species generated from peroxides have an unpaired (free) electron
and are very reactive intermediates with short lifetimes, i.e., halflives of less
than 10- 3 s [5]. According to the overall free-radical grafting mechanism
(Fig. 1.1), the only useful peroxides are those of which the primary free
radicals should be sufficiently reactive to abstract hydrogen atoms from the
polymer chain to form the corresponding macroradicals. Because of their
short halflives and low hydrogen abstracting capacity, azo initiators are
rarely used in free-radical grafting. For example, Smets, Roovers and van
Humbleek [6] attempted to graft methyl methacrylate (MMA) on polysty-
FREE-RADICAL GRAFfING OF MONOMERS ONTO POLYMERS
rene. When azo-bis-isobutryonitrile (AIBN) was used as initiator no grafting

was achieved, as neither the isobutryonitrile radical nor the propagating
MMA radical is sufficiently reactive to abstract a hydrogen from polystyrene. However, when benzoyl peroxide (BP) was used as initiator grafting
was achieved owing to the more reactive phenyl and benzoyloxyl radicals
having a higher capacity of abstracting hydrogen from polystyrene backbone.
Reaction conditions and the reactivity of the initiator should be taken
into consideration when selecting a proper initiator for a given-radical
process. They must be matched so that the grafting reaction can be
successful. The decomposition behaviour of initiators is important for
initiator selection. A good peroxide for a given grafting reaction should meet
at least the following criteria: low toxicity and volatility, appropriate halflife,
high initiator efficiency and corresponding primary free radicals with an
adequate hydrogen-abstracting capacity with respect to the C-H bond of
the concerned polymer backbone.
(a) Halflife. The halflife of a peroxide, t1/2 is a measure of its rate of

decomposition at a certain temperature and other given conditions. It
indicates the time when half of the quantity of the peroxide originally used
has decomposed. The higher the decomposition rate, the shorter this time.
Thus, halflife is one of the most important factors, if not the most important
factor, for selecting a suitable initiator for grafting reactions. Only if a
sufficient amount of primary free radicals is formed in a certain period can
an appropriate rate and amount of grafting be achieved.
The thermal decomposition of organic peroxides under ideal conditions
(in the gas or an inert solvent, i.e., a solvent which does not affect the
decomposition reaction) takes place according to first-order kinetics:
_ de = kC
dt
t1/2
(1.1)
In(:~)/~
(1.2)
(~).
(1.3)
= In
Equation 1.3 indicates that the characteristic value t 1/2 depends only on the
intrinsic rate constant k. This latter is related to three factors: the relative
stability of the radicals formed, i.e., the more stable the radical, the less
stable the peroxide; steric factors, i.e., highly strained peroxides are less
stable because decomposition relieves steric strain energy; and electronic
effects, i.e., electron-donating functions de stabilise and electron-withdrawing
functions stabilise peroxides. These factors are manifested in the activation

energy (~E) and the pre-factor ko in the Arrhenius equation:
(1.4)
Thus the temperature dependence of t 1/2 can be written as

(1.5)
In general, the activation energy of organic peroxides ranges from 100-
150 kllmol or from 25-35 kcaljmol [7,8]. This means that a decrease in
temperature by 5C-lOoC will double the halflife.
Apart from temperature, the halflife of an organic peroxide is also
pressure dependent. This can be explained by the fact that its oxygenoxygen bond stretches in the transition state immediately before splitting.
An increase in pressure makes it more difficult to increase the 'activation
volume', therefore reducing the rate of decomposition compared with
normal pressure and increasing the halflife [9]. Generally pressure has a
much smaller effect on the halflife than temperature. The halflife of an
organic peroxide is approximately twice as long at a pressure of 3000 bars
as that at atmospheric pressure.
In addition to temperature and pressure, the peroxide concentration, the
solvent and other substances present in the system may affect the halflife as
well owing to their eventual interference with the otherwise first-order
kinetics of the peroxide decomposition under ideal conditions (equation
(Ll)). The rate of decomposition of an organic peroxide may be enhanced
and thus its halflife reduced when the peroxide concentration is increased,
the solvent is polar or substances present in the system are reactive toward
the peroxide. This is because the peroxide molecules decompose not only by
thermal influence according to first-order kinetics but also by the attack of
free radicals resulting from the peroxide itself, the solvent or the reactive
substances. This is so-called 'induced decomposition'.
Organic peroxides decompose according strictly to first-order kinetics
only when highly diluted. When the peroxide concentration is high, the risk
of the peroxide molecules being attacked by primary radicals leading to
additional oxygen-oxygen cleavage becomes high. As a result, the rate of
decomposition increases and the radical yield decreases because of radicals
being consumed in this reaction.
The type of solvent used, and its polarity in particular, has a strong
influence on the halflife. Some peroxides may be attacked and split directly
by certain solvents. Also, primary free radicals originating from the peroxide
may attack some solvents to form secondary radicals which in turn can
attack the peroxide molecules.
The decomposition of peroxide induced by primary radicals of the
peroxide or secondary radicals of the solvent or other substances is a
second-order reaction and usually faster than the first-order homolysis of
equation (1.2). Consequently, the decomposition rate in polar solvents or
with high peroxide concentrations can be significantly higher than the true
first-order rates in ideal peroxide systems. In order that the peroxide
concentration follows first-order kinetics and the effect of induced decomposition on the halflife can be negligible, halflives are usually measured in
relatively inert solvents such as benzene or cumene in relatively dilute
concentrations of 0.1-0.2 mol/I. Thus halflives are meaningful and comparable only when the following conditions are clearly specified: temperature,
pressure (where necessary), peroxide concentration and the nature of solvent
and/or other substances.
Tabulated in Table 1.1 are the halflives and activation energies of organic
peroxides mostly used for melt free-radical grafting (see also ch. 2, Table 2.1).
Note that all of them belong to the dialkyl peroxide class. This is because
organic peroxides of this class have suitable thermal stability as well as
relatively long halflives at normal melt grafting temperatures (l50C-300C).
(b) Initiator grafting efficiency. The initiator efficiency, f, is introduced to
a classical polymerisation to accommodate the experimental observation
that the rate of initiation is often less than anticipated from a knowledge of
the rate of decomposition of the initiator. It can be considered as the
fraction of primary radicals originating from initiator decomposition which
react with the monomer. Obviously, this definition is not appropriate for
free radical grafting because in this case the fraction of primary radicals
which react with the monomer (homopolymerisation) is viewed more as a
negative factor. The greater the fraction of primary radicals which react with
monomer, the less important the fraction of primary radicals which will be
available for hydrogen abstraction. The initiator efficiency, f g , for free
radical grafting should be defined as the fraction of primary radicals which
abstract hydrogen atoms from the polymer backbone forming the corresponding macro radicals. According to this definition, fg is directly related
to the relative importance of the fraction of primary radicals used for
hydrogen abstraction and that of polymerisation initiation. The higher the
initiator polymerisation efficiency, the lower the initiator grafting efficiency.
Another important factor affecting the initiator effficiency is the so-called
'cage effect'. The cage effect is related to the fact that primary radicals
originating from the initiator decomposition are formed in a cage made of
solvent, monomer and/or preformed polymer molecules. Not all primary
radicals generated within this cage can diffuse out of it and react with the
DTBPIB
a,a'-di(t-butyl-peroxy)-1,3- and
l,4-di-isopropyl-benzene
di-t-amyl peroxide
t-butyl a-cumyl peroxide
BCP
DTAp
dicumyl peroxide
DCP
Name
Code
CH
CH
CH
CH
I
J
CH
t-c H-OO-C--c-OO-t-c H
CH
CH
CH
3
3
CHCH-C-OO-C-CHCH
3
2 I
I
2
3
CH
CH
CH
I~
t-c 4 H-OO-C
9
,
CH
CH
<0>-'
o y-OO-y'~
0
CH
Chemical structure
142
129
154
152
(kJjmol)
fl.E
120; 116<
118
118; 120c ; 124d
116; 115 c ; 117d
10h
T (0C) for
142
142
138
136
1h
t'/2
in
190
190
180
175
1 min
Table 1.1 Halflives and activation energies of selected organic peroxides largely used in melt free-radical grafting (data obtained with 0.1
benzene)
di-t-butyl peroxide
2,5-di(t-butylperoxy)-2,5dimethylhexyne
DTBpb
DTBHY
t-c
4
CH
CH
CH
J
H-OO-t-C H
CH
CH
3
CH
J
4
9.
t-c H-OO-C-C::C-C-OO-t-c H
CH
CH
I J
I J
t-c H-OO-C-CH CH-C-OO-t-c H
154
152
142
128; 128 c ; 131 d
125; 128 c ; 129d
120; 119c ; 120d
Source: Peroxide - Chemie GmbH Interox, p. 3.2.1, Hoellriegelskreuth.

aO.1 M in styrene.
bDTBP is suspected to be harmful for health and thus forbidden by the US Food and Drug Administration for food applications.
CO.2 M in benzene.
dO.2 M in dodecane.
2,5-di(t-butyl-peroxy)-2,5dimethylhexane
DTBPH
149
146
142
195
190
190
10
RJ-o-o-
~-
_!J._-+_II_
III
~-&-oooo-&-~ __ 2R-too
~-~ -0
CO2 0
J- R-~-OO
+ R + c02
~02C02!]_ 2Ro+2co l
2
1.1
polymer backbone before they terminate their life with other dissimilar
primary radicals resulting from non-deal decomposition of peroxides. This
is depicted by the brackets in reaction 1.1. Besides pathway (1), the peroxide
decomposition may follow other pathways such as II and III, depending on
the nature of the peroxide, the reacting medium and reaction conditions
(temperature, etc.).
(c) Hydrogen-abstracting capacity. As shown in Figure 1.1, the hydrogenabstracting capacity (kH) depends not only on the nature of primary radicals
but also on the type of carbon-hydrogen bonds (C-H). This latter is
associated with the chemical structure of hydrocarbons (R-H). Many
models and theories have been proposed to establish the structure and
reactivity of radicals. However, only the Evans-Polanyi relation [10] is
used frequently as a general basis for discussion. It relates the activation
energy AE to the total enthalpy change AHo by the following equation:
AE = (1.AHo + C,
(1.6)
where (1. and C are constants; AHo is the difference between the dissociation
energy of the bond being broken and that of the bond being formed. This
relation compares the energies required to break covalent bonds homolytically to hydrogen. It is assumed that this energy, the hydrogen bond
dissociation energy (HDBE), reflects the stability and the reactivity of the
radical and those of its precursor [11-14]. It should be noted however that
this assumption is really limited to radical reactivity and selectivity in
hydrogen atom abstraction reactions, and can be misleading for other
reactions [15,16] because of the interference of other factors [17] which
affect the reactivity of a radical: steric hindrance, electron resonance and
polarity.
Table 1.2 shows the dissociation energies for the formation of various
carbon and oxygen radicals from various precursors together with the
activation energies for abstracting a hydrogen atom from some hydrocarbons. According to the theory, the lower the dissociation energy, the easier
the hydrogen atom abstraction and the lower the activation energy for
hydrogen abstraction. Correspondingly, the lower the dissociation energy,
11
Table 1.2 Hydrogen bond dissociation energies (HBDE) and activation energies of hydrogen
abstraction (dE)
Precursor
Example
(RhC-H
HBDE
(kJjmol)"
dEb with CHj (kJjmol)b.c
404
31.4 (36.8)
413
37.7 (42.7)
CH 3-C-CH 3
(RhCH-H
H
H
CH 3-C-C-CH3
I I
H H
H H
I I
H-C-C-H
I I
H H
CH 3-H
RO-H
RCOG-H
C 6 H s-H
HO-H
411
423
43.5
439
439
444
469
498
"Source: Seakins, P.W., Piling, M.J., Niiranen, J.T. et al. (1992) J. Phys. Chern., 96, 9847.
bSource: Baldwin, R.R. and Walker, R.W. (1973) J. Chern. Soc., Perkin II, 361.
CData in parentheses corespond to dE with CH 3 CHj.
the lower the reactivity and the higher the stability of the radical formed by
removal of a hydrogen atom.
Thus, abstracting a hydrogen atom from a bulky tertiary alkane
(RhC-H is easier than from a less bulky secondary alkane (RhCH-H
that in turn is less stable and more reactive than a primary alkane
RCH 2-H. Water molecule HO-H bond is the most stable listed whereas
its corresponding hydroxyl radical is the most reactive radical. Methyl
radicals are more reactive than other primary alkyl radicals and are about
as reactive as alkoxyl radicals. Lower stability and increased reactivity
correspond to less discriminating radical behaviour, resulting in faster
hydrogen atom abstraction. Consequently, methyl radicals and oxyl radicals
are considered as good hydrogen atom abstracting radicals and are suitable
for cross-linking, grafting and degradation reactions. By contrast, substituted carbon radicals, such as the ethyl radical, are ineffective hydrogen-
12
abstracting radicals; thus these radicals are more likely to add to carboncarbon double bonds.
For example, di-t-butyl peroxide (DTBP) is preferred over di-t-amyl
peroxide (DT AP) for grafting, cross-linking or chain degradation, whereas
DTAP is more suited for polymerisation. This is because t-butoxyl radical
and t-amyloxy radical resulting from the thermal decomposition of DTBP
and DT AP may undergo further decomposition by fJ-scission:
t-butoxyl radical:
~H3
CH 3 -?-O
CH 3
~-scission
Slow
1.2
~H3
t-amyloxyl radical:
oII
CH;+ CH:i- C- CH 3
CH 3CH 2 - ~ - O
CH 3
~-scission
1.3
Fast
The decomposition of DTBP is slow and therefore the initiating species

is either the t-butoxyl radical or the methyl radical. Both radicals are highly
reactive and capable of abstracting hydrogen atoms. On the other hand, the
t-amyloxy radical decomposes at a faster rate, to yield an ethyl radical. The
ethyl radical is now the major initiating species. Owing to its stability, it
minimises hydrogen abstraction in favour of polymerisation.
To sum up, the reactivity of a hydrogen atom depends not only on
whether it is a primary, secondary or tertiary one but also on the nature of
free radicals, as shown in Tables 1.2 and 1.3 [18,19]. For example, with
respect to methoxyl radical a tertiary hydrogen atom is 27 times as reactive
as a secondary hydrogen atom, whereas with respect to t-butoxyl radical the
reactivity ratio between tertiary and secondary hydrogen atoms is about 50.
This means that methoxyl radical is less selective than t-butoxyl radical in
terms of hydrogen abstraction. Note that primary hydrogen atoms are
always the least reactive.
Table 1.3 Relative reactivity of primary, secondry and tertiary hydrogen atoms toward several
free radicals
CH~ (liquid, 110C)

CH 3 0* (gas, 250C)
(CH 3 )3 CO *
Cl* (gas, 25C)
Br* (gas) (liquid, 40C)
(RhC-H
(R)zCH-H
46
27
50
6
6300
1900
4.3
8
10
4
250
200
RCH 2-H
13
The above discussion is in line with our early statement that the
hydrogen-abstracting capacity of primary radicals depends primarily on
their precursors - organic peroxides. Interestingly, organic peroxides used
the most for melt free-radical grafting (Table 1.1) bear two common features:
they all belong to the same dialky peroxide class and have relatively long
halflives (in the order of a minute) at normal melt grafting temperatures; and
under the influence of heat most of them can liberate t-butoxyl radicals. As
pointed out earlier, these radicals have a much greater hydrogen abstracting
capacity than do other types of free radicals [20]. As such, these dialkyl
peroxides are best suited to polymer modification and grafting by freeradical chemistry.
1.2.3
Fate of macro radicals: chain scission, branching and cross-linking

and/or grafting
A macroradical, once formed upon hydrogen abstraction by a primary free

radical, can experience several reaction types such as chain scission, crosslinking, and grafting (Figure 1.1). The relative importance of these reactions
depends primarily on the nature of the macroradical and thus the type of
the corresponding polymer backbone.
(a) Chain scission. A macro radical can be highly unstable and the chemical bond (usually a C-C bond) at the location or in the neighbourhood of
this macroradical may break down to two smaller fragments - chain scisison
or degradation (kg). This process causes a reduction in the molecular weight.
The molecular weight distribution becomes more random and the polydispersity approaches two. This characteristic is related to the fact that higher
molecular weight chains have a greater number of C-C bonds thus being
SUbjected to a greater probability of chain scission. Therefore, for broad
molecular weight distributions, usually found for polyolefins, the breadth of
the molecular weight distribution narrows as chain scission proceeds. A
reduction in molecular weight decreases the melt viscosity (or increases the
melt flow index, MFI) and improves processability. An important commercial application of the use of controlled chain degradation is in the
production of controlled rheology PP (CR-PP) (more details are given in
ch. 2). PP is produced commercially with heterogeneous Ziegler-Natta
catalysts. Usually, the resulting polymers have a very broad molecular
weight distribution with a high molecular weight tail, which is responsible
for high elasticity levels. Correlation exists between processability of a PP
resin and its elasticity level.
(b) Branching and cross-linking. Long-chain branches are formed when
macroradicals experience bimolecular termination by combination. If these
14
long chain branching processes continue, a three-dimensional network

(cross-linking) will form with various levels of gel and sol (k c ). The
formation of high molecular weight chains via long-chain branching increases melt strength, die swell and improves strain hardening properties.
High melt strength and good strain hardening properties are particularly
important in thin film applications. For example, to produce thinner films
made of linear low-density polyethylene (LLDPE), small amounts of highly
branched low-density polyethylene (LDPE) are used in a blend in order to
improve strain hardening properties and melt strength. Improving the melt
strength of PP via long-chain branching has also been the subject of intense
studies.
Cross-linking is often considered undesirable. However, sometimes it may
also bring to the original polymer some property enhancement such as
increased service temperature, solvent resistance, flexural modulus, dimension stability.
The relative importance of chain scission with respect to cross-linking
depends very much on the nature of the macroradical, thus the nature of the
polymer backbone. In the case of PE, the corresponding macroradical is a
secondary-carbon-centred radical which is very reactive to couple with
another macroradical leading to a branched or cross-linked polymer (k c ).
By contrast, the macroradical of PP tends to fragment to a secondarycarbon-centred radical and a smaller unsaturated segment by p-scission (k s ).
This difference between PE and PP is related to the fact that the PP
macroradical is a tertiary-carbon-centred radical having a greater stability
and is thus less reactive than a secondary-carbon-centred radical of PE.
Therefore, the probability for PP macroradicals to combine with each other
is lower.
( c) Grafting. Often as the solely desired reaction, grafting of selected
monomers onto polymer chains occurs when the macroradical reacts with
the double bond of the vinyl monomer, forming a branched macroradical
(k gi ). If this branched macroradical continues to react with more vinyl
monomer molecules, longer grafts will form. The grafts onto the polymer
chain are responsible for property improvement. A notable commercial
example is the grafting of maleic anhydride (MA) onto polyolefins, and PP
in particular. As shown in Figure 1.2, MA possesses a double reactivity: free
radical reactivity (unsaturation of the C C double bond) and functional
reactivity (cyclic anhydride). Once grafted onto a polymer backbone in the
form of a substituted succinic anhydride (SA), it provides the polymer
substrate with high reactivity toward various nucleophilic groups (amines,
alcohols, thiols, etc.) or electrophilic groups (epoxies) in the presence of a
catalyst. This high reactivity of SA has been explored for numerous
industrial applications, including adhesion, painting, coating, etc. [21].
15
CH=CH
O=C
C=O
\/
o
Figure 1.2 Chemical structure of maleic anhydride (MA).
Recently, there has been an increasing use of MA modified polymers as in

situ compatibiliser precursors for compatibilising polymer blends in order to
obtain materials of high performance with reduced cost.
The extent to which a vinyl monomer is grafted depends very much on
the reactivity of monomer and macro radical combinations (k gi ). However,
little direct information pertinent to such combinations is available. Nevertheless, the reactivity of such combinations may be analogous to that of
copolymerisation systems. In this latter case, the process is governed
primarily by reactivity ratios. This may allow one to appreciate the inherent
reactivity of monomers or free radicals. Consider the copolymerisation
reactions of a monomer A with a series of other monomers. In this case, the
reciprocal of the ratio, l/ra, is a direct measure of the reactivity of this series
of monomers towards the radical A* as
ra
kaa
p
specific rate of (A * + B)
specific rate of (A * + A)'
(1.7)
and the rate coefficients of all reactions of radical A* are measured with
reference to a common standard, the homopropagation rate coefficient for
monomer A, k~a.
In general, the order of inherent reactivity of radicals is approximately
the inverse of the order for monomers, the most reactive monomers yielding
the least reactive radicals and vice versa. This is easily understood, as a
substituent which decreases the reactivity of a radical by some stabilising
influence would be expected to increase the reactivity of the double bond
precursor because they refer to two conjugated species:
R*
+ CH 2 =
CHX --+ R-CH 2 -CHX

1.4
Table 1.4 shows the reactivities of selected radical-monomer combinations relative to the homopropagation of the radical. It can be seen that
styrene is about 16 times as reactive as the vinyl acetate monomer with
respect to the vinyl acetate radical, whereas the reactivity of the styryl
radical is approximately 200 times less reactive than the vinyl acetate radical
16
Table 1.4 Reactivities of radical-monomer combinations relative to the homopropagation of

the radical (l/r.)
Monomer
Radical
vinyl acetate
acrylonitrile
methyl
methacrylate
glycidyl
methacrylate
styrene
maleic anhydride
vinyl
acetate
acrylonitrile
methyl
methacrylate
glycidyl
methacrylate
1.00
0.21
0.039
20.0
1.00
0.76
21.4
7.25
1.00
0.92
1.37
15.6
14.0
2.25
0.92
1.33
1.00
1.78
2.64
1.99
38.5
2.41
1.00
93.0
0.005
+00
+00
maleic
styrene anhydride
52.6
0.17
0.234
29.0
1.00
Source: Brandrup, J. and Immergut, E.H. (1989) Polymer Handbook, 3rd edn, John Wiley, New
York.
toward vinyl acetate. This clearly shows that the negative stabilising effect
of the benzene ring on the reactivity of the styryl radical is much greater
than that on the reactivity of styrene monomer. A value of ljra greater than
unity means that. the free radical prefers to react with other monomers
than with its double bond precursor. For example, the value of ljra for the
styrene radical-glycidyl methacrylate monomer system amounts to 2.41,
indicating that the styryl radical reacts with glycidyl methacrylate 2.41 times
as fast as with its double bond precursor - styrene. For the maleic anhydride
radical-styrene monomer system, the maleic anhydride radical reacts overwhelmingly with the styrene monomer, for the value of ljra reaches 93.
Moreover, the styryl radical also prefers to react with the maleic anhydride
monomer than with the styrene monomer. This situation results in the
formation of an alternating copolymer. The above discussion suggests that
the reactivity ratios for the classical copolymerisation systems may be of use
for free-radical grafting and especially for selecting comonomers in order to
promote the grafting of otherwise unreactive monomers onto polymer
substrates, as will be shown later.
Apart from a lack of well-established correlations between the structure
and reactivity of monomer and radical combinations, another difficulty
encountered in free radical grafting lies in the fact that the initiating species
for grafting are macroradicals. This type of radical is highly bulky, therefore
rendering bulky monomers which have difficulty accessing these sites. In
other words, the steric effect on the reactivity of monomers should be much
more important for free radical grafting than for classical copolymerisation.
Hence, bulky monomers that are (co)polymerisable may become reluctant
to be grafted onto polymer backbones.
17
1.3 Melt free-radical grafting: particular features

In Section 1.2 we discussed the principles of free-radical grafting, regardless
of the state of the mixture (homogeneous or heterogeneous; in solution or
in the melt). In what follows, we will present particular features that
distinguish melt free-radical grafting from solution free-radical grafting.
The most important feature of melt free-radical grafting is, of course,
related to the fact that free-radical grafting is carried out in the melt without
solvents. Concomitant with this particular feature are three additional
important features for melt free-radical grafting: elevated temperatures, high
viscosity and heterogeneity. These particular features give rise to tremendous
challenges to melt free-radical grafting in terms of reactivity, selectivity and
process control.
1.3.1
Jrenn]1erature ejrects
Owing to the absence of solvent, melt free-radical grafting should be carried

out at temperatures 50C-150C higher than those frequently employed for
solution free-radical grafting: temperatures usually exceed 150C and can be
as high as 300C. Although elevated temperatures highly accelerate the rate
of free-radical grafting, they also complicate virtually all the anticipated
individual steps involved (Figure 1.1).
(a) Peroxide deconn]1osition. The most notable influence of temperature is,

of course, on the rate of organic peroxide decomposition because of its high
activation energy (l00-150 kJ/mol; Table 1.1). As stated earlier, an increase
of 5C-lOOC will reduce the halflife of an organic peroxide by a factor of
two. The halflives of most organic peroxides frequently employed for melt
free-radical grafting are short, being of the order of minutes or seconds at
normal melt grafting temperatures (l50C-300C). This temperature range
will surely complicate the ideal first-order kinetics of the peroxide decomposition. In the case of DTBP, for example, the primary step in decomposition
is rupture of the oxygen-oxygen bond, yielding two t-butyloxy radicals:
CH 3
CH3
CH 3
CH3-C-o-O-C-CH3 -+ 2CH3-C-o*
CH 3
CH 3
CH 3
1.5
However, this latter may undergo p-scission into methyl radical and acetone:
18
CH 3
CH3 -
r
I
-O --> CH 3 -C-CH 3
+ CH;
CH 3
1.6
or enter into hydrogen abstraction reactions with the peroxide (radicalinduced decomposition):
CH 3
CH 3
CH 3
CH 3
CH3
CH 3
CH 3
/0
CH 3
CH 2
CH 3
I
I
I
I
I
CH -C-O + CH -C-O-O-C-CH --> CH -C-OH + (CH ) -C
+ CH -C-O
3
I
3
I
I
3
3
I
32
""
3
I
CH 3
1.7
These secondary reactions become more important at higher temperatures,

reducing therefore the initiator grafting efficiency.
(b) Grafting versus homopoiymerisation, degradation and cross-linking. As
discussed earlier, the relative importance of grafting with respect to
homopolymerisation is determined by the following two reaction constant
ratios: (kH + kHt)lk pi and kgJkp. Thus, the influence of temperature on
grafting and homopolymerisation can be appreciated upon examining the
activation energies of these component reaction constants. Let us assume
that the activation energies for hydrogen abstraction or macro radical
transfer (AE H ), homopolymer initiation (AEpJ, graft initiation (AEgi ), and
homopolymer propagation (AEp) are of the order of 40kllmol (see Table
1.2), 10 kllmol, 20 kllmol and 15 kllmol, respectively. Then the overall
activation energy for kHlkpi is of the order of 20 kllmol and that for kgilk p
5 kllmol. This indicates that an increase in temperature favours hydrogen
abstraction over homopolymer initiation by primary radicals. It also favours, to a much lesser extent, graft initiation by macroradicals over
polymer propagation by monomer radicals. Therefore, an increase in
temperature should favour slightly grafting provided that the initiator
grafting efficiency, monomer loss and/or other factors are unchanged.
The preceding discussion has ignored the possible influence of depropagation reactions on the polymer propagation (k p ) and the graft propagation
(kgp ). The polymer depropagation and the graft depropagation are the
reverse reactions of the polymer propagation (k p ) and the graft propagation
(kgp ). They should be included in the general free-radical scheme shown in
Figure 1.1. The importance of these depropagation reactions increases
rapidly with increasing temperature as the activation energies of polymer
depropagation (k dP ) and graft depropagation (k dgp ) are higher than those of
polymer propagation (k p ) and graft propagation (k gp ), both typically being
of the order of 80 kllmol. Therefore, there should exist a critical temperature
at which the rates of polymer propagation and depropagation are equal, or
the overall rate of polymerisation is zero. This temperature is called the
19
'ceiling temperature' of polymerisation, 7;,p. A similar ceiling temperature

should also exist for graft propagation, and is denoted as 7;,g. Because the
monomer involved in polymerisation and grafting is the same, the ceiling
temperature for grafting is expected to be equal to that for polymerisation.
From a thermodynamic viewpoint, the ceiling temperature 7;, corresponds to the free energy change I1G being zero. Thus
where I1Hp and I1S p are enthalpy and entropy changes in the polymer
propagation reaction, respectively; I1S; is the standard entropy change for a
monomer concentration [M], of 1 moljl (strictly for unit activity of monomer). The thermodynamic driving force for polymer propagation is the
increased enthalpy change, and that for polymer depropagation is the
increased entropy change. Note that 7;, is monomer concentration dependent.
The higher the monomer concentration, the higher the ceiling temperature.
The experimental data of I1H p, I1S; and 7;, for the polymerisation of
selected monomers are gathered in Table 1.5. As the I1S; values for most
monomers are close (of the order of 120 J /K per mol), I1H p is to some extent
a measure of 7;,. From the data reported in Table 1.5, one can calculate
ceiling temperatures for a specified [M] of 1 moljl of various monomerpolymer pairs: styrene/polystyrene, ~ 370C> methyl methacrylate/poly(methyl methacrylate, ~ 210C, oc-methyl styrene/poly(oc-methyl styrene),
~ lOC. This order corresponds to that of I1H p.
The practical consequences are that for monomers of which the ceiling
temperatures are close to the grafting temperature, although an increase in
the grafting temperature increases both the rate of grafting and the rate of
Table 1.5 Thermodynamic data and ceiling temperatures of selected monomer-polymer pairs
-AS:
(kJjmol)
(JjK per mol)
T.CC)
Equilibrium [M] in solution

(moljl)
vinyl acetate
methyl acrylate
acrylic acid
styrene
88.0
81.3
74.4
71.2
111
methyl methacrylate
56.8
117
methacrylic acid
IX-methyl styrene
150
150
155.5
135
9.1 x 10- 4 (benzene)

6.5 x 10- 4 (cyciohexane)
0.82 (o-dichlorobenzene)
0.611 (ethyl benzoate)
56.8
37.9
146
134
Monomer
-AHp
0.76 (tetrahydrofuran)
Source: Brandrup, J. and Immergut, E.H. (1989) Polymer Handbook, 3rd edn, John Wiley, New
York.
20
polymerisation, the equilibrium will be shifted to grafting. Additionally, the

lengths of grafts and polymerised products will be reduced. These two
practical consequences are often what we search for. Thus, to a large extent,
it can be said that high temperature is the most important factor that has
brought tremendous success to melt free-radical grafting both in terms of
increased grafting kinetics and in terms of grafting yield.
In addition to affecting grafting and polymerisation, temperature may
also influence degradation and/or cross-linking. However, cross-linking is
difficult to estimate theoretically.
1.3.2
Viscosity effects
The viscosity of amelt free-radical grafting system can be several orders of

magnitude (10 2 -10 5 Pa. s) higher than that of a solution free-radical grafting system. When the viscosity of the medium is high, the diffusion of
various reacting species may be retarded, thereby imparting more or less
effects to the individual reaction steps involved in free-radical grafting. The
viscosity effect on free-radical (co)polymerisation'reactions has been well
documented. However, so far little effort has been made toward a better
understanding of the viscosity effect on melt free-radical grafting. Nevertheless, one can imagine that it would be difficult to disperse small fractions of
low-viscosity monomers and peroxides into highly viscous polymer melt.
This would render modified polymer non-uniform in terms of grafting yield,
molecular weight, etc.
1.3.3 Heterogeneity effects
Heterogeneity, also called the state of mixedness of a mixture, refers to how
species of interest are distributed spatially in the mixture. We may imagine
two extreme states of mixedness. One extreme state of mixedness would
correspond to a mixture of which all species are mixed at a molecular scale.
Such a mixture is called a microfluid. The other extreme state of mixedness
refers to a mixture of which all molecules are gathered together in the form
of aggregates whose size is small at the macroscopic scale but which
contains a large number of molecules. This mixture is called a macrofluid. A
mixture whose state of mixedness is in between the above two extremes is
called a partially segregated fluid.
A melt free-radical grafting system is typically composed of three types of
reactants: polymer, monomer and organic peroxide. Most monomers for
grafting are liquid at room temperature or grafting temperature and capable
of dissolving organic peroxides. Thus among the various states of mixedness
possible, there are three cases: 1. the whole system is homogeneous; 2. both
the monomer and the peroxide are partly miscible with the polymer;
3. neither the monomer nor the peroxide is miscible with the polymer. These
three situations are better illustrated in Table 1.6. Obviously, the behaviour
of melt free-radical grafting depends on the state of mixedness of the system.
21
Table 1.6 Three primary states of mixedness for a melt free-radical grafting system composed
of three components: polymer, monomer and organic peroxide. The monomer and the peroxide
are mutually soluble
Microfluid
Partially segregated fluid
!,
,
Macrofluid
I
I
The polymer (white), the

monomer and the peroxide
(black) constitute a
mixture that is homogeneous
at molecular scale
The monomer and the peroxide

(black) are partly miscible with
the polymer (white)
The monomer and the

peroxide (black) are
completely immiscible
with the polymer (white)
In case 1 grafting and polymerisation are expected to occur over the entire
system at the molecular scale, the modified polymer should be the most
uniform in terms of grafting yield, molecular weight, etc. In case 2 grafting
will occur only in the polymeric phase, and polymerisation will take place
both in the polymeric phase and in the aggregates. The relative importance
of grafting compared with polymerisaton will be controlled by the solubility
of the monomer and the peroxide in the molten polymer. The polymer thus
modified can be highly non-uniform. In case 3 grafting will occur only at
the interface, and polymerisation will proceed in the aggregates.
1.4
Challenges facing melt free-radical grafting
We have seen in the preceding sections that the chemistry of free-radical

grafting is complicated. This is especially true in the molten state because of
the influence of various additional physical parameters such as high temperature, high viscosity and heterogeneity of the reacting medium. These
complications render systematic studies on melt free-radical grafting difficult.
Efforts to modify polyolefins by free-radical grafting of polar monomers,
and of MA in particular, have been in progress since the 1960s, with most
of them reported in the patent literature [22,23]. One of the most important
challenges facing melt free-radical grafting was to obtain a sufficient amount
of grafted MA onto the polymer backbone while retaining the mechanical
properties and thus the molecular weight of the virgin polymer. Melt
free-radical grafting of MA onto hydrocarbon polymer backbones such
as PP, PE and random copolymers of ethylene, propylene and polypropylene (EPR) and of ethylene, propylene and diene (EPDM) is a good
example of the problem.
22
1.4.1
Grafting versus degradation, cross-linking and homopoiymerisation
In 1968, Ide, Kamada and Hasegawa [24J published pioneering work on the
melt grafting of MA onto an isotactic PP in a Brabender batch mixer using
benzoyl peroxide (BP) or dicumyl peroxide (DCP) as a free radical generator. They showed that despite a notable difference in the rates of decomposition, these two peroxides gave virtually the same grafting yields at 185C.
In order to reach sufficient conversion (30%-40%), the peroxide concentration had to be high (0.4-1.8 parts per one hundred resin (phr)) causing,
therefore, important PP degradation (the intrinsic viscosity, [ryJ, of the virgin
PP in tetrahydronaphthalene at 135C was 1.96 dl/g and reduced to a low
value ranging from 0.7-0.85 dl/g). Temperature had a negative effect on MA
grafting yield owing, at least in part, to the fact that MA tends to sublime
(the boiling point of MA is 202C at 760 mm Hg). They also showed that
MA melt free-radical grafting was a very rapid process because grafting yield
and [ryJ of modified PP started levelling off after one minute of reaction.
Hogt [25J carried out the melt free-radical grafting of MA onto PP in a
Berstorff 25 mm co-rotating twin screw extruder (screw speed 200 rpm;
barrel temperature 200C-240C; throughput 2 kg/h) using 1,3-bis(t-butyl
peroxyisopropyl) benzene (DTBPIB). He found that although an increase
in the peroxide concentration increased the MA grafting yield (the magnitude of increase reduced with increasing peroxide concentration) it caused
further PP degradation. When 2 phr MA and 1 phr DTBPIB were added,
only 0.4 phr or 20% of the total MA was grafted, and the PP thus modified
was highly degraded with an MFI greater than 1600 g per 10 min (230C
and 2.16 kg).
Although the above two studies concern a particular PP /MA system,
they clearly reveal a common problem facing the melt free-radical grafting
of monomers onto PP reported in the literature: there is serious competition
between the desired grafting and the undesired PP degradation by f3scission. The higher the MA grafting yield needed, the greater the peroxide
concentration should be and the more severe the chain degradation of the
resulting PP becomes. In the case of PE, EPR or EPDM, most studies
reported in the literature reveal the difficulty of reaching a high monomer
grafting yield along with an acceptable degree of cross-linking. Another
problem facing virtually all melt free-radical systems, regardless of the
nature of monomers, polymer substrates and/or free radical generators, is
the possible homopolymerisation of monomers.
Early attempts made by some researchers to minimise PP degradation or
PE cross-linking without inhibiting grafting involved adding organic substances. Studies of this type seem to have initially been made by Gaylord et
al. [26-31J in the 1970s and 1980s concerning the melt free-radical grafting
of MA. Since then there has been little subsequent study. They tested
numerous what they called 'electron-donating' organic additives such as
23
dimethylformamide (DMF) and dimethylacetamide (DMAC). They found

that as opposed to what they had hoped for, those that were capable of
reducing PP degradation or PE cross-linking also reduced MA grafting
yield. To some extent, an organic additive such as DMF or DMAC would
simply behave as a free-radical scavenger.
1.4.2 Effects of processing parameters
Like other chemical reactions in the molten state, melt free-radical grafting
has to be carried out in special reactors. Reactors that have been used most
often for melt free-radical grafting are batch internal mixers and screw
extruders. The fundamental basis behind the successful use of these types of
machines in melt free-radical grafting is primarily related to their ability to
handle and mix highly viscous polymer fluids.
The centrepiece of a batch internal mixer such as that of the Haake
Rheocord type is a mixing chamber which is made of three metallic plates.
The temperature of each plate is regulated by a temperature controller.
Within the mixing chamber are placed two sigma-shaped rotators which
turn in opposite directions, with one of them rotating 50% faster than the
other in order to promote mixing. Despite this particular design, the mixing
capacity of this mixer is much less important than that of a twin screw
extruder. The mixing chamber of the mixer is not perfectly sealed. This may
bring about complications when adding liquid monomers and/or other
types of reactants whose boiling points are low compared with the temperature in the mixing chamber. In such a case, loss of liquid and/or easy-tosublime reactants can be important. Also, if they are highly immiscible with
the molten polymer, they may cause additional problems.
Despite its limitations, a batch internal mixer is often preferred over a
screw extruder as a chemical reactor for achieving a fundamental understanding of melt free-radical grafting. This is because the time reacting
species stay in a batch mixer is, a priori, the same whereas they do not
necessarily stay for the same period of time in a screw extruder - known as
the residence time distribution (RTD). The use of a batch mixer allows one
to eliminate the influence of the RTD on melt free-radical grafting. A batch
internal mixer also bears other useful features:
its ability to mix highly viscous polymers;
the relatively small capacity of the mixing chamber (50 cm 3 for example),
which permits trials with expensive or exotic chemicals and facilitates
temperature control;
the possibility of varying the following processing parameters which
resemble more or less those encountered in a screw extruder: temperature,
mixing time, mixing intensity, via the rotating speed of the rotors, and the
mode with which reactants are charged to the mixing chamber.
24
In fact, so far a batch internal mixer is considered as a unique device that

best suits the need to understand the chemistry of melt free-radical grafting
necessary for subsequent continuous processing in a screw extruder.
The performance of melt free-radical grafting is affected not only by the
particular chemistry involved but also by the type and geometry of the
reactor as well as processing conditions. This is particularly so in screw
extruders.
Callais and Kazmierczak [32,33] carried out the melt grafting of MA
onto LDPE, LLDPE and a PP in a Killion single screw extruder
(diameter = 19 mm; ratio of length-to-diameter, LjD = 24) using 2,5di(t-butyl-peroxy)-2,5-dimethylhexane (DTBPH) as the free-radical
initiator. They found that whereas the MFI was not greatly affected by the
screw speed or residence time, grafting was favoured by lowering the screw
speed or increasing the residence time. An increase in barrel temperature
increased the MFI with a slight increase in grafting yield. In the case of PP,
the MFI generally increased with increasing barrel temperature, decreasing
screw speed or increasing residence time. By contrast, these parameters had
no significant effect on the grafting efficiency.
Oostenbrink, Borggreve and Gaymans [34] studied the melt grafting of
MA onto EPDM in a co-rotating twin screw extruder of Berstorff type
(diameter 25 mm) using DTBPIB as the free radical initiator. They observed
that at low barrel temperatures (140C-195C) the throughput had no effect
on the MA grafting yield. However, at high temperatures (135C-220C)
the MA grafting yield decreased from 34% to 23% when the throughput
increased from 0.25 kgjh to 1.5 kgjh. Also, an increase in peroxide concentration increased the grafting yield with a concomitant increase in crosslinking.
Ganzeveld and Janssen [35] investigated the melt grafting of MA onto a
high-density polyethylene (HDPE) in an intermeshing counter-rotating twin
screw extruder. They found that increasing the screw speed caused a
minimum in the grafting yield. This was explained by the fact that an
increase in screw speed resulted in a decrease in residence time, therefore the
time available for the grafting was reduced. On the other hand, an increase
in screw speed increased mixing in the extruder, therefore favouring the
grafting. The combined effect led to a minimum in the grafting yield.
Despite the fact that a few attempts have been made to understand the
effects of processing parameters on the performance of melt free-radical
grafting conducted in screw extruders they have been largely neglected and
consequently remain poorly understood. This is not only because of the
complicated melt free-radical grafting scheme, the various particular characteristics of the reacting medium (high temperature, high viscosity and
heterogeneity) but also because of the complicated flow, mixing and heat
transfer in a screw extruder. Also, virtually all studies in this field examine
the grafting yield and molecular architecture (degradation or cross-linking)
25
at the die exit only, and little information is available concerning their
evolution within and along the entire screw extruder. We believe that such
information is crucial for a better understanding of melt free-radical grafting
in such a machine, as will be shown later.
1.4.3
Grafting mechanisms and microstructure of grafts
There is a common consensus in the literature that the overall free-radical

grafting mechanism can be more or less depicted by Figure 1.1. However,
little quantitative information is available about each individual step involved in this overall reaction scheme. Also, experimental evidence for the
microstructure of grafts (grafting sites, graft length, graft sequence distribution) is limited. Thus we often have to speculate about the mechanisms
of free-radical grafting or microstructures of the resulting grafts.
In polyolefins there may be several different types of hydrogen atoms
which are susceptible to free-radical attacks. For example, in PE and
especially in HDPE there are almost exclusively methylene carbons or
secondary hydrogen atoms, whereas in PP each repetitive unit bears three
different carbon or hydrogen atoms: methyl, methylene and methine which
corespond to primary, secondary and tertiary hydrogen atoms, respectively.
As discussed earlier (Tables 1.2 and 1.3), these different types of hydrogen
atoms do not have the same free-radical reactivity and the corresponding
macroradicals are not equally reactive toward the monomer to be grafted.
Despite the complexity of the problem, it has been generally found that PP
is less reactive than PE in a free-radical grafting process [36]. Moreover, as
ethylene is incorporated into PP, the free-radical grafting reactivity of PP
increases [37]. The lower free-radical reactivity of PP compared with PE
cannot be explained on a type-of-hydrogen count basis (Table 1.3). Table
1.7 shows a repetitive unit of PP contains one tertiary, two secondary and
three primary hydrogen atoms, whereas that of PE has four secondary
hydrogen atoms. According to Table 1.3, the 'total reactivity' of a PP repeat
unit towards t-butoxyl radical is equal to 73 whereas that of a PE repeat
unit is 40. On this basis, the free-radical reactivity of PP should have been
greater than that of PE. Obviously, other factors are involved in the
free-radical grafting process. The main important one is steric hindrance: the
tertiary hydrogen atoms of PP which are the major free-radical grafting sites
are more sterically hindered than are the secondary ones of PE. Steric
hindrance also explains the fact that the free-radical reactivity of PP
increases with increasing ethylene content. If ethylene were to be incorporated into PP, the reactivity of PP would not be expected to change much
on the type of hydrogen count basis as four secondary hydrogen atoms (an
ethylene unit) are even less reactive towards alkoxy radicals than are two
secondary hydrogen atoms and one tertiary hydrogen atom. However, the
steric effects would be much less in both the ethylene and the adjacent
26
Table 1.7 Types of hydrogen atoms in PP, PE and EPR

Polypropylene
CH
CH
I J
I J
I J
-Cli----cli----cli--2 I
2 I
2 I
H
LJ
Ethylene and propylene copolymer
Polyethylene
CH
Propylene unit: 1 tertiary H;

2 secondary H;
4 primary H
-Cli--Ii--Ii--Ii--Ii--H-2
LJ
Ethylene unit:
4 secondary H
yH J
yHJ yHJ
-CH-<:--cI+-CH-<:I+-C--cH-<:2 I
2
2
2 I
2 I
HULJ H
Ethylene
Propylene
propylene units. Therefore, higher reactivity would be expected, as observed

experimentally [36,37].
Detailed reactions involved in a free-radical grafting process are still
poorly understood. Based on the IR spectra of MA-modified PP in the
presence of BP as free-radical initiator, Ide, Kamada and Hasegawa [24]
suggested that the probable termination reaction was the recombination
between macroradicals PP-MA* and primary radicals R* and that the
termination by disproportionation between macro radicals PP-MA* is
improbable. By contrast, based on the IR spectra of MA-modified PP at
180C in the presence of DTBP as free-radical generator, Gaylord and
Mehta [31] suggested that the termination by disproportionation between
macroradicals PP-MA * was the most important termination reaction.
De Vito et al. [38] studied solution free-radical grafting of MA onto EPR.
Their IR spectra of MA-modified EPR tended to show that grafts were
composed of single SA moiety, but they could not tell whether a particular
termination reaction had prevailed.
Compared with IR, 13C or 1H NMR may better suit the need to
characterise the microstructure of grafts onto polyolefins. However, so far
studies of this type are limited because of experimental difficulties. In fact,
one often has to work in solution at high tempertures ('" 140C) using
deuterated dichlorobenzene, trichlorobenzene, decahydronaphthalene or
tetrachloroethane as solvent. Also, as the percentage of grafts onto a
polyolefin rarely exceeds a few per cent, it is necessary to have a highfrequency NMR apparatus along with many accumulations that would last
for several hours or days in order to obtain a reasonable spectrum.
Rengarajan et al. [39] used 13C NMR (75 MHz) to characterise MAgrafted PP in a-dichlorobenzene-nitrobenzene (d s) and in the solid state.
They found that the spectrum obtained in solution did not display any
peaks that could be attributed to the SA grafts whereas in the solid state the
spectrum showed two shoulders, at 177 ppm and 130 ppm. Those two peaks
were attributed to the carboxylic group and the C=C double bond of the
grafted MA, respectively. However, it appears that the intensity of the peak
27
corresponding to the C=C bond is greater than that of the carboxylic

group. Thus, this C=C double bond may originate from that contained in
the free-radical initiator BP, as claimed by Ide, Kamada and Hasegawa
[24].
Aglietto et al. [40] studied the grafting of diethyl maleate (DEM) onto
PE in the presence of DCP. With the help of 13C NMR they characterised
the structure of grafts upon comparing with model molecules. They concluded that grafts were composed of single saturated DEM moiety.
To sum up, so far little convincing and consistent experimental evidence
has been generated concerning the microstructure of grafts onto polymer
backbones owing primarily to the grafts being present in only low percentages. For example, a PP containing as high as S wt% SA with an average
molecular weight of SO 000 g/mol corresponds to about 3 SA units per 100
propylene moieties. This level of SA units in a PP backbone is too low to
be detected by analytical techniques such as IR and NMR. Nevertheless,
most studies reported in the literature have speculated that the predominant
graft structure consists of single SA units when MA is grafted at high
temperatures. This speculation is based mainly on the well-known fact that
MA does not homopolymerise unless conditions are drastic [41].
In order to circumvent the problem associated with too weak graft
concentrations onto PE and PP, Russel et al. [42-46] replaced the polymer
substrates by model hydrocarbons, n-eicosane (n-C 2o H 42 ) and 2,6,1O,1S,
19,23-hexamethyltetracosane (squalane), respectively.
Russell and Kelushy [42] analysed the nature of the SA grafts onto
n-eicosane by 1Hand 13C NMR (Bruker AM 400 NMR) and found that the
grafts consisted of single SA rings when formed at 16SoC and at low MA
concentrations 0.02 M). Supporting evidence for this conclusion comes
from a comparison of the 1H NMR spectra of poly(maleic anhydride)
(PMA) with those of the MA-modified eicosane products. They also argued
that under those conditions, PMA was above its ceiling temperature (4SC)
and SA radicals preferred to terminate their lives upon abstracting a
hydrogen atom from a methylene group rather than undergo addition to a
further MA unit.
Lee and Russell [44] analysed the molecular architecture of the grafts of
N -methylmaleimide [49] onto n-eicosane, squalane or a low molecular
weight PE of Estaman Chemicals (approximately 2000 g/mol) obtained at
130C-170C in the presence of 2,S-(di-t-butyl-peroxy)-2,S-dimethylhexyne
(DTBHY). They concluded that, similar to MA, those grafts consisted of
single N-methylsuccinimide units.
If the major factor preventing the formation of long side-chain grafts is
ceiling temperature, an increase in monomer concentration and a drop in
reaction temperature should cause a significant change in the microstructure
of the grafts. In order to verify this point, Russell [4S] and Wong Shing,
28
Baker and Russell [46] studied the grafting of MA onto n-eicosane and
squalane at low temperatures (60C-80C) in 1,2-dichlorobenzene using BP
as the free-radical source. The MA concentration was chosen to be on the
order of 1 M so that the reaction temperature (60C-80C) is below the
ceiling temperature of PMA. (The estimated ceiling temperatures for
homopolymerisation of MA are 108C for 1 M monomer and 90C for 0.4 M
monomer.) They found that in the absence of the hydrocarbon and with
monomer concentrations of the order of 1 M, low molecular weight PMA
(500-1500 g/mol) was formed. On addition of the hydrocarbon, the main
product was grafted material, and very little homopolymer was formed. The
grafts consisted primarily of single SA units but some of them were short
PMA chains. They concluded that ceiling temperature considerations controlled the formation of homopolymer in the absence of hydrocarbon
substrate, whereas in the presence of a hydrocarbon the main factor
controlling the graft length was the ratio between the rate of intramolecular
and/or intermolecular macroradical transfer and that of monomer addition
to SA radicals. If this ratio is high, the graft length should be short, and vice
versa.
More recently, Heinen et al. [47] studied reaction products from the
free-radical initiated grafting of 13C-enriched maleic anhydride ([2,313C2]MA) onto PP, HDPE, LDPE and EPR of various ethylene-topropylene ratios using noise-decoupled and 1D inadequate 13C NMR
spectroscopy. The advantage of using 13C-enriched maleic anhydride is to
enhance NMR signals when the amount of MA is small. They found that
MA attached to the HDPE and LDPE was in the form of single succinic
anhydride moieties and short oligomers. In EPR and PP, MA grafts were
mainly in the form of single succinic anhydride moieties. They also concluded that single succinic anhydride rings are attached to the chain ends of
PP and EPR when the propylene content of this latter is high (75% in mol).
This was explained by a chain scission reaction which involves a hydrogen
transfer from a macroradical to a succinic anhydride molecule attached to
a tertiary carbon atom of PP. The corresponding succinyl radical is unstable
and undergoes p-scission leading to a succinic anhydride attached to the
chain end of PP. That longer succinic anhydride grafts are formed in the
HDPE and LDPE and only single MA moieties are attached to the PP and
EPR is consistent with the statement made earlier (Section 1.2.1) that the
length of grafts depends very much on the kH/kgp ratio which measures the
relative importance between the rate of intramolecular and/or intermolecular macroradical transfer and that of monomer addition to macroradicals.
If this ratio is high, the graft length should be short, and vice versa. There
are more abundant tertiary hydrogen atoms in PP and EPR than in HDPE
and LDPE. Therefore, the intramolecular and/or intermolecular hydrogen
transfer between a succinyl macroradical and a macromolecular chain is
29
easier with PP and EPR. Consequently, MA grafts should not be longer

onto PP and EPR than on HDPE and LDPE.
We have seen above that despite 30 years of research in the field of
free-radical grafting of monomers, and MA in particular, onto polymer
substrates, and notably polyolefins, certain problems remain not only in
terms of our fundamental understanding of the mechanisms that govern the
overall grafting and of the microstructure of grafts, but also in terms of the
importance of side reactions. It has been shown that when MA is to be
grafted onto PP, the major problems are limited MA grafting yields and
significant reduction in PP molecular weight by p-scission and therefore an
important loss in the mechanical properties of the virgin material. Also,
when large amounts of MA are added, say, greater than 2 phr, modified PP
becomes yellowish, even brown.
Numerous tentative suggestions have been reported in the literature to
improve the MA grafting process. However, most of them tend to remedy
the problem by using electron-donating organic substances in order to
reduce PP chain degradation. As shown earlier, this approach has not
yielded desired results because the addition of electron-donating organic
substances not only reduces PP chain degradation but also decreases the
MA grafting yield. As far as the grafting mechanisms and the microstructure
of grafts are concerned, our knowledge is largely incomplete. Many speculations are involved in the mechanisms and/or microstructure of grafts
proposed in the literature.
1.5 Recent advances in melt free-radical grafting
In what follows, we discuss recent advances in melt free-radical grafting
upon taking two systems investigated in our Reactive Extrusion Laboratory
as examples: the grafting of MA [48-50] and glycidyl methacrylate (GMA)
[51-53] onto PP. The chemical structure of MA is shown in Figure 1.2 and
that of GMA in Figure 1.3. GMA bears a double bond (free-radical
reactivity) and an epoxy group (functional reactivity). This epoxy group
possesses reactivity toward various functional groups such as -COOH,
-OH, -SH, and -NH 2
The reason for choosing these two systems is that the MA grafting system
reveals mainly the chemical aspect of the melt free-radical grafting whereas
in the case of the GMA grafting system both the chemical and the
processing aspects of the problem are addressed. Also, the MA system is
pretty much classical in the sense that much has been written out about it.
The GMA system, on the other hand, has not received much attention until
recently. Nevertheless, our recent results have shown that because of its
versatile functional reactivity, GMA can play an important role in the
30
CH
I 3
CH=C-C-O-CH-CH-CH
II
Figure 1.3 Chemical structure of glycidyl methacrylate (GMA).
chemical modification of existing polymers as well as in reactive blending.

It is hoped that the complementarity of both systems will provide readers
with a reasonably complete sketch of melt free-radical grafting.
1.5.1
Description of the grafting systems and reactors used
Table 1.8 shows selected characteristics of stabilised PP used for the MA

and GMA grafting, unless specified otherwise. The advantage of using a
powdery or porous PP lies in its ability to absorb much larger amounts of
liquid monomers than PP in granular form, thus facilitating material feeding
and reducing monomer loss.
The MA, GMA, styrene (St) and other monomers are from Aldrich and
used as received. 2,5-Di(t-butyl-peroxy)-2,5-dimethyl hexane (DTBPH) is
employed exclusively for the MA grafting, unless specified otherwise. As for
the GMA grafting, both DTBPH and DTBPIB are used. They are supplied
kindly by Akzo Company and used as received (halflives are shown in Table
1.1).
Both the MA and GMA grafting systems are investigated first in a batch
mixer of Haake Rheocord (50 cm 3 ) type and then in a co-rotating selfwiping twin screw extruder of Werner & Pfleiderer ZSK-30 type (W&P)
This W&P machine has a screw diameter of 30.7 mm and a length-todiameter ratio of 42. A major feature of this type of machine lies in its
Table 1.8 Selected characteristics of the stabilised PP used for the MA and GMA grafting. The
molecular weights reported here are obtained by high-temperature size exclusion chromatography
PP for MA Grafting
Supplier
Physical state
Weight average molecular
weight, Mw (g/mol)
Number average molecular
weight, Mn (g/mol)
Melt index (g per 10 min)
(230C; 2.16 kg)
Remarks
PP for GMA grafting
Elf-Atochem, France
Powdery
308000
Himont, Belgium
Porous
654000
72000
141000
5.0
0.3
Homopolypropylene
Copolymer with 9 wt% ethylene
I~
200C
>
1-
Sampling
230C
240C
Venting
-I ""'<: ...----
Sampling
'> I
~Pling
Figure 1.4 (a) Screw profile used for the MA grafting onto a stabilised and powdery PP. Temperature range = IS0C - 200C;
screw speed = SO rpm; throughput = 6 kgjL; mean residence time = 180 s; (b) screw and temperature profiles of the extruder used
for the free-radical grafting of GMA onto a stabilised and porous PP. Figure 1.4(b) reproduced with permission from Sun, Y.-J.,
Hu, G.-H. and Lambla, M., Journal of Applied Polymer Science, 57, 1043- 54; published by John Wiley & Sons, Inc., New York,
Copyright 1995 John Wiley & Sons, Inc.
(b)
PP + monomers + peroxide
(a)
PP + MA (+ St) + DHBP
32
modular design in terms of barrel and screw elements. This modularity

provides great processing flexibility for feeding, melting, mixing, reaction,
devolatilisation, temperature control. The temperature of the extruder
barrels is regulated by electrical resistance and water circulation inside the
barrels.
The MA and GMA grafting in the batch mixer is done at 215C-220C
and 200C-205C, respectively. The mixing time is usually 15 minutes and
the mixing speed of the rotors 64 rpm, unless specified otherwise. As far as
the MA and GMA grafting in the W&P twin screw extruder is concerned,
their screw and temperature profiles are shown in Figures 1.4(a) and 1.4(b),
respectively. The screw and temperature profiles for the GMA grafting are
so chosen as to fit a subsequent process for the in situ compatibilisation of
PP and poly(butylene terephthalate) blends by one-step reactive extrusion
[54,55].
Both for the MA and for the GMA grafting systems, the powdery or
porous PP is premixed with chosen amounts of a mixture of monomers and
peroxide at room temperature and then fed into the hopper of the extruder
by a weight-loss screw feeder of type K-Tron KIOS. For all runs, devolatilisation is ensured by a vacuum pump. This pump is placed near the
die and it creates a pressure of about 25 mm Hg. The extruder is always
starved fed. Thus, the screw speed (N), feed rate (Q) and specific throughput
(Q/N) can be varied independently.
In the case of the GMA grafting, in order to follow the entire grafting
process inside and along the extruder and to investigate the effects of
chemical and processing parameters on this process, samples of modified
PP are taken not only at the exit of the die but also at two other positions
upstream (Figure 1.4(b)). These two sampling holes are located at 36% and
50% of the total screw length from the feeding point, respectively. These
holes are closed when the machine is running. After the extrusion process is
in a steady state, samples are taken while the machine is running. They are
then quenched quickly in liquid nitrogen to stop the reaction.
1.5.2
Maleic anhydride (MA) onto polypropylene (PP)
(a) Grafting of MA alone. As the grafting of MA (see Figure 1.2 for its
chemical structure) onto PP has been studied the most in the literature, we
start our discussion with this grafting system. Figure 1.5 shows the MA
grafting yield as a function of the amount of MA introduced. In agreement
with the literature, the grafting yields are relatively low 0.65 phr).
Moreover, the PP molecular weight reduction is significant: at the maximum grafting yield of MA, which corresponds to 4.0 phr MA introduced,
the Mn and Mw of the PP are decreased from the original values of 72000
g/mol and 307000 g/mol, respectively, to 29000 g/mol and 52000 g/mol,
respectively. This high level of PP chain degradation is not surprising
considering the presence of a high dose of DTBPH (0.5 phr) in the system.
33
0.7,..---------------,
0.6
ij
0.5
0.4
10.3
0.2
0.1
10
MA introdtmd (ptr)
Figure 1.5 MA grafting yield onto a powdery PP as a function of the initial amount of MA
introduced in the batch mixer: 0.5 phr DTBPH; temperature = 215C-220C; mixing
speed = 64 rpm; reaction time = 15 min. Reproduced with permission from Hu, G.-H., Flat,
1.-1. and Lambla, M., Makrornol. Chern., Macrornol. Syrnp., 75,137-57; published by Hiithig &
Wepf, Zug, 1993.
More interestingly, the MA grafting yield is not a monotonic function of

its initial concentration. In fact, it initially increases with increasing MA
concentration and reaches a maximum when about 4 phr MA introduced
and then decreases with a further increase in MA concentration. The
existence of a maximum for the MA grafting yield is associated with a
limited solubility of MA in the molten PP. In fact, the solubility of MA in
toluene is only 0.2% at 25C, and 0.35% at 150C [42]. Therefore, it is
plausible that with increasing MA content, the PP/MA/DTBPH mixture
changes from a single phase to a biphasic system with MA/DTBPH droplets
dispersed in the molten PP. The formation of MA/DTBPH droplets not
only reduces the effective concentrations of MA and the peroxide for
grafting but also promotes MA to homopolymerise within these MA/
DTBPH droplets. This latter is more like a suspension polymerisation. It is
this homopolymerisation of MA leading to the formation of PMA that is
believed to be responsible for PP coloration during MA free-radical grafting. The more MA is homopolymerised, the more severe the PP coloration
becomes.
The existence of a maximum in MA grafting yield with respect to the
initial MA concentration was also observed by Oostenbrink, Borggreuve
and Gaymans [34] and Hogt [25]. The former studied the MA grafting
onto EPDM in a co-rotating twin screw extruder of Berstorff type. They
found that the MA grafting yield reached a maximum when about 2 phr
MA was added. Hogt observed a similar phenomenon when MA was
34
grafted onto PE in a Brabender mixer. Furthermore, it was shown that such

a maximum apparently depended on the solubility of the peroxide used for
grafting (see ch. 2).
As shown in Figure 1.1, there exists a competition between grafting and
degradation for PP macroradicals. Once they are formed they will undergo
either degradation or grafting. Those that are not consumed for grafting will
cause degradation by p-scission. Because of the instability of PP tertiary
macroradicals associated with their tertiary character, the degradation
process is extremely fast and important at elevated temperatures. Therefore,
low MA grafting yields together with severe PP degradation must be
attributed to the weak free-radical reactivity of MA. In fact, the low
free-radical reactivity of MA is a well-known fact. It results from the
following inherent structural characteristics of MA:
a strong steric hindrance arising from the di-substitution of the two
adjacent carbonyl groups at positions 1 and 2 of the double bond,
a deficiency of electron density around the C=C double bond of MA
because of the electron-attracting nature of the carbonyl groups, and
the symmetry of the double bond and the corresponding electron cloud.
This clearly indicates that an improved MA grafting yield together with a
reduced PP chain degradation can be possible by promoting the free-radical
reactivity of the double bond of MA. This can be done by 'activating' the
double bond of MA such that the occurrence of the desired grafting between
MA and PP macroradicals precedes the PP chain degradation at these
macroradical points by p-scission. It is hoped that in this way smaller
amounts of peroxide will be enough to obtain sufficient MA grafting yields
with reduced PP chain degradation. For this purpose, we have explored
three methods to activate chemically the free-radical reactivity of the double
bond ofMA:
addition of an electron-donating monomer such as St that is capable of
forming a charge transfer complex (CTC) with MA,
addition of a diene such as 1,3-cyclopentadiene (CPO) which is capable
of forming an adduct of type Diels-Alder with MA which can further
decompose into activated MA,
substitution of one of the hydrogen atoms of MA by a strong electrondonating or attracting group. In this case, MA is replaced by an MA
derivative such as bromomaleic anhydride (BrMA).
It turns out that indeed all three methods have been very successful in
improving the MA grafting yield and reducing PP chain degradation [48].
Because of space limitations, below we will constrain ourselves to describing
the first approach only.
(b) Concept of charge transfer complex (CTC). The electron density of

the double bond of MA is largely shifted to its two electron-attracting
'C==C"
I
35
r==::!"~
-,
O=C, "C=O
Figure 1.6 Formation of a charge transfer complex (CTC); example: MA/St.
carbonyl groups. As a result, MA is reluctant to be grafted onto PP

backbones. One way to render MA more reactive is to add a second
monomer which is capable of donating electrons to MA. One will then have
a mixture composed of an electron-donating monomer (D) and an electronaccepting monomer (A) with monoelectronic transfer from the D to the A.
As a result, the symmetric character of the double bond of MA will be
modified with the formation of a radical anion. This latter is a so-called
charge transfer complex (CTC), as depicted in Figure 1.6 in which the
mixture of MA-St is taken as an example. It is hoped that the MA involved
in the CTC will show high grafting reactivity. For any pair of AjD, the
equilibrium for the formation of a CTC can be described as:
K.
A+O~CTC
t=o
[A1o [010
1>0
[A]
[CTC]
[OJ
1.8
The stability of the CTC can be characterised by the equilibrium constant

K s ' which is defined as
[CTC]
Ks = [A][D]'
The higher is K s ' the greater is the stability of the CTC, and the higher is
the electron-donating capacity of the D. Also for a particular electrondonating/electron-accepting system, the concentration of the CTC is temperature dependent. Usually it decreases with increasing temperature.
However, it is not always easy to determine the stability of a CTC system.
This is true even for a classical system such as MA/St. Various analytical
36
techniques have been used for this purpose; UV and NMR are probably
employed the most. The ability of 1 H NMR to characterise the stability of
a CTC is related to the fact when an electron-accepting monomer such as
MA is complexed with an electron-donating monomer, the chemical shift in
IH NMR of free MA, br, is shifted to be. The difference between be and br,
AH, varies depending on the stability of the CTC. For a particular
electron-accepting species, this variation depends primarily on the nature
and the concentration of the electron-donating monomer. Thus, for a
particular electron-accepting monomer, 1 H NMR is expected to be suitable
for ranking the electron-donating capacity of different electron-donating
monomers.
If the double bond of MA can indeed be activated upon formation
of a CTC with an electron-donating monomer, the free-radical reactivity
of the activated MA will depend on the stability of the CTC formed,
which in turn will depend on the nature of the electron-donating monomer.
Among possible electron-donating monomers, we may consider styrene
(St), a-methyl styrene (a-MeSt), N-vinyl pyridone (NVP), trimethoxyvinylsilane (TMVS), methyl methacrylate (MMA), methyl acrylate (MAc),
I-dodecene (OU2), iso-butylvinylether (IBVE), and vinylcyclohexane
(VCH).
The electron-donating capacity of these monomers is ranked by measuring the chemical shift difference of the protons of MA, AH, by 1 H NMR
1~.------------------------.
120
100
20
o~~~~
__~~~~~~
234
Cormriration r:I eIec:Iron<loret'll rmromer (M)

Figure 1.7 I1H, or the electron-donating capacity, of various monomers toward MA according
to NMR 'H in CDCl 3 at 22e. Mixture: = BrMA/St; <) = MA/St; ~ = MA/IX-MeSt;
\j = MA/NVP; ... = MA/TMVS; 1:::. = MA/MMA; = MA/MAc; 0 = MA/0L12; EB=
MA/18VE; 0 = MA/VCH. Reproduced with permission from Hu, G.-H., Flat, I.-I. and
Lambla, M., Makromol. Chem., Macromol. Symp., 75, 137-57; published by Hiithig & Wepf,
Zug,1993.
37
(200 Hz) in deuterated chloroform (CDCI 3 ) at room temperature (22C).

They follow the order (Figure 1.7): St > ~-MeSt NVP > TMVS
MMA> MAc ~ 0L12 ~ IBVE > VCH. St and ~-MeSt appear to have the
strongest electron-donating capacity whereas VCH, which bears a saturated
cyclohexane ring rather than a benzene ring, has the weakest electrondonating capacity.
( c) Grafting of eTC systems. N ow we see whether the efficiency of
electron-donating monomer-assisted MA grafting, in terms of the MA
grafting yield and PP chain degradation, matches the electron-donating
capacity of this monomer. For this purpose, the batch mixer (Haake
Rheocord) is used.
The MA grafting yield as a function of its initial concentration with or
without externally added electron-donating monomer is shown in Figure
1.8. For all the electron-donating monomers selected, their presence improves more or less the MA grafting yield, with the exception of NVP.
Furthermore and much to our surprise, the magnitude of increase in MA
grafting yield corresponds exactly to the electron-donating capacity of the
co-monomer added (Figure 1.7). This is an important finding because it
shows that regardless of the mechanism(s) (involvement of a CTC?) by
which a co-monomer contributes to the increased MA grafting yield, 1H
NMR is indeed a technique capable of selecting electron-donating comonomers that will likely promote MA melt free-radical grafting.
ao~----------------------~
2.5
0.5
4
6
8
M6. iliraiJced (r:h)
10
Figure 1.8 MA grafting yield as a function of its initial concentration. 0.5 phr DTBPH;
temperature = 215C; mixing speed = 64 rpm; reaction time = 15 min; 0 = MA alone;
/:), = St; = IX-MeSt; 0 = MMA; = 0L12; 0 = VAc; T = NVP. Reproduced with permission from Hu, G.-H., Flat, J.-J. and Lambla, M., Makromol. Chem., Macromol. Symp., 75,
137-57; published by Hiithig & Wepf, Zug, 1993.
38
The magnitude of the MA grafting increase is more important when the

amount of MA added is higher: above 3 phr, the effect of adding a
co-monomer is visible, regardless of its nature; below this concentration, the
magnitude of improvement is small, except for styrene (St). Keep in mind
that styrene is the electron-donating monomer that improves the MA
grafting yield to the greatest extent over the entire MA concentration range.
The presence of its derivative, 0(- MeSt, also promotes MA grafting, but to a
lesser extent than St. As St and 0(- MeSt are two electron-donating
monomers with which MA interacts the most, it appears that the formation
of a CTC would have contributed to the activation of the double bond of
MA and consequently to a significant increase in the MA grafting yield.
The positive effect of the presence of other co-monomers on the MA
grafting at high MA concentrations (> 3 phr) may also be related to their
ability to solubilise MA in the molten PP - a 'vector effect'. In fact, such a
vector effect is very interesting and has been explored in the past [56,57].
For the present MA/PP system, this vector effect has surely played an
important role. This is because, in the absence of co-monomer, when the
initial MA concentration exceeds some critical value (2-4 phr), the PP/MA
system is phase separated with MA/DTBPH droplets dispersed in the
molten PP. As a result, the MA grafting yield is decreased, the amount of
PMA is increased and the modified PP becomes more coloured. This
phenomenon is no longer observed when a co-monomer is added, regardless
of its chemical structure or electron-donating capacity. In this case, the MA
grafting yield keeps increasing with increasing MA concentration over its
entire range (0-10 phr).
Disregarding NVP, the addition of a co-monomer such as St also allows
the preservation of the molecular weight of the modified PP compared with
the case when MA alone is grafted onto PP (Figure 1.9). Co-monomers
which have the strongest interactions with MA at room temperature are the
most efficient in terms of the increase in MA grafting yield and reduction in
PP degradation. This clearly shows that when MA is activated upon
addition of an electron-donating monomer, the PP macroradicals are better
used for grafting, minimising therefore PP degradation by fJ-scission.
Of all the electron-donating co-monomers tested, NVP is the only one
which does not improve the MA grafting yield, despite its relatively high
interaction with MA. Instead, it decreases the MA grafting yield compared
with the case where MA alone is grafted onto PP. Actually, NVP is also the
only co-monomer which contains a nitrogen atom. It is plausible that NVP
simply serves as a free-radical scavenger. Its presence in the grafting system
consumes free radicals, therefore doing no good at the MA grafting.
However, it should preserve the molecular weight of the PP. This is indeed
confirmed by the fact that the reduction in PP molecular weight is the
smallest when NVP is added as a co-monomer compared with other
co-monomers. Similar results were also obtained by Gaylord and Mishra
39
100~~------------------------~
140~
130~
-I::::g
120~
110~
..9
~ 100~
OO~
80~
70~
OO~+-~
__~~~~--~-r~__~-4
10
4
6
8
tv1A introducaj (phr)

Figure 1.9 The average molecular weight, Mw, of the PP after MA grafting with or without
co-monomers in the batch mixer. D = MA alone; t:,. = MA/St; = MA/MMA; = MA/
0L12; A = MA/NVP. Reproduced with permission from Hu, G.-H., Flat, J.-J. and Lambla,
M., Makrornol. Chern., Macrornol. Syrnp., 75,137-57; published by Hiithig & Wepf, Zug, 1993.
[30] when using DMF or DMAC as a co-monomer. The ability for NVP,
DMF and DMAC to minimise PP degradation during MA free-radical
grafting is related to their particular chemical structure: they all bear an
amide or a lactam group with a free doublet of the nitrogen atom. This free
doublet is delocalised by the carbonyl group in the (X position. It can interact
with the single electron of free radicals present in the system, therefore
deactivating their free-radical reactivity. As a result, all free-radical reactions
such as grafting and fJ-scission will be reduced.
In addition to the increased MA grafting yield along with reduced PP
degradation, another important benefit of adding a strong electron-donating
co-monomer such as St is the reduction in PP coloration. MA-modified PP
without co-monomer in the molten state is highly coloured (brown, even
dark). The degree of coloration depends, among many other things, on the
initial concentration of MA: the higher the MA concentration, the higher
the degree of coloration due to accrued amount of PMA formed. By
contrast, when St is added, the degree of coloration is much reduced.
Obviously, a reduced formation of PMA contributes to this discoloration
by the presence of a strong electron-donating co-monomer such as St. When
St is added, more MA is converted to grafted species onto PP chains, thus
the amount of MA available for homopolymerisation is reduced. Also, in
the presence of St, the polymer formed is likely to be a copolymer of MA
and St other than a homopolymer of MA alone. Such a copolymer is less
40
coloured than pure PMA, or is virtually colourless, depending on the molar

ratio of St and MA.
(d) Effects of various parameters. We have shown that addition of a
strong electron-donating co-monomer, especially St, is highly capable of
activating the double bond of MA by a charge transfer mechanism. As such,
the free-radical grafting reactivity of MA is increased: the MA grafting yield
is greatly increased and the PP chain degradation reduced. Below we
examine the effects of various other parameters such as temperature, the
nature and concentration of peroxide, the omission of added peroxide,
mechanical mixing, the presence of a substance containing nitrogen atoms,
the presence of a second co-monomer and even the physical state of PP
(granules, powder).
Effect of the physical state of PP. As a batch mixer of type Haake
Rheocord is not a completely sealed system, there may be some loss of
volatile monomers such as the pair MA/St. The degree of MA/St loss
depends, among other things, on the physical state of PP. A PP in powdery
form should be better than a PP in granular form because the former is
capable of absorbing larger amounts of liquid monomers. Thus MA grafting
yields with a powdery PP are expected to be greater than with a granular
PP and especially at high temperatures. This is confirmed by the results
shown in Table 1.9 in which the MA grafting yields obtained with a granular
PP are compared with those of a powdery PP of the same molecular
characteristics. As a matter of fact, the grafting yields with the powdery PP
are approximately twice as high as those with the granular PP under the
specified grafting conditions. In what follows, only the powdery PP is used
as a basis for discussion.
Effect of temperature. The overall free radical grafting process may be
influenced by temperature as both the kinetic and thermodynamic aspects
of all the elementary reactions involved are temperature dependent. However, the outcome of temperature effect is difficult to predict because of the
Table 1.9 Effect of the physical state of PP on MA grafting in a Haake

mixer. 4 phr MA + 4.25 phr St; 0.5 phr DTBPH; temperature = 215C;
mixing speed = 64 rpm; reaction time = 15 min. Both PP contain the
same stabilising additives
MA introduced (phr)
MA grafted (phr)
1.0
2.0
4.0
6.0
PP granules
PP powder
0.25
0.46
0.41
0.84
0.69
1.37
0.90
1.95
41
Table 1.10 Temperature dependence of MA grafting yield, [MA]g, onto the

powdery and stabilised PP in the batch mixer. 0.5 phr DTBPH; 4 phr MA + 4.25
phr St; mixing speed = 64 rpm; reaction time = 15 min
T (0C)
172
184
198
213
229
240
[MA]g (phr)
Torque (Nm)
1.36
1.52
1.32
0.84
1.32
0.46
1.57
0.44
1.34
0.42
1.44
0.40
complicated reaction scheme. For example, although an increase in temperature increases the rate of peroxide decomposition forming the desired
primary free radicals, it may aggravate secondary reactions as well. These
latter would reduce the initiator efficiency and consequently the grafting
yield. An increase in temperature also increases the rate of polymerisation
and to a slightly greater extent the rate of grafting. Thus the overall
temperature effect is expected to be weak in terms of the grafting yield. This
is indeed the case for St-assisted MA melt free-radical grafting onto PP over
a relatively large temperature range (Table 1.10).
Effect of mechanical mixing. Mechanical mixing may affect the melt

free-radical grafting system if the system is heterogeneous and the reaction
is diffusion controlled. The mixing intensity in a batch mixer can be varied
by changing the speed of the rotors in the mixing chamber. It turns out that
for the system composed of 100 phr PP + 4.0 phr MA + 5.09 phr
St + 0.5 phr DTBPH, the overall MA grafting yield is independent of
mixing (Table 1.11). This implies that the significant contribution of St to
the MA grafting results not only from its ability to activate chemically the
double bond of MA by formation of a CTC, but also from its solvating effect
which tends to increase the MA solubility in the molten PP.
MA grafting without externally added peroxide. Organic peroxides are
the major sources of free radicals necessary for initiating a melt free-radical
grafting process. Nevertheless, Gaylord et al. [58,59] claimed that the
grafting of MA/St or other systems prone to thermal copolymerisation
can be grafted onto polyolefins without any externally added free-radical
Table 1.11 Effect of mechanical mixing on the MA grafting yield,

[MA]g, onto a powdery and stabilised PP in the batch mixer. 4.0 phr
MA + 5.09 phr St + 0.5 phr DTBPH; temperature = 215C; reaction
time = 15 min
Mixing speed (rpm)
[MA]g (phr)
16
32
64
128
256
1.46
1.42
1.43
1.33
1.42
42
Table 1.12 Comparison between stabilised and non-stabilised PP in terms of MA grafting yield
[MAJ., without externally added organic peroxide. [St]j[MAl = ;:~ mol/mol; temperature = 215C; mixing speed = 64 rpm; reaction time = 15 min. Subscript i indicates initial
concentration
[MAl (phr)
Stabilised PP:
MA/St
[MAJ. (phr)
torque (N m)
Non-stabilised PP:
MA/St
[MAJ. (phr)
torque (N m)
MA alone
[MAJ. (phr)
torque (N m)
10
0.06
3.2
0.12
3.2
0.10
3.6
0.11
3.55
0.10
3.6
0.74
1.34
0.06
0.67
0.87
1.78
0.16
0.74
0.50
1.90
0.11
1.08
0.50
1.78
0.08
1.35
0.52
1.68
0.07
1.51
initiators. It was argued that the CTC (MA/St) was sufficiently active to be
inserted in a C-H bond of a polyolefin in the form of dimers or trimers.
Obviously, it would be highly advantageous if sufficient MA grafting
yields could be achieved by a non-free-radical mechanism or by limited
amounts of free radicals generated mechano-chemically without the need of
adding an organic peroxide. In this case, complications associated with
organic peroxides (toxicity, material handling) could then be avoided. Also,
difficulties in achieving adequate dispersion of organic peroxides into molten
polymers would be non-existent.
However, our results (Table 1.12) are not as promising as those claimed
by Gaylord et al. Without externally added peroxide, the MA grafting yields
are very low when MA/St is grafted onto the powdery PP which contains
an industrial stabilising package. Correspondingly, the molecular weights
characterised by torque are relatively high. This level of MA grafting yields
(",0.1 phr) would not be high enough for most classical applications
involving PP-g-MA. Also, as opposed to Gaylor et al.'s assumption that the
grafting of the CTC (MA/St) is of ionic character, our results tend to suggest
that it is of free-radical character. Supporting evidence is that the CTC
grafting is inhibited by the antioxidants added to the PP. If the CTC
grafting were of ionic character, it would not have been sensitive to the
presence of antioxidants.
In the case of a powdery and non-stabilised PP (antioxidant free) which
is otherwise identical to the stabilised PP, results are very different. When
MA alone is grafted onto it, the concentration of free radicals originating
from the atmospheric oxygen is not high enough to ensure sufficient MA
grafting because of its low free-radical reactivity. Moreover, the molecular
weight of the modified non-stabilised PP characterised by torque is much
43
lower than that of the stabilised one. By contrast, when St is present, the
double bond of MA is so activated by the formation of the CTC that free
radicals resulting from the air are high enough to obtain appreciable MA
grafting yields (0.74 phr grafted MA for 2.0 phr MA introduced). Also, the
PP degradation is much reduced when compared with the case of MA alone.
Therefore, it can be concluded that for the MA/ST (CTC) system, free
radicals provided by the atmospheric oxygen under the said melt grafting
conditions may be sufficient to reach appreciable MA grafting yields onto a
non-stabilised PP free of free-radical consuming additives.
Effect of the nature and the concentration of peroxide. As free radicals
are necessary for MA melt grafting, their nature and concentration should
also be important. The nature and concentration of primary free radicals
depend, in turn, on those of organic peroxides employed. The initiator
grafting efficiency of several organic peroxides of different thermal stability
is compared in Table 1.13 in terms of the MA grafting yield and the
molecular weight of the corresponding PP under the same grafting conditions. One notes that the molecular weights of the modified PP samples are
virtually the same for all the peroxides tested, with the exception of
DTBHY, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane (HMCN) and
tert-butyl hydroperoxide (TBHP). DTBHY yields the lowest PP molecular
weight, and TBHP yields the highest.
It is surprising that the use of DTBHY reduces the PP molecular weight
so much. This is particularly so when compared with DTBPH. Apparently,
these two organic peroxides should not differ much. In fact, they all have
similar chemical structures and are capable of generating the effective
t-butoxy radical for grafting (Table 1.1). Moreover, their halflives are of the
same order of magnitude. The above analysis forces us to speculate that the
important PP degradation caused by DTBHY might be the result of an
accrued solubility in the molten PP. In this way, the peroxide concentration
in the PP phase would be much greater than in the case of DTBPH. The
least degradation in the case of TBHP is easier to understand. Its halflife is
very long (about 60 min at 200C). In other words, it releases primary free
Table 1.13 Initiator grafting efficiency for the MA/St melt grafting onto a stabilised PP. 4 phr
MA + 4.25 phr St + 0.5 phr organic peroxide; temperature = 215C; mixing speed = 64 rpm;
reaction time = 15 min
Peroxide
DCP
BCP
DTBPH
DTBP
DTBPHY
HMCN
TBHP
T ee) (t 1/2 = 1 min)
175
1.54
132
43
180
1.63
123
35
190
1.42
116
41
190
1.83
121
35
195
1.63
205
1.24
126
47
260
0.91
161
42
(phr)
Mw (kg/mol)
Un (kg/mol)
[~A]g
'PP samples are highly degraded.
44
radicals at a rate that is much slower than that of other classical organic
peroxides for grafting. Thus the time available for the monomers to escape
from the batch mixer is highly increased before they are grafted. Also,
because of a reduced release rate of primary free radicals, both the grafting
yield and the PP chain degradation are reduced.
The initiator grafting efficiency follows the order: DTBP > DTBHY ~
BCP > DCP > DTBPH > HMCN TBHP for a given concentration
(0.5 phr). This order does not match that of the amount of active oxygen
contained in these peroxides, which follows the order: DCP < BCP <
DTBPH ~ DTBP ~ DTBHY < HMCN < TBHP. This implies that apart
from the weight concentration of the peroxide or the effective concentration
of the active oxygen, the chemical nature of the primary free radicals, and
consequently the type of peroxide, should also be important in the grafting
process. In fact, a grafting process is believed to start with the abstraction
of hydrogen atoms from the PP chains by primary free radicals generated
from the thermal decomposition of a peroxide. The peroxides mentioned
above generate free radicals of different chemical structures. Their hydrogen
abstraction efficiency may not necessarily be the same. However, a reasonable estimate of their grafting efficiency is difficult to make owing to seveal
factors involved. Nevertheless, it appears that organic peroxides that generate t-butoxyl radicals would be the most effective for MA melt grafting. In
fact, this type of free radical is known for its ability to abstract hydrogen
atoms from alkanes. It is worth mentioning that DTBP is not recommended
for industrial use for safety reasons despite its high grafting efficiency.
Instead, DTBPH is employed the most.
For a given peroxide, the concentration dependence of the MA grafting
yield on the peroxide concentration can be complicated for the MA/St
system. In the case of DTBPH as a free-radical generator, for example, the
MA grafting yield is not a monotonic function of the DTBPH concentration
(Figure 1.10). It first increases with increasing DTBPH concentration,
reaches a maximum at about 0.1 phr DTBPH and then decreases with a
further increase in DTBPH concentration. The PP degradation characterised by the reduction in torque is increasingly important with increasing
DTBPH concentration. Interestingly, the dependence of the MA grafting
yield on the DTBPH concentration for the PP/MA/St/DTBPH system is
analogous to its dependence on the MA concentration for the PP/MA/
DTBPH system (Figure 1.5). However, the causes responsible for the
existence of a maximum in the MA grafting yield appear to be different. As
mentioned earlier, in Section 1.5.2(a) when the MA concentration exceeds a
critical value ( '" 3 phr), the PP/MA/DTBPH system will be phase separated
with MA/DTBPH droplets dispersed in the molten PP. The side reaction
between MA and DTBPH increases with increasing MA concentration. By
contrast, the PP/MA/St/DTBPH system should be homogeneous over the
entire MA concentration range under the said grafting conditions because
45
3.0...---.------------,
\ ---0
~\o-o
--------.0
'C'
~ 1.0
to.s
.~
-------.
0.0+---r-~-r_~__r--.-:r_-..--__r-1
0.0
0.5
1.0
1.5
2.0
[Df-BJjj (plY)
Figure 1.10 Initial peroxide (DTBPH) concentration dependence of the MA grafting yield,
[MA]g' and the PP degradation characterised by torque. Mix = 4.0 phr MA + 4.25 phr St;
temperature = 215C; mixing speed = 64 rpm; reaction time = 15 min; 0 = grafting yield;
= torque.
of the solvating effect of St. In this case, an increase in the DTBPH

concentration favours not only the desired MAjSt grafting but also the
undesired co-polmerisation of MA and St. The outcome will depend on the
relative importance of these two opposing effects. Our results would imply
that under the said grafting conditions, the copolymerisation between MA
and St would benefit more from an increase in the DTBPH concentration
than would MAjSt grafting.
Effect of adding a second electron-donating monomer. We have seen that
addition of a strong electron-donating monomer, and St in particular, to the
PPjMA system promotes greatly the MA melt free-radical grafting onto PP.
It would be interesting to know whether addition of a second electrondonating monomer to the PP jMAjSt system would further promote the
melt free-radical grafting of the MAjSt system. Table 1.14 shows the effect
of adding MMA or Q(-MeSt as a second electron-donating monomer on the
MA grafting yield and the PP chain degradation characterised by torque.
Interestingly, the MA grafting yield is not increased but decreased upon
addition of a second electron-donating monomer. The sole improvement lies
in the increased torque of the system and thus a reduced PP degradation
when Q(-MeSt is added as a second electron-donating monomer. At first
glance this rather negative effect of adding MMA or Q(-MeSt as a second
electron-donating monomer is surprising. One would have expected a
positive effect because addition of MMA or Q(-MeSt to the PPjMAjSt
46
Table 1.14 Effect of adding a second electron-donating monomer (MMA or IJ(-MeSt) on the
MA grafting yield, [MAJ., and the PP molecular weight characterised by torque for the MA/St
system. [MA);: [St);: [third co-monomer); = 1: 1.2: 1.2 by mole; temperature = 21SOC; mixing
speed = 64 rpm; reaction time = 15 min
[MA);: CSt); (phr:phr)
MA alone
[MAJ. (phr)
torque (N m)
MA with MMA
[MAJ. (phr)
torque (N m)
MA with IJ(-MeSt
[MAJ. (phr)
torque (N m)
2:2.55
4: 5.09
6:7.64
8: 10.19
10: 12.73
0.75
0.64
1.43
0.88
1.87
1.22
2.36
1.64
2.70
1.72
0.63
0.62
1.08
0.82
1.48
1.00
1.37
0.84
1.74
0.86
0.55
0.94
0.94
2.35
0.94
3.05
0.83
3.45
1.48
4.00
system would amount to increasing the St concentration and consequently

the CTC concentration. However, one should not forget that when a second
electron-donating monomer is added, the probability of MA copolymerising
with this co-monomer is also accrued.
From the above analysis, one may realise that the beneficial effect of
adding an electron-donating monomer is not without limit. MA is known
for its weak free-radical reactivity. As a result, both the MA grafting onto
PP and the MA homopolymerisation are low. In the presence of an
electron-donating monomer, the double bond of MA is activated and its
free-radical reactivity increased. An increased MA free-radical reactivity not
only favours grafting but also favours copolymerisation. Therefore, there
must exist an optimal concentration for an electron-donating monomer that
corresponds to a maximum MA grafting yield. This point will now be
discussed further.
Effect of adding an electron-donating solvent. If an accrued copolymerisation is indeed responsible for the reduced MA grafting yield when an
excess of an electron-donating monomer is added to the PP/MA/St system,
then one may think of replacing a copolymerisable electron-donating
monomer by a non-copolymerisable and electron-donating solvent. Such a
solvent could be an organic compound containing a nitrogen atom, such as
DMF or DMAC. In fact, Gaylord and Mishra [30] already used such
compounds to reduce PP chain degradation. They found that addition of
such a compound to the PP/MA system did reduce PP chain degradation,
but it also decreased the MA grafting yield. According to Gaylord and
Mishra a reduced PP chain degradation is related to deactivation of cationic
intermediate products involved in the MA grafting process. In our opinion,
this is probably not true.
47
Table 1.15 Effect of adding an electron-donating solvent (DMEU or DMF) on the MA grafting
yield, [MAJ., and the torque for the PP/MA/St system. [MAl: [Stl = 1: 1.2 mol/mol;
temperature = 215C; mixing speed = 64 rpm; reaction time = 15 min
[MAl: [Stl (phr: phr)
MA alone
[MAJ. (phr)
torque (N m)
MA with DMEU (0.5 phr)
[MAJ. (phr)
torque (N m)
MA with DMF (0.5 phr)
[MAJ. (phr)
torque (N m)
2:2.55
4:5.09
6:7.64
8: 10.19
10: 12.73
0.75
0.64
1.43
0.88
1.87
1.22
2.36
1.64
2.70
1.72
0.46
1.06
0.97
1.02
1.05
1.16
1.26
1.46
1.00
1.76
0.30
0.54
0.55
0.62
1.14
1.04
1.48
1.30
1.50
1.64
Table 1.15 shows the effect of adding an electron-donating solvent to the

PP/MA/St system in terms of the MA grafting yield and torque. For two
solvents tested, DMF and 1,3-dimethyl 2-imidazolidinone (DMEU), the PP
chain degradation is reduced compared with the case where such a compound is not added. Moreover, the MA grafting yield is decreased. As we
have shown earlier that the MA grafting is not of ionic but free-radical
character, the presence of DMF or DMEU must serve only to capture free
radicals and consequently decrease the MA grafting yield. This means
that in practice it would be better to reduce the dose of the peroxide than
to add an electron-donating solvent in order to minimise the PP chain
degradation.
(e) Grafting in a twin screw extruder. Basically, the free-radical grafting
behaviour of MA onto PP in a co-rotating intermeshing twin screw extruder
of type ZSK-30 is qualitatively similar to that in the Haake batch mixer. In
the case of the PP/MA system, an increase in the DTBPH concentration
increases the MA grafting yield (Figure 1.11). However, the grafting yield
does not exceed 0.3 phr, regardless of the initial MA concentration. In fact,
large amounts of peroxide (0.5 phr DTBPH) have to be added in order to
reach this level of grafting yield. As a result, the PP molecular weight
reduction is important (Mw is reduced from 307 kg/mol to 115 kg/mol).
Interestingly, when compared with the grafting of MA alone onto PP in the
batch mixer, the MA grafting yield obtained in the extruder for the same
MA and DTBPH concentrations is significantly lower. For example, for
2 phr MA and 0.5 phr DTBPH charged, the MA grafting yield is about
0.53 phr in the batch mixer and only 0.27 phr in the extruder. As will be
discussed below, a lower MA grafting for the PP /MA system is probably
related to a reduced contribution of free radicals originating from air.
48
1.6
1.4
1.2
1.0
0.6
fO.8
MAsystem
0.4
02
0.0
~
1.0
'V
"l-
1.5
2.0
2.5
3.0
[~i (phr)
Figure 1.11 Grafting yield of MA, [MAJ., onto a powdery and stabilised PP as a function of
MA concentration with or without St with various amounts of DTBPH. [DTBPH]: 0 = 0.05
phr; 0 = 0.1 phr; L. = 0.2 phr; V = 0.5 phr;. = 0.05 phr;. = 0.1 phr; A = 0.2 phr; ... = 0.5
phr. Reproduced with permission from Hu, G.-H., Flat, J.-J. and Lambla, M., Makromol. Chem.,
Macromol. Symp., 75, 137-57; published by Hiithig & Wepf, Zug, 1993.
When St is added as a co-monomer, the MA grafting yields are increased

significantly even at low DTBPH concentrations (Figure 1.11). With 0.05
phr DTBPH, 40% of the total MA introduced is already grafted onto PP
and the modified PP less degraded (M w :::::; 170 kg/mol; Figure 1.12). If more
DTBPH is charged to the grafting system, the PP degradation becomes
more important whereas the MA grafting yield increases, but to a limited
extent. Also noteworthy is that for the PP/MA/St system, the MA grafting
yield does not level off but increases virtually linearly with increasing MA
concentration, regardless of the DTBPH concentration.
The only notable difference between the Haake batch mixer and the twin
screw extruder is revealed when MA/St is grafted onto a powdery and
non-stabilised PP without any externally added peroxide. Recall that in the
case of the batch mixer, appreciable MA grafting yields were obtained (0.74
phr grafted MA for 2 phr MA introduced; Table 1.12). However, in the case
of the extruder, the MA grafting yields are zero or virtually zero, even
though the nitrogen purge system in the hopper is not employed. Obviously,
this difference must be related to the fact that the Haake batch mixer is a
semi-open system whereas the extruder is better sealed against oxygen. The
grafting system is expected to have greater contact with air in the batch
mixer than in the extruder.
230
220
--g
'I
210
+~+
200
190
180
~~ 170
l:e 160
150
140
130
-----+
.-------.------.
-------. ------,,-------,,----"
4_A
1.0
3.0
1.5
49
2.0
2.5
~i (pIT)
3.5
Figure 1.12 Molecular weights of MA/St-modified P in the presence of various amounts of

DTBPH. The PP used is stabilised except for the case of 0 phr DTBPH in which the PP is
un stabilised. [DTBPH]: + = 0 phr; = 0.05 phr; = 0.1 phr; .... = 0.2 phr; T = 0.5 phr.
Subscript i indicates initial concentration.
1.5.3
Glycidyl methacrylate (GMA) onto polypropylene (PP)
Similar to MA, the free-radical grafting reactivity of GMA alone is weak

(see Figure 1.3 for the chemical structure of GMA). For example, when
GMA alone is grafted onto porous and stabilised PP (ex Himont) in the
Haake batch mixer, the grafting yield is merely 0.38 phr with respect to 5.8
phr GMA introduced in the presence of 0.24 phr DTBPH at 200C. In other
words, only 7% of the total GMA is grafted under these conditions. When
the DTBPH concentration is raised to 0.44 phr, there is not much increase
in the GMA grafting yield. In this case, only 9% of the total GMA is grafted
onto the PP chains. In fact, grafting yields of the same order of magnitude
were also reported by Liu, Xie and Baker [60J under similar reaction
conditions. Thus, Gallucci and Going's [61J claim that GMA cannot be
grafted onto PP using a melt grafting process is not surprising.
The weak free-radical grafting reactivity of GMA alone implies that
GMA is not reactive enough toward the tertiary PP macroradicals. In order
to promote GMA grafting one would have to search for a second monomer
that is sufficiently reactive toward the PP macroradicals. Once reacted, the
resulting radical is then capable of reacting with the GMA monomer. In
other words, the strategy is that instead of grafting GMA directly onto PP
chains, one uses a second monomer that is capable of serving as a mediator
to bridge the gap between the PP macro radicals and the GMA monomer.
50
(a) Styrene-assisted GMA grafting. Inspection of the data of r;: 1 reported

in Table 1.4 tends to suggest that St would be a suitable candidate as a
'mediator monomer' for the grafting of GMA onto PP because the styryl
radical reacts well with the GMA monomer. The remaining question would
be whether or not the St monomer is capable of reacting with the PP
macroradicals faster than the GMA monomer. If St does react faster than
GMA, there would be, a priori, no reason that addition of St as a mediator
monomer should not help the GMA grafting.
Free-radical grafting of GMA, St and a mixture of GMA/St. Table 1.16
shows a comparison of the free-radical grafting of GMA, St and a mixture
of GMA/St onto PP (ex Himont) in the batch mixer. This comparison is
based on the same initial molar concentrations of St and GMA (0.043 mol
per hundred grams of resin (mhr), corresponding to 4.5 phr St or 6.1 phr
GMA). Very interestingly, the grafting yield of St alone is five times as high
as that of GMA alone: 0.014 mol grafted St against 0.003 mol grafted GMA.
In the case of the equimolar mixture of GMA/St, the GMA grafting yield is
increased by a factor of more than 3, namely, 0.10 mol GMA grafted. By
contrast, the St grafting yield is reduced from 0.14 mol to 0.006 mol.
As far as the PP molecular weight is concerned its reduction is not
significant, regardless of the monomer used. Nevertheless, the reduction in
PP molecular weight is more important with GMA alone than with St
alone. When St is added to the PP/GMA system, the PP molecular weight
degradation is virtually retained compared with that of the pure PP.
Correlation between [GMA]g and [St1. Figure 1.13 shows a correlation
between the GMA grafting yield, [GMA]g, and the initial St concentration,
[StL for a given initial GMA concentration, [GMA1. Note that [GMA]g
increases almost linearly with increasing ESt]; for a particular initial GMA
concentration, [GMA]i. For [GMA]i = 6.0 phr, the GMA grafting yield is
0.38 phr in the absence of St. When the molar ratio of [Stl/[GMA1 is 1.5,
Table 1.16 Comparison of the free-radical grafting reactivity between GMA, styrene and their
mixture at 200C for 15 min. [x], = initial moles of monomer x per 100 grams of PP resin (phr);
[x]. = moles of monomer x grafted onto 100 grams of PP resin (phr); mhr = moles per 100
grams of PP resin
[DTBPH],
(phr)
[GMA],
(mhr)
CSt],
(mhr)
[GMA].
(mhr)
CSt].
(mhr)
0.2
0.2
0.2
0
0.043
0.043
0.043
0
0.003
0.010
0.014
0.043
0.006
Mw
Mn
(kg/mol)
(kg/mol)
314283
229
327
lOS"
91
80
99
-Molecular weights of the pure PP alone subjected to 15 min of mixing at 200C in the batch
mixer.
51
2.0-.---------------,
1.5
:e
S 1.0
,.-,"
~ 0.5
0.0
0.5
0.0
1.0
[Stl
[GMA.l (mol/mol)
1.5
Figure 1.13 Grafting yields of GMA and St onto a stabilised and porous PP as a function of
the initial molar ratio of [St];/[GMA]i' [GMAl = 6.0 phr; [DTBPH] = 0.2 phr; temperature = 200C; mixing speed = 64 rpm; reaction time = 15 min; = [GMA].; 0 = [St] .
Subscripts i and g indicate the initial concentration and grafting yields, respectively. Reproduced with permission from Sun, Y.-J., Hu, G.-H. and Lambla, M., Die Angewandte Makromoleculare Chemie, 229,1-13; published by Hiithig & Wepf, Zug, 1995.
350
:IX)
~
-=
~
250
I i 200
""
Q
I~
150
100
13
50
0.0
II
0.5
ZI
1.0
1.5
[St]j
(rnoVrnol)
[GMA.l
Figure 1.14 Mw and Mn respectively of GMA-modified PP as a function of the initial molar

ratio of [St];/[GMA1. PP alone was mixed for 15 min in the mixer.. = initial Mw;'" = Mw;
0= initial Mn; b. = Mn. Reproduced with permission from Sun, Y.-J., Hu, G.-H. and Lambla,
M., Die Angewandte Makromoleculare Chemie, 229, 1-13; published by Hiithig & Wepf, Zug,
1995.
52
it is multiplied by a factor of about 5, reaching 1.8 phr. Also, when St is

added, there is a slight increase in number and weight average molecular
weights, Mn and Mw , respectively, of the modified PP samples (Figure 1.14).
(b) Kinetics. The rate of decomposition at normal grafting conditions is
rapid for most commonly used organic peroxides. For example, the halflife
of DTBPH is about 25 s at 200e. According to Equation 1.2, decomposition of an organic peroxide is virtually completed within a period that is
about five times the halflife, or 5t 1/ 2 . For the sake of brevity, this period will
be called the lifetime of the peroxide. If the rate of decomposition of an
organic peroxide is the rate-limiting step, then the overall free-radical
grafting should be accomplished within the lifetime of the peroxide employed. This means that when DTBPH is used as a free-radical generator,
free-radical grafting will be finished in about 2 min.
Indeed the free-radical grafting of an equimolar mixture of GMA and St
onto PP is a very rapid process using DTBPH (0.2 phr) as a free-radical
generator. Their grafting yields reach a plateau within 2 or 3 min of mixing
time at 200 e (Figure 1.15). It should be pointed out that a mixing time of
2 or 3 min is virtually the least time interval necessary for generating
meaningful data in the batch mixer. This is because when a grafting mixture
is charged to the batch mixer, a certain period of time is needed for melting
the polymer and homogenising the whole mixture. Thus the real time
0
2.0.,..---------------,
,._e-----------e
1.5
'i:'
.s::.
.e:
'C
1.0
Cl
&:
~o-o----------o
CJ 0.5 : ....
..,,
...,
12
8
Reaction time (min)
16
Figure 1.15 Grafting yields of GMA and styrene St onto a stabilised and porous PP as a
function of mixing time in the batch mixer. Initial concentrations: [GMAl = 6.0 phr;
[DTBPHl = 0.20 phr; [GMAl = 6 phr; and [Stl/[GMAl = 1.0 mol/mol. Grafting yield:
= [GMA]g; 0 = [St]g. Subscripts i and g indicate the initial concentration and grafting
yield, respectively. Reproduced with permission from Sun, y'-J., Hu, G.-H. and Lambla, M.,
Die Angewandte Makrornoleculare Chern ie, 229, 1-13; published by Hiithig & Wepf, Zug, 1995.
53
necessary for a complete grafting may be shorter than 2 or 3 min. This is

confirmed by grafting results generated in the extruder, as will be described
later.
The above results seem to suggest that if the melting and homogenisation
of the grafting system is very fast with respect to the rate of decomposition
of the peroxide employed, this latter will be rate-limiting in the overall rate
of free-radical grafting. How can one justify theoretically the speculation
that the decomposition of peroxide is the rate-limiting step for free-radical
grafting? We know that there are three important and consecutive reaction
steps necessary for grafting a GMA molecule onto a PP chain: the
generation of primary radicals upon thermal decomposition of the peroxide;
the formation of PP macroradicals by hydrogen abstraction; and the
grafting of GMA onto PP. Are these three reaction steps diffusion-controlled as a result of the highly viscous grafting medium? Obviously, this
question does not necessarily make sense for the decomposition of peroxide
as it involves only a single reacting species. In this case, the rate of
decomposition is characterised only by the halflife of the peroxide, t 1/2' As
far as the formation of PP macroradicals or GMA grafting are concerned,
they involve a small molecule (a primary radical or a GMA molecule) and
a macromolecule (a PP chain). If the rate of diffusion and that of reaction
(hydrogen abstraction or GMA grafting) can be characterised by characteristic diffusion and reaction times, to and t R, respectively, then the question
now is whether or not tl/2 is much larger than tR or to. The value of to can
be estimated as h 2 /D, with h being a characteristic diffusion length and D
the diffusion coefficient. If h is in the order of 1 x 10 - 7 m and D is in the
order of 1 x 10 - 14 m 2 Is for the reacting species involved in the hydrogen
abstraction and the GMA grafting, then to is in the order of 1 s, which is
one order of magnitude shorter than t 1/2' Thus it is likely that the rate of
diffusion of primary radicals or GMA monomers is faster than the rate of
decomposition of the peroxide. In other words, it is likely that the rates of
peroxide decomposition, hydrogen abstraction and GMA grafting are not
diffusion-controlled but determined only by their respective intrinsic reactivities; their reactivities can be characterised by their respective rate
constants, kd' kH and kgi (Figure 1.1) as well as their concentrations in the
grafting system. However, accurate data for these constants under melt
free-radical grafting conditions are scarce.
As for the plateau values for the GMA and St grafting yields, which
amount to 1.6 phr and 0.7 phr, respectively, they are well below their initial
concentrations: 6.0 phr and 8.2 phr, respectively. In other words, only about
30% of the total GMA and less than 10% of the total St are grafted onto
PP. The limited grafting yields should be related to the short lifetime of the
peroxide. When the halflife of the peroxide is short, the concentration of the
primary free radicals is high at the beginning of the grafting such that there
is a lack of the primary free radicals at longer times. As a result, the grafting
54
process ceases. In practice, stepwise peroxide addition may be employed to

raise grafting yields.
( C) Effects of various parameters
Effect of temperature. Recall that the free-radical grafting of MAjSt

onto PP is insensitive to temperature in terms of the MA grafting yield
(Table 1.10). A similar behaviour is observed for the GMAjSt system
(Figure 1.16). In fact, both the GMA and the St grafting yields are slightly
lower at a lower temperature (IS0C) than at a higher temperature (200C).
It is likely that the weak temperature dependence of grafting yield is a
general behaviour of melt free-radical grafting. However, it is conceivable
that temperature may have a pronounced effect on the molecular architecture of the resulting polymer as well as on the microstructure of the grafts.
More experimental evidence is needed to confirm this point.
Effect of the nature and the concentration of peroxide. Figure 1.17 shows
the grafting efficiency of two organic peroxides of similar chemical structures
and halflives (DTBPH and DTBPIB) over a relatively large concentration
range (0-0.44 phr). As expected, both peroxides display similar grafting
2.0...-----------------,
Figure 1.16 Temperature dependence of the GMA and St grafting yields onto St onto a
stabilised and porous PP in the batch mixer. [GMAl = 6.0 phr; [DTBPH] = 0.2 phr;
temperature = 200C; mixing speed = 64 rpm; reaction time = 15 min; 0 = [GMA]. at IS0 a C;
= [GMA]. at 200 a C; D = CSt]. at IS0 a C; = CSt]. at 200 a e. Subscripts i and g indicate
the initial concentration and grafting yield, respectively.
.?
2.5
2.0
1.5
0.5
55
f~
O~O
O~O
0
O.Oo-~---r~-..--~-,.-~-.--~-i
0.0
0.1
0.2
Percdde CD
0.3
0.4
ICe" aial (JiT)
0.5
Figure 1.17 Comparison of the grafting efficiency between DTBPH and DTBPIB.
[GMA]i = 6.0 phr; [styrene]J[GMA]i = 1.5 mol/mol; temperature = 200C; mixing
speed = 64 rpm; reaction time = 15 min. Grafting yields, by peroxide added:. = [GMA]g with
DTBPH; 0 = [St]g with DTBPH; = [GMA]g with DTBPIB; 0 = [St]g with DTBPIB.
Subscripts i and g indicate initial concentration and grafting yield, respectively. Reproduced
with permission from Sun, Y.-I., Hu, G.-H. and Lambla, M., Die Angewandte Makromoleculare
Chemie, 229, 1-13; published by Hiithig & Wepf, Zug, 1995.
efficiency. Over the entire range of the peroxide concentration, the GMA
and St grafting yields are slightly higher with DTBPIB. Also, unlike the
MA/St system in which there is an optimal peroxide concentration for a
maximum MA grafting yield, both the GMA and St grafting yields constantly increase with increasing peroxide concentration. This indicates that
the ultimate GMA and St grafting yields are dictated by the concentration
of primary free radicals. This concentration in turn depends on the initial
peroxide concentration.
The Mw and Mn of the GMA/St-modified PP as a function of the initial
DTBPIB concentration are shown in Figure 1.18. Overall, they decrease
with increasing peroxide concentration. Interestingly, unlike the PP/MA/St
system in which the PP molecular weight decreases constantly with increasing DTBPH concentration (Figure 1.9), the PP chain degradation of the
PP/GMA/St system is most important at low peroxide concentrations
(0.05 phr). A further increase in the peroxide concentration does not cause
any significant PP degradation. This implies that the hydrogen abstraction
reaction between the primary free radicals and the tertiary hydrogen atoms
of PP is very fast. Moreover, the resulting PP macroradicals are very
unstable and decompose rapidly into two fragments by p-scission.
56

~.----------------------.
300
e _ e______
100
0"
0------0------____ 0
O+-,_~_.~--r_~,_--_.~~
0.0
0.1
0.2
0.3
[DTBPIBl i (phr)
0.4
0.5
Figure 1.18 The average molecular weight and number Mw and M.. respectively of GMAmodified PP as a function of the initial concentration of DTBPIB, [DTBPIB1. [GMAl = 6.0
phr; [StJd[GMAl = 1.5 mol/mol; temperature = 200C; mixing speed = 64 rpm; reaction
time = 15 min;. = Mw; 0 = MD' Reproduced with permission from Sun, Y.-J., Hu, G.-H. and
Lambla, M., Die Angewandte Makromoleculare Chemie, 229, 1-13; published by Hiithig &
Wepf, Zug, 1995.
(d) Grafting in a twin screw extruder. As compared with a batch mixer of

the Haake Rheocord type which is a semi-open reactor, a co-rotating twin
screw extruder of type W&P ZSK-30 is better sealed. Apart from this
difference, a more fundamental difference between these two types of
reactors lies in that the former operates in a batch manner whereas the latter
operates in a continuous way. In the batch mixer the grafting yield is a
function of time, whereas in the twin screw extruder, owing to its tubular
feature, it is a function of the screw length. Thus a better understanding of
melt free-radical grafting in the extruder requires not only information at
the exit of the extruder but also point-to-point information within and along
the entire extruder. Only in this way can the effects of chemical and
processing parameters be evaluated properly. This is the reason that, for the
grafting of GMA onto PP, in addition to measuring the GMA grafting
and/or the molecular characteristics of the modified PP at the exit of the die
these quantities are also evaluated at two other positions upstream, located
at 36% and 50% of the total screw length from the feeding point, respectively (Figure 1.4(b. The effects of important chemical and processing
parameters are examined and described in the following five subsections.
Effect of the presence of styrene. Figure 1.19(a) shows the GMA grafting
yields with and without St along the screw length. Being in agreement with
.-/
XQ,.-------------,
1.0..-------------,
0.8
~ 0.6
S
tQ.
02
0.0
(a)
600
''500
o-.-L
~
~Xl
/0-
0.4
Ii 300
200
10
20
15
3)
57
100
40
(b)
10
20
-----
15
Figure 1.19 Compari!!on of the GMA grafting yields, [GMAJ., and the corresponding !,P
molecular weights, Mw with and without styrene: (a) GMA grafting yields, (b) PP Mw'
[GMAl = 3.0 phr; [DTBPIBl = 0.30 phr; feed rate, Q (virgin PP) = 3.5 kgjh; screw
speed = 150 rpm. [StJ./[GMA1: = 1.40 mol/mol; 0 = 0 mol/mol. Subscript i indicates
initial concentration; L = screw length; D = screw diameter. Reproduced with permission from
Sun, Y.-J., Hu, G.-H. and Lambla, M., Journal of Applied Polymer Science, 57, 1043-54;
published by John Wiley & Sons, Inc., New York, Copyright 1995 John Wiley & Sons, Inc.
the GMA grafting in the batch mixer, grafting yields are low (the order of
10%) when GMA alone is grafted onto PP. Addition of St brings about a
significant increase in the GMA grafting yields: they are multiplied by a
factor of about 3. At the same time, the PP molecular weight reduction is
much less pronounced (Figure 1.19(b)): the Mw of the modified PP without
St is 220000 gjmol and is raised to 350000 gjmol in the presence of st. In
other words, there is a 130000 gjmol difference between the GMA alone and
the GMAjSt-modified PP in terms of Mw' Correspondingly, these two
modified PP should have different physical, mechanical and rheological
properties.
Also, the GMA grafting yield reaches a plateau beyond a certain screw
length downstream: more than 70% of the ultimate GMA grafting yield is
achieved by the first sampling point (36% of the total screw length
downstream from the hopper, or a length-to-diameter ratio, LjD, of 15.5).
Almost 100% of the ultimate grafting yield is obtained in the second
sampling point (halfway downstream from the hopper, LjD = 21). In other
words, in addition to accomplishing solids conveying, melting and homogenisation, the first half screw is already long enough for the grafting yield
to reach its ultimate value. Because grafting should not occur in the
solids-conveying zone, it should take place primarily in the melting zone.
Note that the ultimate grafting yield is far below 100%: even in the presence
58
of St, only about 30% of the total GMA is grafted onto PP. The limited
grafting yield is dictated by the concentration of the primary free radicals:
this concentration decreases considerably along the screw length as the
temperature is 200C in the first zone between the feeding point and the first
sampling point and the corresponding halflife of the peroxide used
(DTBPIB) is only about 30 s. The decrease in the concentration of the
primary free radicals should be more abrupt beyond the first zone, because
the barrel temperature is raised to 240C after the first sampling point.
Consequently the halflife of the peroxide is reduced to 2 s. As a result, most
of the free-radical grafting has proceeded in the first zone, which encompasses the melting zone. This implies that free-radical grafting in a screw
extruder is not necessarily characterised by the whole screw length
(LID = 42) or the overall residence-time distribution (between the hopper
and the exit of the die). It must be related to the residence time in the first
zone, in which free radicals are not depleted completely. The length of this
zone is determined by the rate of decomposition or roughly the lifetime of
the peroxide under the processing conditions. Put another way, for a
particular zone of interest, if the concentration of the primary free radicals
at the exit of this zone is literally greater than zero, the GMA grafting yield
will be affected by the residence-time distribution therein. On the other
hand, if the primary free radicals are totally depleted before exiting this zone,
the residence-time distribution in this particular zone may not have any
impact on the GMA grafting yield. In this case, the grafting yield measured
at the exit of the extruder may no longer be an indication of the effect of a
processing parameter.
The existence of a plateau for the GMA grafting yield as a function of
screw length in the extruder is analogue to the existence of a plateau for the
GMA grafting yield as a function of mixing time in the batch mixer. In the
batch mixer, the grafting is completed within less than 2 or 3 min, which
corresponds approximately to the lifetime of the peroxide. In the extruder,
the grafting is virtually finished in the first half of the total screw length. The
mean residence time in this part of the extruder is about 2 min, which is also
in the same order of magnitude as the lifetime of the peroxide. This analogy
implies that, basically, the performance of a particular melt free-radical
grafting system is dictated by two critical parameters: the rate of melting and
the lifetime of the peroxide under real free-radical grafting conditions,
regardless of the type of reactor (batch mixer or screw extruder).
Unfortunately, the rate of melting and the lifetime of the peroxide are
difficult to estimate under practical processing conditions. Thus it is often
difficult to quantify the effects of chemical and processing parameters on the
performance of a particular free-radical grafting system. This is particularly
true in a screw extruder. An alternative that we propose is to choose a
segmental screw length such that the concentration of the primary free
radicals at the exit of this zone is not zero. In practice, the end of this zone
59
0.5..-----------------,
/;~
0.4
:E'
..s
0.3
S2.
0.2
.~O
0.1
0.0
10
20
30
40
15
Figure 1.20 Effect of adding St on the amount of homopolymer or copolymer of GMA,
[GMAJ p , during the free-radical grafting of GMA onto St onto a stabilised and porous PP in
the extruder. [Stll[GMA]; = 1.4 mol/mol; [DTBPIB]; = 0.30 phr; feed rate, Q (virgin
PP) = 3.5 kg/h; screw speed, N = 150 rpm. Barrel setting temperature profile: 200C between
the hopper and the first sampling point; 230C between the first and second sampling points;
240C between the second sampling point and the die exit. Initial concentration of GMA,
[GMA];, by presence of St: = 3.0 phr, no St; = 1.4 phr, no St; 0 = 3.0 phr, with St;
o = 1.4 phr, with St. Subscript i indicates initial concentration; L = screw length; D = screw
diameter. Reproduced with permission from Sun, Y.-J., Hu, G.-H. and Lambla, M., Journal of
Applied Polymer Science, 57, 1043-54; published by John Wiley & Sons, Inc., New York,
Copyright 1995 John Wiley & Sons, Inc.
should be so chosen that the objective function (grafting yield, for example)
at this location is sensitive to changes in the processing parameters of
interest. In our cases, this zone is between the feeding point of the grafting
system (PP, monomers and peroxide) and the first sampling point. This
zone will subsequently be called the target zone. In the present case, it may
be extended to the second sampling point.
In addition to a highly increased grafting yield of GMA and reduced PP
chain degradation, the presence of St suppresses the amount of the
homopolymer and/or copolymer of GMA, [GMAJ p (Figure 1.20). This
implies that when St is added, styrenic radicals attached to PP react with
GMA more rapidly than do PP macroradicals, generating more grafted
GMA and reducing the yield of polymerised GMA.
Effect of the concentration of the peroxide. The GMA grafting yield
increases with increasing DTBPIB concentration (Figure 1.21(a)). Actually,
an increase in the DTBPIB concentration serves to raise the plateau value
60
1.5
tS2.
(a)
1.0
I "'-----
nD,----------------------,
0.5
20
L
I5
(b)
Figure 1.21 (a) GMA grafting yield, [GMA]., and (b) average molecular weight, Mw , of the
GMA/St-modified PP along the screw length at various initial DTBPIB concentrations.
[GMA]j = 3.0 phr, [St]j[GMAl = 1.40 mol/mol; feed rate, Q = 3.5 kg/h; screw speed,
N = 150 rpm. Barrel setting temperature profile: see Figure 1.20. [DTBPIB1: l::,. = 0.70 phr;
D = 0.50 phr; 0 = 0.30 phr. Subscript i indicates initial concentration; L = screw length;
D = screw diameter. Reprinted with permission from Sun, Y.-J., Hu, G.-H. and Lambla, M.,
Journal of Applied Polymer Science, 57, 1043-54; published by John Wiley & Sons, Inc., New
York, Copyright 1995 John Wiley & Sons, Inc.
of the GMA grafting yield. This finding is in line with the above argument
that the limited GMA grafting yield is related to a limited concentration of
primary free radicals. This result also agrees with what is found in the batch
mixer. The molecular weights of the modified PP samples are shown in
Figure 1.21(b). As expected, an increase in the peroxide concentration causes
a further decrease in the PP molecular weight.
Effect of the initial GMA concentration. At a particular DTBPIB
concentration (0.3 phr) with a constant ratio of [StJ;/[GMAl of 1.40
mol/mol, both the GMA and the St grafting yields increase (Figure 1.22(a))
with increasing [GMAl and their conversions decrease. Moreover, the PP
degradation is less pronounced when increasing initial GMA concentration
(Figure 1.22(b)). This implies that, indeed, increasing the grafting is an
effective way of reducing PP degradation (Figure 1.22(b)). This dependence
on initial GMA concentration of the Mw of the GMA/St-modified PP is
different from the case of the PP/MA/St system. In this latter case, the Mw
of the modified PP tends to decrease with increasing initial MA concentration (Figure 1.12).
To sum up, as far as the effects of the three chemical parameters (addition
of St, peroxide and GMA concentrations) in the extruder are concerned,
61
./
12~---------------------,
0.9
I: I
:i
-S
(a)
eoo
~ _ _ _ _ _o
I/O
0.0
~~--------------------,
eoo
Ii 400
0 ____
3D
[GMA\ (phr)
200
(b)
10
Zl
1..
31
<40
Figure 1.22 (a) GMA grafting yield, [GMA]g, and (b) average molecular weight, Mw of the
GMA/St-modified PP and as a function of the initial GMA concentration. [St];/
[GMAl = 1.40 mol/mol; [DTBPIBl = 0.30 phr; feed rate, Q = 3.5 kgjh; screw speed, N = 150
rpm. Barrel setting temperature profile: see Figure 1.20. Figure 1.22(a): = GMA; 0 = St.
Figure 1.22(b):. = a [GMAl of 1.4 phr; 0 = a [GMAl of 3.0 phr. Subscript i indicates initial
concentration; L = screw length; D = screw diameter. Reproduced with permission from Sun,
Y.-J., Hu, G.-H. and Lambla, M., Journal of Applied Polymer Science, 57, 1043-54; published
by John Wiley & Sons, Inc., New York, Copyright 1995 John Wiley & Sons, Inc.
they agree, at least qualitatively, with those observed in the batch mixer.
This is because the grafting rate as well as the ultimate grafting yield are
controlled by the same fundamental parameters: the concentration and the
lifetime of the peroxide employed, regardless of the type of reactor (batch
mixer or screw extruder) in which the GMA grafting is carried out. In a
screw extruder, the lifetime of the peroxide dictates the residence time and
consequently the screw length necessary for reaching the ultimate grafting
yield. If the lifetime of the peroxide exceeds the overall residence time
available in the extruder, the total screw length will not be long enough for
the grafting yield to reach its ultimate value. In this case, the grafting yield
at the exit of the extruder will depend on processing parameters that affect
residence time. On the other hand, if the lifetime of the peroxide is shorter
than the overall residence time available in the extruder, only part of the
total screw length will be needed for the grafting yield to reach its ultimate
value. In this case, the overall residence-time-related processing parameters
may not affect the ultimate grafting yield any more.
In principle, the lifetime of peroxide (St I/2 ) should be used as a first guide
to estimate the residence time necessary for obtaining a desired grafting
yield. This will then allow one to define an adequate extrusion window for
melt free-radical grafting. In practice, an adequate extrusion window can be
quite large. This is particularly so with a modular twin screw extruder. In
62
this case, the residence time can be adjusted by numerous processing

parameters: screw profile, barrel temperature profile, screw speed, throughput and even sidestream addition. This is the reason that twin screw
extruders have gained widespread applications in melt free-radical grafting.
As pointed out before, the co-rotating self-wiping twin screw extruder
used here is always starved fed. Thus screw speed (N), feed rate (Q) and
specific throughput (Q/N) are independent. With particular screw and
temperature profiles, variation in N or Q affects both macromixing, characterised by residence-time distribution, and micromixing. Micromixing is
related to the intimate contact between reactive species. In general,
residence-time distribution is shifted to a short time domain when N or Q
increases. On the other hand, mechanical mixing increases with increasing
N or decreasing Q. Therefore, for a particular reaction, it is often difficult
to know whether the effects of Nand Q are exerted by residence
time, mechanical mixing, or both. In the next subsection the effects of N,
Q and Q/N on the GMA grafting will be examined upon choosing a
given composition: [GMAJj = 1.4 phr, [StJj/[GMAJj = 1.40 mol/mol and
[DTBPIBl = 0.30 phr.
Effect of screw speed (N) or feed rate (Q). The GMA grafting yields
along the screw length at two different screw speeds (150 rpm and 240 rpm)
with a given feed rate (for PP this is 5.6 kg/h) are shown in Figure 1.23.
0.5
0.4
:E'
0.3
0.2
=-'
0.1
0.0
10
20
30
D
Figure 1.23 Grafting yield of GMA, [GMA]g, along the screw length at two different screw
speeds for a given PP feed rate of 5.6 kgjh. Screw speed: = 150 rpm; 0 = 240 rpm; L = screw
length; D = screw diameter. Reproduced with permission from Sun, Y.-J., Hu, G.-H. and
Lambla, M., Journal of Applied Polymer Science, 57,1043-54; published by John Wiley & Sons,
Inc., New York, Copyright 1995 John Wiley & Sons, Inc.
63
0.6,------------,
0.5
0.4
S 0.3
'?;0Il
~
0.2
0.1
O.OCl"-~-_r_-~__r-~___r-~-r_'
10
20
40
D
Figure 1.24 Grafting yield of GMA, [GMA]g, along the screw length at various feed rates of
PP for a given screw speed (90 rpm). PP feed rate: 6 = 2.1 kg/h; 0 = 3.4 kg/h; 0 = 5.6 kg/h;
L = screw length; D = screw diameter. Reproduced with permission from Sun, Y.-J., Hu, G.-H.
and Lambla, M., Journal of Applied Polymer Science, 57,1043-54; published by John Wiley &
Sons, Inc., New York, Copyright 1995 John Wiley & Sons, Inc.
They are consistently higher at the lower screw speed (150 rpm) than at the
higher screw speed (240 rpm). The GMA grafting yields along the screw
length at three different feed rates for a given screw speed (N = 90 rpm) is
shown in Figure 1.24. With increasing Q, the GMA grafting yield at a
particular location of the screw decreases.
The above results indicate that there is an equivalence between an
increase in N and an increase in Q because both bring about a decrease in
the GMA grafting yield. An increase in N or Q shortens the residence time
in the target zone. On the other hand, an increase in N enhances mechanical
mixing intensity whereas an increase in Q reduces it. Thus, the equivalence
in terms of the grafting yield between Nand Q can only be conciliated
through residence time in the target zone - local residence time. In other
words, the local residence time is the primary parameter that affects the
overall performance of the extruder with respect to free-radical grafting. The
effects of Nand Q on the free-radical grafting are exerted mainly through
changes in the local residence time; variations in mechanical mixing intensity are apparently unimportant.
Effect of specific throughput (QIN). In order to support further the
argument that residence time is the key parameter that controls the overall
grafting yield, the effect of specific throughput is examined. Specific throughput is defined as the ratio of throughput to screw speed, Q/N. As discussed
64
elsewhere [3, 53], it is measured in kg/turn of screw speed and it measures,

to some extent, the pumping capacity of a particular twin screw extruder:
the amount of material each turn of the screw can pump. It also characterises the degree of fill of the twin screw extruder for partly filled zones. The
reciprocal of Q/N, N /Q, is measured in screw turns/kg and can be viewed as
the number of screw rotations a unit material has experienced. Thus, it
measures the intensity of mixing the material has experienced through the
partly filled zones. If the pressure flow in a twin screw machine owing to the
die and/or other pressure consumers is unimportant, Q/N and N /Q are
expected to characterise the degree of fill and the intensity of mixing of the
overall machine, respectively. If so, unlike a change in Q or N which affects
not only macromixing but also micromixing, variations in Q and N at the
same time for a particular value of Q/N will change residence-time distribution only. The residence-time distribution functions f(t) as a function of
time for three different throughputs and screw speeds at a given value of
Q/N
kg/h/rpm) are shown in Figure 1.25(a). The corresponding dimensionless residence distribution functions f(r) as a function of dimensionless
time -r (time divided by the mean residence time, t/i) are shown in Figure
1.25(b). The f(t) curve is shifted to a short time domain when Q and N are
increased (Figure 1.25). Interestingly, the three f(t) versus t curves in Figure
1.25(a) superimpose well when they are converted to the f(-r) versus -r form
a3
0.016
..\
~
I.
0.012
~
I"
...
2.5
(a)
IJ\,
P... 000
I
150
:m
450
Time(s)
II
~
1.0
0.5
!.
0\
0.000
1.5
f~. ~A~
$,
0.004
~8
1.0
\00
O.IUI
II
II
2.0
II
II
tII
tn
,~.
II
-llll II
-Em
0.0
0.0
750
(b)
0.5
1.0
1.5
2.0
2.5
3.0
't"
Figure 1.25 The residence-time distribution function as a function of time for three different
throughputs and screw speeds with a particular throughput (Q/N of -A kg/h/rpm). Polymeric
fluid: polystyrene. (a) Residence-time distribution as a function of time, t(f(t, and (b)
residence-time distribution as a function of time t divided by the mean residence time t (f(t .
= 5.6 kg/h throughput, 240 rpm screw speed; 0 = 3.5 kgfh throughput, 150 rpm screw
speed; f:::,. = 2.1 kg/h throughput, 90 rpm screw speed. Reproduced with permission from Sun,
Y.-J., Hu, G.-H. and Lambla, M., Journal of Applied Polymer Science, 57, 1043-54; published
by John Wiley & Sons, Inc., New York, Copyright 1995 John Wiley & Sons, Inc.
65
0.5,--------------,
0.6
0.4
':f
~
0.5
-c..c:
.3
0.3
0.4
':f 0.3
0.2
:::!:
~ 0.2
0.1
10
20
(a)
30
75
(b)
Figure 1.26 GMA grafting yields, [GMA]., at various screw speed and throughputs for given
and (b) Q/N =A Screw speed. .6. = 90 rpm; 0 = 150
specific throughputs, Q/N, (a) Q/N =
rpm; 0 = 240 rpm; L = screw length; D = screw diameter. Reproduced with permission from
Sun, Y.-J., Hu, G.-H. and Lambla, M., Journal of Applied Polymer Science, 57, 1043-54;
published by John Wiley & Sons, Inc., New York, Copyright 1995 John Wiley & Sons, Inc.
tr,
(Figure 1.25(b). This supports the above argument that mechanical mixing
intensity and associated longitudinal flow pattern (longitudinal micromixing) do not vary much upon varying Q with a concomitant change in N for
a particular value of Q/N, and only residence-time distribution (macromixing) changes.
The GMA grafting yields along the screw length at three different screw
speeds for two given Q/N ratios U7 and 413 kg/h/rpm) are shown in Figures
1.26(a) and 1.26(b). When the ratio Q/N is constant, the GMA grafting yield
increases with decreasing Q and N as a result only of longer residence times
in the zone of temperature 200C.
1.5.4 Mechanisms of melt free-radical grafting
In what preceded, the melt free-radical grafting of MA and GMA onto PP
carried out in a batch mixer and a twin screw extruder was addressed. From
the viewpoint of chemistry, the intrinsic free-radical grafting reactivity of
both monomers is weak: their conversion rarely exceeds 15% under normal
melt grafting conditions. It has been shown clearly that addition of St as a
co-monomer greatly promotes their grafting reactivity: their conversion is
increased by a factor of 3 to 5.
But how does St promote the grafting reactivity of MA and GMA? Is it
by the same mechanism that St promotes the grafting reactivity of both
monomers? Which monomer is grafted first onto the PP chain? Are grafts
66
long or short, alternated or random? Questions can go on! Below is some

experimental evidence that may help shed light on these questions and
eventually raise more questions.
(a) The MAjSt system. It has been implicitly stated before that the great
contribution of St to the MA grafting onto PP originates from the
activation of the double bond of MA by St upon formation of a CTC.
Important supporting evidence is that electron-donating co-monomers that
interact with MA most strongly at room temperature give the highest MA
grafting yields (Figures 1.7 and 1.8). For example, St is an electron-donating
monomer with which MA interacts the most. It is also the one that leads to
the greatest improvement in MA grafting yield.
The presence of eTC at normal melt grafting temperatures. If the
formation of the CTC is indeed responsible for the accrued MA grafting
reactivity, one has to prove that the CTC exists not only at room temperature but also at the actual grafting temperatures, close to 215C. Therefore,
one needs to know how the equilibrium of the CTC formation shifts upon
varying temperature. Interestingly, the equilibrium constant for the CTC
formation between MA and St is as a weak function of temperature, as
revealed by 1 H NMR in a de ute rated decahydronaphthalene solution
(Table 1.17). Note that as opposed to CDCI 3 , deuterated decahydronaphthalene does not interact with the MAjSt system. Thus, the values obtained
characterise the true equilibrium constant Ks of the MAjSt system. If the
experimental data generated at low tempertures (22C-120C) can be
extrapolated to normal melt grafting temperatures (200C-220C), then
about 3.5% of the total MA is in the CTC form for a mixture composed of
0.1 M MA and 0.1 M St (or approximately 1 phr MA in the molten PP), and
about 14% of the total MA is in the CTC form for a mixture composed of
0.5 M MA and 0.5 M St (corresponding roughly to 5 phr MA in the molten
PP). This means that when St is present there is indeed a small fraction of
MA which is in the CTC form at normal melt grafting temperatures. But
the question remains as to whether this amount of CTC is high enough to
explain the contribution of St to MA grafting.
Table 1.17 Equilibrium constants of the CTC formation between

MA and St at various temperatures. Those at 22C, 70C and 120C
are experimental data and those at 200C and 220C are extrapolated
data based on the following equation: In K, = -I1SIR + I1HIRT
K, (lImo))
22
70
120
200
220
0.59
0.48
0.45
0.38
0.37
67
Table 1.18 Compositions of the MA and St grafts onto a stabilised PP in the

presence of DTBPH and a non-stabilised PP without externally added
peroxide. 0.5 phr DTBPH, temperature = 215C; reaction time = 15 min. The
compositions of the MA and St grafts are obtained with FTIR and/or 1 H
NMR
Initial MA/St composition:
[MAJ; (phr)
[St]; (phr)
[StJ)[MA]; (moljmol)
[MAcTcJ/[MAJ; (%)
Stabilised PP:
[MAJg (phr)
[StJg (phr)
[StJg/[MAJg (moljmol)
Non-stabilised PP:
[MAJg (phr)
[StJ g (phr)
[StJg/[MAJg (moljmol)
2.00
2.55
1.20
2.8
4.00
5.09
1.20
5.4
6.00
7.64
1.20
10.1
8.00
10.19
1.20
18.0
10.00
12.73
1.20
24.3
1.10
1.60
1.46
1.60
2.40
1.42
2.00
2.60
1.20
2.70
4.20
1.49
3.30
4.80
1.37
0.74
1.34
1.23
0.87
1.78
1.23
0.50
1.90
1.57
0.50
1.78
1.52
0.52
1.68
1.10
The role of eTC in improving MA grafting. If the grafting species are

exclusively the CTC species and if free MA molecules do not participate in
the grafting one would expect two consequences. First, the molar ratio of
the grafted St and MA, [StJJ[MAJ g, should always be one, regardless of
the initial molar concentrations of St and MA. Second, for a particular MA
concentration, the MA grafting yield should increase with increasing St
concentration because of the increase in CTC formed.
The first expectation does not agree with experimental results. For
example, when MA/St mixtures with a particular molar ratio [StJJ[MAJj
of 1.2 are charged to the semi-open batch mixer, the molar ratios [StJ g /
[MAJ g are, on average, 1.36 (Table 1.18). This is true not only for the
stabilised PP grafting system in the presence of DTBPH but also for the
non-stabilised PP grafting system without externally added peroxide, regardless of the initial MA and St concentrations. In other words, the value
ofthe ratio [StJg/[MAJ g is not 1.0 - the theoretically predicted value based
on the assumption that only the CTC species participate in the grafting
process. In fact, the ratios are closer to 1.5 in value considering the fact that
the loss of St is more important than that of MA in the batch mixer at
220C. This means that in addition to the MA/St CTC species, the free MA
and St molecules must also participate in the grafting. Moreover, free St
molecules should be more reactive than free MA molecules. In fact,
considering the observed molar ratio [StJg/[MAJ g of 1.5, one tends to
speculate that among all the St species that have participated in the grafting,
half are in the CTC form and the other half are free molecules. As for the
grafted MA units, they originated solely from the CTC species.
The second expectation is not in line with the experimental results either.
For example, for a given initial MA concentration of 4.0 phr, the MA
68
REACTIVE MODlFlliRS FOR POLYMERS
o
~ 5
o4
"0
Qi
.s;.
g3
(!J
[Stl;
[MAli (mol/mol)
Figure 1.27 Composition of the grafts onto a powdery and stabilised PP and the ratio of
grafting yields, [St]./[MA]., as a function of the ratio of initial concentrations [St];/[MA]i for
a particular MA concentration (4 phr). [DTBPH] = 0.5 phr; temperature = 215C; reaction
time = 15 min. 0 = [St].; 6. = [St]./[MA].; D = [MA].; .--- -. = the experimental-value
"curve" for the ratio [St]./[MA]. for the assumption to hold that only the charge transfer
complex species participates in the grafting process.
grafting yield does not always increase with increasing St concentration (the
molar ratio [St];/[MA]; varies from 0.25 to 3.0). Instead, it goes through a
maximum when the molar ratio [St];/[MA]; is somehow between 1.0 and
2.0 (Figure 1.27). On the other hand, the St grafting yield always increases,
virtually linearly, with increasing St concentration. As far as the molar ratio
[St]g/[MA]g is concerned, it also increases with increasing St concentration.
The magnitude of increase seems to increase with increasing St concentrations. The dashed line in the figure corresponds to the molar ratio [St]g/
[MA]g being equal to 1.0. This value is respected if the assumption that only
the CTC species participate in the grafting process holds. The experimental
value of [St]g/[MA]g is below this dashed line when the value of the
[St];/[MA]; ratio is below approximately 0.6. It is above this dashed line
when the value of [St];/[MA]; exceeds 0.6. These results are in line with the
above statement that, apart from the CTC species, the free St molecules
should also have participated in the grafting process. Obviously, the
participation of free St molecules becomes more important with increasing
initial St concentration.
The microstructure of MA and St grafts. It is not easy to probe the

microstructure of grafts because they usually weigh less than 5% in the PP.
69
Difficulties are better appreciated upon taking as an example a highly

grafted PP obtained with a mixture of 10.0 phr MA, 12.73 phr St and 0.5
phr DTBPH at 215C for 15 min. Under these grafting conditions, about
24% by mole of the total MA would be in the CTC form at the beginning
of the reaction. The resulting PP has a number average molecular weight of
47000 g/mol bearing 4.2wt% St and 2.7wt% SA, corresponding to a
mixture of St to MA of 60 to 40 by mole. Even with this highly grafted PP,
there are only about 16 units of SA and 22 units of St per PP chain (1120
units of propylene).
The DSC curve of this grafted PP does not display any significant
differences from that of the virgin PP. The melting peak and the crystallinity
of the virgin PP are almost undisturbed by grafting. The only visible
difference lies in the fact that the grafted PP starts melting earlier than the
virgin PP possibly owing to the presence of shorter PP chains. Thus, it can
be said that DSC is not sensitive to the SA and St units present in the PP.
This insensitivity of the DSC is obviously related to too low a weight
percentage of the SA and St grafts. It also implies that there would be a lack
of long SA and St grafts onto PP. Otherwise, DSC would have detected
their presence (6.9 wt% of St and MA grafts) and the crystallinity of the
virgin PP would have been decreased.
13C and 1H NMR are supposed to be best suited for characterising the
microstructure of the SA and St grafts onto PP. Figure 1.28 shows the 13C
NMR (200 Hz) spectrum of the grafted PP obtained in a deuterated
tetrachloroethane solution containing 10% wt per volume of the PP at
115C after 1200 scans for a period of 10 s. When compared with the
spectrum of a copolymer of St and MA (1: 1 molar ratio), denoted as SMA,
this grafted PP spectrum displays, in addition to the three peaks characteristic of PP (at 21 ppm, 29 ppm and 48 ppm), a small peak between 126 ppm
and 132 ppm. This small peak corresponds to the five non-quaternary
aromatic styrenic units. However, the peaks of the quaternary carbon C 1 of
the grafted styrenic units (136-148 ppm) as well as those of the carbonyl
carbons (171-174 ppm) are not seen. Because of the fact that these peaks are
the basis for estimating the sequence distribution of MA and St monomers
in their copolymers, their absence in the MA and St grafted PP does not
allow for any evaluation of the microstructure of the grafts by 13C NMR.
Examine now the sensitivity of 1H NMR to the microstructure of the SA
and St grafts in the above-mentioned PP. Figure 1.29 shows the 1H NMR
(200 Hz) spectrum of the grafted PP obtained in a deuterated tetrachloroethane solution at 120C after 3000 scans collected within a period of
10 s. The spectra of three SMA copolymers (Copos A-C) of different
compositions are also shown for comparison (Table 1.19). Inspection of
these four spectra shows that, apparently, the 1H NMR spectrum of Copo
B is the closest to that of the grafted PP. Nevertheless, it is difficult to make
a valid conclusion based simply on this visual comparison.
70
....
t5
o'"
'"
()
PP-g-(St-co-MA)
'E
~
o
en
SMA 1:1
180
160
140
120
100
80
60
40
20
ppm
Figure 1.28 Comparison of the PP-g-(St-co-MA) NMR 13C spectrum at 11SoC with that of an
SMA copolymer (St: MA = 1: 1 by mole) reported in the literature.
In order to compare the MA and St grafts onto PP with the SMA

copolymers on a more quantitative basis, Mochel's method [62,63] is
adopted. According to this method, the aromatic region of the 1 H NMR of
an SMA copolymer is composed of three peaks: two of them correspond to
the sequential styrenic units and the third one to the isolated styrenic units.
The percentages of the sequential and isolated styrenic units of the grafted
PP as well as the three SMA copolymers are evaluated by this method and
the values are reported in Table 1.20. It is found that, indeed, the micro-
71
...
5
o
C\I
C\I
()
8.4 8.2
8.0
7.8
7.6
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8 5.6
ppm
Figure 1.29 Comparison of the PP-g-[St-co-MA) NMR lH spectrum with those ofthree SMA
copolymers, Copos A-C.
structure of the MA and St grafts onto PP is the closest to that of Copo B,

with approximately half of the total styrenic units sequential and the other
half isolated. It infers that the molar ratio [StJg/[MAJ g of this grafted PP
should be approximately 1.5. Interestingly, this value corresponds to the one
deduced from the results obtained by FTIR and 1 H NMR measurements
(Table 1.18). This agreement tends to suggest that when the molar ratio
[StJd[MAJi is 1.2, half of the grafted St originates from the CTC species
and the other half from the free St molecules under the above-mentioned
grafting conditions, regardless of the initial MA and St concentrations.
Nevertheless, one has to be careful about the applicability of Mochel's
theory for short SA and St chains (less than 5 monomer units for example).
Table 1.19 Overall compositions and sequence distributions of three different SMA copolymers
(Copos A-C)
CopoA
Copo B
CopoC
MA(%)
St (%)
SSS (%)
MSS (%)
38
31
28
62
67
2
20
43
29
32
23
72
Source: Buchak, B.E. and Ramey, K.C. (1976) J. Polym. Sci., 814, 401.
SSM (%) MSM (%)

29
32
23
39
13
12
72
Table 1.20 Percentages of the sequential and isolated styrenic units present
in three SMA copolymers (Copos A-C) and the grafted PP. Data in
parentheses correspond to those determined by Buchak and Ramey using
13C NMR
Sequential St (%)
Isolated St (%)
Copo A
Copo B
Copo C
Grafted PP
37 (61)
64 (39)
47 (87)
53 (13)
54 (88)
46 (12)
48
52
Reactivity of St towards PP macroradicals and MA. Considering the

fact St has a greater free-radical grafting reactivity than MA when they are
grafted separately onto PP, it is plausible that in the case of a mixture of
MA and St, the latter, whether in free or complexed form, would be expected
to have a much greater probability to react first with PP macroradicals.
The fate of ungrafted MA and St molecules. In practice, more than half
of the initial MA and/or St molecules are not grafted onto PP in a normal
MA grafting process in the batch mixer. The experimental approach
described below helps to illustrate the fate of ungrafted MA and St.
Let us examine an MA/St-modified PP sample obtained in the batch
mixer under typical grafting conditions at 215C, with a mixture of a
stabilised PP, 10 phr MA, 12.7 phr St and 0.5 phr DTBPH. This PP sample
is dissolved in xylene under reflux and then precipitated in a large excess of
acetone. After removal of the precipitated PP, the solution containing MA
and St residues in a mixed solvent of xylene/acetone (20: 80) is concentrated.
A white powder is then obtained. This white powder is soluble in acetone
but not in xylene. Below are results revealed by FTIR and SEC about this
white powder.
The FTIR spectrum of the white powder is shown in Figure 1.30 together
with that of a copolymer composed of 44% by mole MA and 56% by mole
St, for comparison. Inspection of both spectra show that they are identical.
This leads to the conclusion that this white powder is a copolymer.
Moreover, it does not contain short PP chains. A quantitative analysis of
this copolymer by FTIR shows that it contains 38% MA and 62% St by
mole. This composition corresponds to a molar ratio [St]/[MA] of 1.6, a
value close to 1.5. This indicates that this copolymer formed during grafting
is not stoichiometric as far as the molar ratio [St]/[MA] is concerned.
Similar to the overall composition of the SA and St grafts onto PP, the
copolymer is also richer in St units than it is in SA units. Is this similarity
in terms of the overall SA and St composition between the grafts and the
copolymer a pure coincidence or something else?
The molecular weight of the copolymer formed during the grafting, as
measured by SEC, ranges from 10 3 g/mol to 106 g/mol. A fractionated SEC
73
4000
3490
2980
2470
1960
1450
940
430
Wavenumbers
Figure 1.30 Comparison of the FTIR spectrum of the white powder with that of an SMA
copolymer (St: MA = 56: 44 by mole). See page 72, for a description of how the white powder
was obtained.
analysis of this copolymer shows that more St units are found in the domain
of smaller molecular weights. The relatively high molecular weight of this
copolymer may cast doubt about our belief that the SA and St grafts onto
PP are short and composed primarily, if not exclusively, of single SA and
St moieties. This is because there are, a priori, no reasons that the length of
the SA and St grafts would be different from that of the copolymer.
Nevertheless, one should keep in mind that the length of grafts depends not
only on the thermodynamics of the system characterised by ceiling temperature (Section 1.3.1(b), but also on the ratio kH/kgp (in the beginning of
Section 1.2). This ratio measures the relative importance between the rates
of intramolecular and/or intermolecular macro radical transfer and of monomer addition to macroradicals. If this ratio is high, the graft length should
be short, and vice versa. Owing to the high free-radical reactivity of the
tertiary hydrogen atoms of PP, this ratio can be high.
From the above discussion, it can be concluded that for a mixture of MA
and St there is indeed a small fraction of MA which is in the form of the
eTC at normal melt grafting temperatures. Moreover, apart from the eTC
species, free MA and St molecules also participate in the grafting process.
The grafting process of the free MA and St molecules should follow the
74
classical principles of copolymerisation - that is, be determined by reactivity

ratios - yet at much higher temperatures. However, the relative importance
between the CTC species and the free MA molecules in the overall grafting
process remains a puzzle. On the one hand, one may argue that, although
only a small percentage of MA is in the CTC form in the normal MA and
8t concentration range at normal melt grafting temperatures, it should be
emphasised that there is an equilibrium between the CTC species and the
free MA and 8t molecules. This equilibrium can be established so rapidly
that the free MA and 8t molecules can constantly compensate for the
amount of the highly reactive CTC species grafted onto PP chains. In fact,
one should also keep in mind that if all the CTC species formed during the
whole grafting process of an MA and 8t mixture were grafted, then the
ultimate MA grafting yield should be smaller than the initial CTC concentration. For example, if the ultimate MA grafting is 50%, then the initial
percentage of MA in the CTC form should be smaller than this value.
Otherwise the contribution of the CTC will be inexplicable. This is because
the final amount of the CTC formed should be greater than its initial
amount owing to the equilibrium shift in favour of the CTC as grafting
proceeds. On the other hand, one may also argue that, because the total
amount of the CTC formed during the grafting is largely unknown, doubt
still remains about the contribution of this small fraction of the CTC species
to the overall MA grafting. In any event, if the contribution of the small
fraction of the CTC is truly unimportant, the crucial role that 8t plays in
the MA grafting then has to be explained by the classical copolymerisation
principles - that is, by the reactivity ratio. At this point, we realise that
controversy also persists in the literature concerning the participation of the
CTC in the copolymerisation of MA and 8t. Thus, considering all that has
been said about the importance of the formation of the CTC in the MAj8t
grafting, further debate on this subject would become purely philosophical.
(b) The GMAjSt system. When the GMA monomer alone is grafted onto
PP, the resulting GMA grafting yields are low owing to the low reactivity
of GMA towards PP tertiary macroradicals. The original approach to solve
the problem is to use a co-monomer (8t) which is more reactive towards the
PP macro radicals. The resulting macroradicals (styryl) are then capable of
reacting with the GMA monomer. In this way, instead of grafting GMA
directly onto PP chains, the co-monomer (8t) serves as a mediator to bridge
the gap between the PP macro radicals and GMA monomer. This approach
is based on the classical copolymerisation principles involving reactivity
ratios. Despite its great success, the validity and generality of this approach
should be questioned.
Are there any specific interactions (CTC) between GMA and St? If the
free-radical grafting of the GMAj8t system is indeed dictated by classical
75
copolymerisation principles, one should ascertain that there are not any
specific interactions of CTC type between GMA and St. Analysis of GMA
and St mixtures of various weight proportions by 1 H NMR and EPR shows
that unlike the MA/St system in which MA and St form a CTC, there are
no specific interactions between GMA and St between room temperature
and 120C, as expected.
What is the effect of adding rx-MeSt, a derivative of St? Unlike the
addition of St, addition of rx-MeSt does not improve the GMA grafting yield.
This is surprising at first glance. One may wonder why the presence of St
improves the GMA grafting yield but not the presence of its derivative,
rx-MeSt. This is because unlike St rx-MeSt is less reactive than GMA with
respect to the tertiary PP macro radicals. Thus it cannot play the role a
mediator monomer should do in promoting the GMA grafting. In fact, the
free-radical grafting reactivity follows the order: St rx-MeSt ~ GMA ~
MA. One may recall that addition of rx-MeSt increases the MA grafting yield
onto PP (Figure 1.8). This is because rx-MeSt, like St, is also a good
electron-donating monomer capable of activating the double bond of MA
upon formation of a CTC (Figure 1.7).
A comparison between the GMA/rx-MeSt and MA/rx-MeSt systems in
terms of the effect of adding rx-MeSt indicates again the importance of the
CTC in the MA/rx-MeSt system. If the CTC were not important for the
MA/rx-MeSt system, addition of rx-MeSt to the PP/GMA system should also
have had a positive effect on the GMA grafting.
All that precedes is in line with the idea that the great contribution of St
to the PP/GMA system originates from its role as a good mediator
monomer. Nevertheless, a problem deserves explanation concerning the
relationship between the ratios [StJd[GMAl and [StJg/[GMAJ g.
Recall that in the case of the MA/St grafting system, the value of
[StJg/[MAJ g in the MA and St grafts is always higher than the value of
[StJd[MAl of the mixture introduced. This is because half of the St is
grafted in the form of the CTC and the other half in the form of free St
molecules. Different results are obtained with the GMA/St grafting system.
In this case, the value of [StJg/[GMAJ g in the GMA and St grafts is always
lower than the value of [StJd[GMA]; of the mixture introduced. An
example for the GMA/St grafting in the batch mixer is shown in Table 1.21.
This relationship between [St]J[GMAl and [StJg/[MAJ g is surprising.
Because of the greater free-radical grafting reactivity of St alone, when
compared with GMA alone, with respect to the tertiary PP macro radicals
one would expect that more St becomes grafted than is the case with GMA.
However, one should not forget that this greater free-radical grafting
reactivity of St alone means that in a mixture of St and GMA the St
molecules are expected to have greater probability of reacting with PP
macroradicals. However, this does not provide any information about the
76
Table 1.21 Relationship between [Stl/[GMAl an [StJ./[GMAJ. for the

GMA/St grafting system in the batch mixer. [GMAl = 6.0 phr; [DTBPH] = 0.2
phr; temperature = 200C; mixing speed = 64 rpm; mixing time = 15 min
[Stl/[GMAl (phr:phr-l)
0.00
0.50
0.80
1.00
1.50
0.00
0.30
0.36
0.40
0.56
composition of St and GMA in the grafts. This is dictated by the reactivity

ratios of the St and GMA systems under real grafting conditions. Under
classical copolymerisation conditions, in which temperature ranges from
60C to 90C, the values of r;: 1 are: 2.41 for the styryl-radicaljGMAmonomer combination, and 1.78 for the GMA-radicaljSt-monomer combination. This means that the tendency for the styryl radical to react with the
GMA monomer is higher than that of the reaction of the GMA radical with
the St monomer. Consequently, the ratio of [StJg/[GMAJ g in the GMA and
St grafts should be smaller than the ratio [St]J[GMAJj. Another fact is
that, unlike the MA/St system in which MA and St form a more bulky CTC,
there are no specific interactions between GMA and St. The loss of St may
become more important from the GMA/St system than it is from the MA/St
system.
Is St a universal comonomer? In the case of MA, St is capable of

activating its free-radical grafting reactivity as a result of the formation of a
CTC. As for GMA, the reactivity ratio between St and GMA is in favour of
an increased free-radical grafting of GMA. This gives the impression that St
is a universal co-monomer for promoting the free grafting of any monomer
onto polymer backbones such as PP. This is unfortunately not the case. For
example, when the reactive monomer, ricinoloxazoline maleinate (OXA),
which bears an oxazoline functionality (Figure 1.31), is used in the grafting
CH=CH
I
I
O=C
C=O
I
I
o 0
I
I
CH CH-CH-CH=CH-(CH )-C~NI
3 I
2
2 7
' 0---.1
H
(T 2\
CH
Figure 1.31 Chemical structure of ricinoloxazoline maleinate (OXA).
77
//:
i~~ f:;;/
1.6
1.4
0.4
to. .---.
0.2 ( /
0.0 '-~--.--~--.--~--.--~-----I
0.0
0.2
0.4
0.6
0.8
[DTBPIBl i (phr)
Figure 1.32 The negative effect of adding St as a co-monomer on the free-radical grafting of
OXA onto a porous and stabilised PP (Himont) in a batch mixer. Temperature =
204C ~ 210C; rotor speed = 64 rpm; COXA]; = 3.0 phr; CSt]; = 0.72 phr (if St added) .
= COXA]. without St; 0 = COXA]. with St; ... = [St] . Subscripts i and g indicate initial
concentration and grafting yield, respectively.
reaction on PP in the presence of St a reduction in the grafting efficiency of

OXA-PP is observed (Figure 1.32). This is because the OXAjSt pair does
not benefit from the CTC mechanism nor from a favourable reactivity ratio.
In the latter case, it means that a styryl macro radical, PPjSt*, is incapable
of reacting with OXA. This has been confirmed experimentally [64]: OXA
does not homopolymerise and it can copolymerise with St only when St is
in large excess with respect to OXA. Moreover, both the conversion and the
molecular weight of the resulting copolymer are low. The above example
shows that St is not a universal co-monomer. More importantly, it points
out that in order for the copolymerisation principle to be effective in
promoting the free-radical grafting of a monomer, not only should the
co-monomer be more reactive toward PP macro radicals than the monomer
to be grafted, but also the co-monomer should co polymerise easily with the
monomer. If the co-monomer fails to meet one of these two conditions, it
will not be efficient.
1.6
Concluding remarks
Despite intensive scientific research and industrial practice, for over 30 years
melt free-radical grafting of monomers onto polymer chains has become
controllable only recently. In the past, the main concern in melt free-radical
grafting was the lack of efficient methods to achieve two opposing
78
requirements: the attainment of a sufficient grafting yield with a minimum

change in molecular architecture of the original polymer substrates. Very
often, attainment of a sufficient grafting yield was accompanied by a drastic
change in molecular architecture and consequently in physical, rheological
as well as mechanical properties of the original polymer substrates. For
example, a large dose of peroxide had to be added to raise the MA grafting
yield onto polyethylene (PE) or polypropylene (PP), thereby causing crosslinking of the PE or molecular degradation of the PP.
It has been learnt that a free-radical grafting process starts with formation of macroradicals upon hydrogen abstraction by primary radicals. These
macro radicals face one of two opposing fates, depending on their own
chemical structure as well as other chemical species (monomers) surrounding them: recombination of macro radicals leading to cross-linking (e.g., PE)
or fragmentation by fJ-scission (e.g., PP) causing chain degradation; or
reaction with monomers leading to grafting. Hence, the effective utilisation
of macro radicals for the sake of grafting must be the only way out to reduce
side reactions responsible for changes in molecular architecture and corresponding physical as well as mechanical properties of the original polymer
substrates. It is also a good way of minimising monomer homopolymerisation.
Two grafting systems of great interest have been described in this chapter
in order to illustrate methods that have been developed in the authors'
Reactive Extrusion Laboratory in which macro radicals are utilised in favour
of grafting reactions. The first one concerns the grafting of maleic anhydride
(MA) onto PP, and the second one the grafting of glycidyl methacrylate
(GMA) onto PP.
The first grafting system is probably the most classical and has been
much documented in the literature. Nevertheless, the problem of low MA
grafting, along with accrued PP chain degradation, persisted for a long time.
Only recently, based on the charge transfer complex (CTC) concept, have
efficient methods been developed that are highly capable of activating the
otherwise weak free-radical reactivity of the double bond of MA. More
specifically, strong electron-donating monomers such as styrene (St) were
shown to be very effective in promoting the MA grafting efficiency. As a
result, high MA grafting yields have been obtained and the PP chain
degradation has been largely reduced. This is true not only in a batch mixer
of a Haake Rheocord type but also in a twin screw extruder of a Werener
Pfleiderer type. More importantly, the MA grafting mechanism in the
presence of St has now been elucidated. The existence of the CTC at normal
grafting temperatures has been clearly confirmed by 1 H NMR. It appears
that the formation of the CTC plays a crucial role in the grafting process.
As far as the GMA grafting system is concerned, it has received much less
attention. Nevertheless, a few studies showed that the GMA free-radical
grafting efficiency is very low and grafting yields rarely exceed 10%.
79
Recently, efficient methods have been developed to solve the problem and
these are based on classical copolymerisation principles, involving reactivity
ratios. The idea is to search for a co-monomer which is more reactive
towards the PP macro radicals. The resulting macroradical is then capable
of reacting with the GMA monomer. In this way, instead of grafting GMA
directly onto PP chains, the co-monomer serves as a mediator to bridge the
gap between the PP macroradicals and the GMA monomer. It turns out
that St is such a mediator monomer. Addition of St has led to a rise in the
grafting efficiency of GMA by a factor of 3 to 5, with limited PP chain
degradation.
It should be noted, however, that addition of a co-monomer is efficient
only when the co-monomer activates the free-radical reactivity of the
monomer in question by some specific interactions (e.g., as in the MA/St
system) or makes the reactivity ratio of copolymerisation favourable for the
free-radical grafting (e.g., as in the GMA/St system). In the latter case, the
co-monomer should meet the following two conditions: it should react with
PP macroradicals more rapidly than does the monomer, and the resulting
radical should copolymerise readily with the monomer. If the co-monomer
fails to meet one of these two conditions, its presence in the grafting system
will be useless. An example is the free-radical grafting of ricinoloxazoline
maleinate (OXA) onto PP. In this case, the presence of St plays a negative
role because, although St reacts with a PP tertiary macro radical much faster
than does OXA, the resulting styryl macroradical (PP/St*) is unable to
copolymerise with OXA.
Finally, because of the high reactivity of the epoxy group towards
numerous other functional groups, the GMA grafting system is expected to
receive much more attention in the future. Some interesting new materials
have been developed in the authors' laboratory, based on GMA modified
polymers.
Appendix I.A
1.A.1
I.A.I.I
AIBN
BCP
BP
BrMA
CDCl3
CPD
CR/PP
DCP
DEM
DMAC
DMEU
DMF
DTAP
DTBHY
DTBP
DTBPH
DTBPIB
EPDM
EPR
GMA
HDPE
HMCN
IBVE
LDPE
LLDPE
M
MA
MAc
oc-MeSt
MMA
NVP
0L12
OXA
Polymers and chemicals

Azo-bis-isobutryonitrile
T-butyl oc-cumyl peroxide
Benzoyl peroxide
Bromo-maleic anhydride
Deuterated chloroform
1,3-Cyclopentadiene
Controlled rheology PP
Dicumyl peroxide
Diethyl maleate
Dimethylacetamide
1,3-DimethyI2-imidazolidinone
Dimethylformamide
Di-t-amyl peroxide
2,5-Di(t-butyl-peroxy)-2,5-dimethylhexyne
Di-t-butyl peroxide
2,5-Di(t-butyl-peroxy)-2,5-dimethylhexane
oc,oc 1-Di(t-butyl-peroxy)-1,3- and 1,4-di-isopropyl-benzene
Random copolymer of ethylene, propylene and diene
Random copolymer of ethylene and propylene
Glycidyl methacrylate
High-density polyethylene
3,3,6,6,9,9-Hexamethyll,2,4,5-tetraoxa cyclononane
Iso-butylvinylether
Low-density polyethylene
Linear low-density polyethylene
Monomer
Maleic anhydride
Methyl acrylate
oc-Methyl styrene
Methyl methacrylate
N-vinyl pyridone
I-Dodecene
Ricinoloxazoline meleinate
PE
PMA
PP
R*
RM*
ROOR'
SA
SMA
St
TBHP
TMVS
VCH
1.A.l.2
A
CTC
D
DSC
L1E
EPR
f(t)
f(r)
FTIR
L1H
HDBE
IR
L/D
Mn
Mw
MFI
N
NMR
phr
Q/N
ra
RTD
SEC
~
t 1/2
UV
Polyethylene
Poly(maleic anhydride)
Polypropylene
Primary free radical
Monomer radical
Organic peroxide
Substituted succinic anhydride
Copolymer of styrcne and maleic anhydride
Styrene
T -butyl hydroperoxide
Trimethoxyvinylsilane
Vinylcyclohexane
Miscellaneous
Electron-accepting monomer
Charge transfer complex
Electron-donating monomer
Differential scanning calorimeter
Activation energy
Electron paramagnetic resonance
Residence-time density function
Dimensionless residence-time density function
Fourier transform infra-red spectroscopy
Difference between the chemical shift in NMR of A
alone and that when A forms a complex with D
Hydrogen bond dissociation energy
Infra-red spectroscopy
Length-to-diameter ratio of a screw extruder
Number average molecular weight
Weight average molecular weight
Melt flow index
Screw speed
Nuclear magnetic resonance spectroscopy
Parts per one hundred resin
Feed rate
Specific throughput
Reactivity ratio of copolymerisation
Residence-time distribution
Size exclusion chromatography
Ceiling temperature
Halflife of a free-radical initiator
Ultraviolet spectrophotometer
81
82
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Comprehensive Polymer Science, vol. 3 (eds. G. Allen and J.C. Bevington), Pergamon Press,
Oxford, ch. 8.
21. Trivedi, B.e. and Culberson, B.M. (1982) Maleic Anhydride, Plenum, New York.
22. Nowack, RW. and Jones, G.D. (1960) U.S. Pat. 3177,269; U.S. Pat. 3177,270.
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(1970) KG.C.P., 47(4), 487.
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27. Gaylord, N.G. (1975) J. Macromol. Sci. Rev., Macromol. Chem., 13,235.
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1368-70.
33. Callais, P.A. and Kazmierczak, RT (1990) ANTEC'90 Technical Papers, Dallas, TX, pp.
1921-23.
34. Oostenbrink, AJ., Borggreve, RJ.M. and Gaymans, RJ. (1989) Paper presented at the PPS
European Regional Meeting, Rolduc.
35. Ganzeveld, KJ. and Janssen, L.P.B.M. (1992) Polym. Eng. Sci., 32(7), 467.
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37. Myers, c.L. (1995) Free radical grafting on polypropylene. Paper presented at the
Intersociety Polymer Conference, Baltimore, MD, 10 October.
38. de Vito, G., Lanzetta, N., Maglio, G. et al. (1984) J. Polym. Sci., A22, 1335.
39. Rengarajan, R., Parameswaram, V.R., Lee, S. et al. (1990) Polymer, 31, 1703.
40. Aglietto, M., Bertani, R., Ruggeri, G. and Segre, A.L. (1990) Macromolecules, 23, 1928.
41. Regal, W. and Schneider, C. (1981) Makromol. Chern., 182, 237.
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Modification of polypropylene by organic peroxides

A.H. HOGT, J. MEIJER and J. JELENIC
2.1
Introduction
2.1.1 Modifications of polyolefins
Many new technologies are developed and applied in the area of production
and modification of polyolefins. Besides the development of new polymers
by reactor technology with new Ziegler-Natta [1] or metallocene catalysts
[2] the post-reactor modifications of polymers represent additional techniques. Such modifications can be performed by oxidation [3,4], or
halogenation [5-7], high-energy irradiation [8-12] or by thermal [13],
mechano-radical [14] or chemical means involving radical initiators [12, 15,
16]. In many cases, polymerizable monomers may be applied to form grafts
or graft-copolymers [17,18]. These modifications are most attractive for
improving processing characteristics and end-use properties of commodity
polymers such as polyolefins, in particular polypropylene (PP).
2.1.2
Polypropylene
PP is the fastest growing commodity thermoplastic resin, with an annual

growth of 8% since the late 1980s and a global production of over 19 million
tonnes in 1995 [19,20]. Major end-uses are injection-molded articles, fibers,
film and blow-molded products. Developments in PP polymerization and
blending technology lead to advanced polymer grades, such as high impact
and reinforced grades, allowing the penetration into 'lower end' engineeringrelated applications [21].
Modification of PP by copolymerization of propene with functional
monomers in the polymerization process in PP is very difficult because of
poisoning of the Ziegler-Natta catalyst and other reactions [22]. The
functionalization of PP or modification with graft-copolymers is technically
feasible and in general more flexible and economical using a post-reactor
process. Owing to their hydrocarbon nature and their low polarity, polyolefins have a relatively poor chemical reactivity with acidic and alkaline
reactants. However, the polymers are sensitive to oxidative and photochemical reactions, mostly proceeding through free-radical mechanisms. Polymer
modification processes based on radical reactions generally require welldefined initiation and controlled reaction times, which cannot be achieved
Chapman & Hall 1997
MODIFICATION OF POLYPROPYLENE BY ORGANIC PEROXIDES
85
with mechanochemical or oxidative radical production. Therefore, organic

peroxides with defined thermal decomposition and radical production are
generally preferred as initiators in polymer modifications.
2.1.3
Organic peroxides
In the polymer industry, organic peroxides are widely applied as radical

initiators of the polymerization of vinyl chloride, ethylene, styrene and
acrylates [23,24], as curing catalysts in unsaturated polyester resins [25]
and as cross-linking agents in polyethylene (PE), ethylene-vinylacetate
copolymer (EVA), ethylene-propylene copolymer (EPM) and ethylenepropylene-diene monomer terpolymer (EPDM) rubbers [12, 26, 27] and in
linear low-density PE (LLDPE) for the introduction of long-chain branches
[28]. A fast-growing area of application of organic peroxides is the modification of PP.
Inorganic peroxides such as potassium persulphate find very limited use;
their relatively high reactivity necessitates reaction at fairly low temperatures
and their polar nature causes dispersion difficulties in hydrophobic media
[12]. The use of azo-initiators for PP modification is also restricted because
of their relatively short halflives, toxicity (including the decomposition
products) and problems due to the evolution of nitrogen [12]. At present,
practical applications of organic peroxides in PP are mainly controlled
degradation and grafting with (functional) monomers. Many studies have
been conducted and developments are being carried out with the use of
organic peroxides for cross-linking, graft-copolymerization and reactive
blending. However, the literature surveying chemical modifications of PP by
organic peroxides with a focus on the radical chemistry involved is scarce.
2.2
2.2.1
Background
Radical reactions in polymers
Under influence of thermal and/or mechanical energy polymer chain bonds

are subject to rupture [29, 30]. The presence of oxygen may lower the
reaction activation barrier. Macroradicals formed by chain scissions are
short-lived. Transfer reactions, mainly hydrogen transfer, occur at a high
rate even at very low temperatures, the rate and reaction depending on
temperature and polymer type. Electron spin resonance (ESR) data suggest
that radical decay is a second-order reaction with radical stability depending
on polymer composition [31]. Chain scission reactions of molten PP
induced by irradiation were analyzed by 13C nuclear magnetic resonance
(NMR) [32]. A survey of degradation of PP by irradiation is given by
Henman [12].
86
In polymer modification processes various radical reactions have to be

distinguished. Radical pairs terminate by disproportionation or combination the latter leading to cross-linking. Polymer radical-monomer reactions
lead to grafting or graft-copolymerization. Polymer radicals can also lead to
chain scission such as in the case of PP. In PP the methyl group exerts a
positive inductive effect weakening the tertiary C-H bond. The tertiary
hydrogens on PP which are readily removed allow for chain scission by an
intramolecular free-radical mechanism. In linear hydrocarbons fJ-scission is
energetically unfavorable because primary radicals are formed. In PP the
fJ-scission is energetically more favorable forming secondary radicals and
terminal isopropenyl groups. Such electron-rich double bonds are expected
to be less susceptible to additions of nucleophilic macro radicals [33]. In the
presence of oxygen, the reaction of macroradicals with oxygen to macroperoxy-radicals is expected to be extremely fast and energetically favorable
[34]. An extensive review of the mechanism of degradation of polyolefins by
thermal degradation and oxidative processes is given by Stivala, Kimura
and Gabbay [13].
Detection of the primary macoradical is difficult because of their inherent
reactivity. Tests at low temperature and in the absence of air enhance the
possibility of primary radical detection. Also, compounds may be added to
titrate the radicals directly, e.g. calorimetrically, as with 1,1-diphenyl-2picrylhydrazyl, or to convert the primary radical to a resonance-stabilized
radical of longer life for tractable ESR detection [29]. A summary of
macroradicals reported by ESR is available [35]. In modification reactions
of polyolefins, organic peroxides generating oxy radicals are preferred
precursors to form macroradicals.
2.2.2
Organic peroxides
Organic peroxides can be classified into different groups depending on their

chemical structures (Figure 2.1).
The thermally induced homolysis of the peroxidic bonds yield oxy
radicals. The decomposition rate of these peroxides depends not only on the
class of peroxide but also on the type of R group. The reactivity and the
sensitivity of the peroxides to radical attack (induced decomposition)
strongly depends on the structure. Therefore, organic peroxides are radical
initiators with a very broad range of reactivities [36]. This is illustrated in
Figure 2.2 which shows the halflife (t 1 / 2 ) of different peroxides as a function
of temperature.
The decomposition of organic peroxides is a first-order reaction. An
increase in temperature of about lOOC results in a twofold to threefold
increase in decomposition rate. The reactivity of organic peroxides is in the
case of peresters and diacylperoxides affected to a high degree by the type
Hydroperoxides
:R-O-O-H
Dialkylperoxides
:R-O-O-R
Peroxyesters
:R-C-O-O-R
87
o11
oII
Peroxycarbonates
Diacylperoxides
:R-O-C-O-O-R
o11
0
II
:R-C-O-O-C-R
oII
Peroxydicarbonates
0
II
:R-O-C-O-O-C-O-R
Figure 2.1 General structures of different classes of organic peroxides.
of substituents on the carbon atom adjacent to the peroxy bond. Increasing

alkyl substitution on a given peroxyester shortens the halftife by a factor of
more than 60, on diacylperoxides by a factor of 9000. This substitution effect
is much less prominent for other peroxides such as peroxy (di) carbonates
and dialkylproxides where substituents are varied on the fJ-position to the
peroxy group. An extensive review on peroxy compounds is reported by
Sheppard [37].
200
Temperature (0C)
Figure 2.2 Halflives of different organic peroxides as a function of temperature . = EHP; f::,. =
TBPP; = LPO; <> = BPIC; ~ = TBPB; 0 = DTBPH (for abbreviations, see Appendix 2.A).
88
There are several important parameters for the choice of a peroxide for
use in modification reactions of PP. The rate of decomposition is most
critical depending on the processing conditions in the application. The
radicals formed after decomposition must be efficient H-abstractors, for
example: t-butoxy-, phenyl- and methylradicals. The physical form of the
peroxide, e.g. liquid, solid, or diluted in solvent or absorbed on solid carrier,
can be an important parameter. Also, the volatility of the peroxide can be
critical for efficiency or safety reasons. Furthermore, the nature of the
decomposition products (toxicity, volatility, odor, etc.) and the residual
amounts in the final polymer are important requirements for approvals by
authority for food-contact applications.
Decomposition rates of peroxides as determined in solvents are not
necessarily the same in polymeric media [38]. A slight decrease in the rate
of decomposition of dicumyl peroxide is observed in isotactic PP (iPP) in
the solid state. At HOC the rate constants are two to three times lower than
in benzene. The decreased rate of peroxide decomposition in glassy or
crystalline polymers compared with polymers in the rubber or thermoplastic
state is due to the slower dissociation of the peroxide and not simply to the
cage effect giving an increased reversible recombination of the primary
radicals. The viscosity of the polymers in the melt or rubber-like state can
have some effect on the rate of peroxide decomposition [38]. The decomposition of t-butylperoxybenzoate (TBPB) in alkanes and low molecular
weight PE at 150C was found to be influenced by their viscosities [39].
However, in other studies, the rates of decomposition of dicumyl peroxide
(DCP) and bis(t-butylperoxyisopropyl)benzene (DTBPIB) in PE above
100C were found to be in accordance with those determined in low
molecular weight alkane and benzene [40, 41].
2.2.3 Model studies

Quantitative analyses of modified polymers and decomposition and reaction
products of peroxides in polymers are difficult to perform. To obtain more
insight into the reactions and kinetics of modification reactions of polyolefins, low molecular weight model compounds such as pentadecane,
eicosane or squalane are often used in order to simplify the analysis
[42-46]. However, results from model studies with such compounds have
to be treated with caution because in polymers reaction speeds can be
influenced by chemical or physical interactions from adjacent groups in
polymers or be dependent on the molecular weight of the polymer [47].
Model reactions with low molecular weight alkane model compounds are
of limited significance for the investigation of reactions of PP, because
dimerization reactions are generally predominant over scission reactions
[39].
H3
CH 3
CH 3
?H3
CH r y-OO-y-CH 3
89
CH-C-O*
3
CH 3
Dissociation
CH 3
CH 3
!3-Scission
CH-C-O* - - 3
CH 3
CH 3
I
CH -C-O *
3 I
CH 3
CH 3
+ R-H - - -
I
I
CH~-O-H
+ R*
H-abstraction
CH 3
H-abstraction
Figure 2.3 Decomposition reactions of DTBP and hydrogen abstraction reactions from a
substrate.
Model studies using low molecular weight hydrocarbons are still very
useful for investigating the routes, kinetics and products of the decomposition reaction of organic peroxides. A complete analysis of decomposition
products can be obtained by using gas chromatography (GC). In the
following example, results of a decomposition study of di-t-butylperoxide
(DTBP) in pentadecane (R-H) as substrate is shown (Figure 2.3).
Dissociation of DTBP yields two identical t-butoxyl radicals which can
abstract hydrogen from the substrate or undergo fJ-scission forming acetone
and a methyl radical, which also is able to abstract hydrogen from the
substrate. Methyl radicals have comparable tertiary H-abstraction capability to t-butoxyl radicals [48] but are more efficient in combination reactions.
In such decomposition studies a mass balance on the decomposition
products of more than 95% can be obtained. From decompositions performed at different temperatures, reaction kinetics and changes in amounts
of decomposition products formed can be determined. The rate of fJ-scission
of t-butoxyl radicals increases with temperature (Figure 2.4).
Because of the high volatility and very low flashpoint of DTBP (55C
under nitrogen), the handling and dosing at high temperatures is difficult.
Therefore, in practice the dialkyl bisperoxide 2,5-di-t-butylperoxy-2,5-dimethylhexane (DTBPH) is mostly used. From the decomposition of
DTBPH the same decomposition products as from DTBP are formed,
acetone formation is increased, but much less t-butylalcohol is formed than
from DTBP. Some additional decomposition products are formed from the
90
2.0 , - - - - - - - - - - - - - - - - - - , 0 . 8
~
.so 1.5
0.6 ~
::::.
o
.s
"0
:::l
~Q.
r::::
1.0
0.4
'ti
.2
.~
f"O>-_----B----lO. 2 ~
~ 0.5
en
~
125
150
175
200
Temperature (0C)
225
Figure 2.4 Dependence of levels of acetone and t-butyla1cohol (TBA) decomposition products
of DTBP and dimer of pentadecane from the reaction temperature. 0 = acetone; /:::,. = TBA;
+ = dimer.
dimethylhexane part. The mass balances of the t-butoxy-derived decomposition products and on the dimethylhexanedioxy-derived decomposition
products of DTBPH is greater than 90%.
The rate of H-abstraction from the substrate molecule increases with the
type of H atom, in the order primary, secondary and tertiary both for
methyl and for t-butoxyl radicals [48]. Various reactions occur with the
substrate molecule radical after H-abstraction, presented schematically in
Figure 2.5.
The ratio of the rate of disproportionation to combination increases in
the order: alkyl-methyl, alkyl-alkyl, alkyl-t-butoxy pairs. It increases also
in the order: primary, secondary, tertiary alkyl radicals [49]. Disproportionation reactions considerably increase with the number of p-H-atoms
relative to a C-centered radical (increasing number of alkyl substituents)
[50].
R * + R * _ R-R
Combination
R * + R * - R-R'
Cross-combination
R* + R* _
R - H + R(-H)
Disproportionation
R*+R* -
R(-H)+R'-H
Cross-disproportionation
Figure 2.5 Combination and disproportionation reactions of substrate molecules. R' denotes a
methyl or t-butyloxy radical other than the substrate radical.
91
In the model substrate pentadecane combination products of t-butoxylradicals and methylradicals with pentadecylradicals could not be traced
[39]. In the literature there is also no description of combination reactions
of t-butoxyradicals with alkyl radicals generated from dialkylperoxides. As
an example of a combination reaction after decomposition of t-butylperoxypivalate (TBPP) in pentadecane at 88C di-t-butylether was detected
at a few mol%. Examples of combination products of acyloxyradicals with
alkylradicals are well known from the decomposition of diacylperoxides
[51,52]. The extent of substrate dimer formation of the low molecular
weight substrate can be used to define the cross-linking efficiency of organic
peroxides [39].
Summaries of rate constants of H -abstraction, combination and disproportionation of alkyl (methyl) and t-butoxy radicals are given in the literature [49,
53,54]. However, the kinetic data available from model studies are mostly not
useful because the absolute rate constants have been measured at relatively
low temperatures which is different from commonly used conditions.
2.2.4
Summary
Organic peroxides suited for use in radical reactions in polymers can have a
variety of characteristics depending on their chemical structure and reactivity. Organic peroxides can be classified into different groups depending on
their chemical structure: hydroperoxides, dialkylperoxides, peroxyesters,
diacylperoxides, peroxycarbonates and peroxydicarbonates. The reactivity of
the peroxides depends not only on the class of peroxide but also on the type
of substituents. For application in modification reactions of PP, important
parameters for the choice of a peroxide are: the rate of decomposition at the
processing conditions; the H-abstraction capability of the radicals formed;
the physical form, volatility; and the nature of the decomposition products.
Although organic peroxides have a decreased rate of decomposition in
polymers in the glassy or crystalline state, their decomposition rate in
polymer melts can be decreased depending on the viscosity. The rate of
p-scission of t-butoxy radicals to acetone and methyl radicals increases with
temperature. The reaction rate of H abstraction from PP by peroxideinduced free radicals increases in the order primary, secondary, tertiary H
atoms. Methyl radicals have a comparable H-abstraction capability to
t-butoxyl radicals but are more efficient in combination reactions. The study
of radical reactions with organic peroxides is performed in low molecular
weight model substances because of the analytical difficulties of detecting
free radicals, decomposition and reaction products in polymers. Crosslinking efficiencies of different peroxides have been determined in pentadecane. However, reactions of macromolecules such as chain scission in PP
may not occur in analogous low molecular weight model substances.
92
2.3
Modifications of PP by organic peroxides
Post-reactor modification processes can in principle be performed with the

polymer in the solid state as powder, film or fiber, dissolved in a solvent or
suspended in a non-solvent or water or in the melt phase (bulk).
Modification reactions are more economical and can be larger-scale when
performed with the polymers in the solid state or melt state than when in
suspension or solution, avoiding the necessity to remove the solvent and
allowing a continuous process. Modification of polymers by chemical
reactions in the melt phase by using internal batch or continuous mixers
[55] or continuous kneaders or (twin-screw) extruders [56], also termed
'reactive processing', is gaining increasing importance [57-63]. A comprehensive review report on reactive processing of polymers with over 650
references has been written by Brown, Coates and Johnson [16].
Radical reactions of PP with organic peroxides in the polymer solid state
or in solution or suspension can be conducted relatively slowly and
isothermally, with an approximately constant rate of initiation. However, in
most reactive processes in extruders the decomposition of the peroxides in
the polymer melt occurs rapidly and under non-isothermal conditions
because of the short residence times and relatively high polymer melting and
reaction temperatures (see ch. 1, sec. 1.5.3.d). Modeling of the reaction
kinetics is therefore useful to optimize the reaction conditions [41,63].
In the following, various PP-modification processes involving the use of
organic peroxides will be treated. These are: controlled degradation, crosslinking, peroxidation, grafting with monomers and reactive blending with
other polymers. Table 2.1 gives a survey of organic peroxides frequently
reported or practically used in modification processes of PP. Physical forms
and reactivities of the products are also given.
2.3.1
Controlled degradation of PP
Polymerization reaction grades of PP can be made with various molecular

weights resulting in grades with different melt flow indices (MFIs). The
conventional polymerization technology gives a relatively broad molecular
weight distribution, which results in resins with impaired processability
owing to a high melt elasticity. Reduction of the high molecular weight tail
responsible for this high elasticity and the consequent narrowing of the
molecular weight distribution by a random chain scission process yields the
so-called controlled-rheology PP (CR-PP) [58,59]. Both the lowering of the
molecular weight and the narrowing of the molecular weight distribution
(MWD) have profound effects on the flow behavior. The shear viscosity is
decreased to a more Newtonian character and the elongational viscosity is
reduced in magnitude but tends to become an increasing function of stretch
rate [64,65]. Advantages of CR-PP grades are mainly lower melt processing
93
temperatures, higher speeds in melt spinning of thin fibers and nonwovens,

extrusion of thin films and thin-walled injection mouldings.
The first techniques used for controlled degradation of PP were extrusion
processes using high temperatures [66], reaction with oxygen [67], high
shear gradients [68] and a combination of heat and shear under air
conditions [59, 69]. Oxygen can be used for degradation of PP, but
difficulties met are inaccurate feeding and the occurrence of side reactions
leading to color and odor problems. The use of organic peroxides for PP
degradation was firstly published in the early 1960s [70,71]. Dialkylperoxides such as DTBPIB, DCP and 2,5-bis(t-butylperoxy)-2,5-dimethylhexyne
(DTBPHY) were originally applied in a PP extrusion process [72].
(a) Mechanism. The degradation of PP by organic peroxides occurs
through a sequence of radical reactions: peroxide decomposition, H-abstraction, chain scission and termination (see Figure 2.6).
As the overall degradation rate is controlled by the peroxide decomposition rate with first-order kinetics, processing times should be equivalent to
about six or seven halflives of the peroxide to ensure practically complete
decomposition. Dialkyl-type peroxides can complete the reaction in less
than 1 min at 200C. The secondary decomposition reaction of the tbutyloxy radical to acetone and a methyl radical has no effect on the
degradation of PP as CH~ is equally reactive in H-abstraction from PP (see
also section 2.2.3). The occurrence of a propagation step in the radical
reactions leading to new chain scissions also cannot be excluded.
(b) Modeling. Comprehensive studies of peroxide-induced degradation of
PP have been carried out [73-84]. The authors of these studies developed
general kinetic models for the peroxide-induced degradation of PP in a
single screw extruder. Molecular weights and weight distributions were
predicted by using plastication extruder models and residence-time distribution measurements. Pabedinskas, Cluett and Balke [84] combined a
kinetic model of the PP-degradation reaction with a simplified model of the
melting mechanism in the extruder and found significantly improved predictions of the experimentally determined molecular weight distributions and
molecular weight averages.
In the kinetic models an initiator efficiency can be defined as the number
of primary free radicals causing chain scission divided by the total number
of primary free radicals generated [79,80]. It is generally observed that in
the peroxide-induced degradation of PP this maximum theoretical efficiency
is typically not reached [85]. The degree of chain scission is linear with the
amount of initiator used [78]. However, the initiator efficiency may decrease
with increasing initiator concentrations [85]. The trends observed may also
depend on the polymer and conditions used. Values for initiator efficiency
ranging from 0.22-0.93 with an average value of about 0.5 are reported from
DCP (Perkadox BC)
TBPB (Trigonox C)
BPIC (Trigonox
BPIC-C75)
TBPEH (Trigonox 21)
BPO (Lucidol)
Peroxide"
CH;)
yH,
CH,
CH.
~-o-O-y-CH'
yH,
Hs
CHI
CH l
~TH.
r;_ ~ ?-o-o-?c~
r;_ ~
f_ ~
0-0
tH3I
CH'-CH-O-~-O-O-~-CH.
C2H.s
CHI-(CH2);,-CIH-H-o-o-{-CH:t
~~-O-O-~~
Chemical structure
Powder
Liquid
Liquid
Liquid
Powder
Physical
form"
50
14
8.1
0.38
0.37
Halflife at
lOOC (h)
5.5
1.7
1.0
0.27
0.32
Halflife at
200C (s)
Table 2.1 Organic peroxides reported and/or used in modifications of PP (for abbreviations, see Appendix 2.A)
Grafting of monomers;
reactive blending
Cross-linking; grafting
of monomers
Grafting of silanes
Graft-copolymerization of styrene
Cross-linking; grafting of
monomers
Applications
,
TH
TH,
~~
H,
eH,
-0 - 0 -
~~
CH.
CH J
CH l
-CH,
-CH J
H,
T
1
H,
iH'
CH,
c~-~-o-o-~-c~
eH,
CH~-T -0
H,
T -o-T-c:::;c
T -1T"
CH'_!_O_O_1~T-O-OH,
~~ CH,
H.
TH,
IH'
-0-0- -CH,
H,
-CHJ~CH,-
H,
IH,
IH,
H~
I"
CH,- -0-0-
Liquid
Liquid
Flakes
Liquid
139
125
60
67
15
16
6.5
6.0
Controlled degradation
Grafting of monomers
Controlled degradation; grafting

of monomers; reactive blending
Controlled degradation; grafting

of monomers; reactive blending
'Source: Akzo Nobel Chemicals (1992) Initiators for Polymer Production, product catalogue, Amersfoort, The Netherlands.
DTBP (Trigonox B)
DTBPHY (Trigonox
145-E85)
DTBPIB (Perkadox
14S-fl)
DTBPH (Trigonox 101)
96
R-O-O-R'
R-O'
---
'O-R'
R-O
R-OH
1~-scission
............
~+ .~/
Figure 2.6 Peroxide decomposition, H abstraction and chain scission of PP.
different tests [78,84]. Assuming that the initiator efficiency should remain
constant, varying results in the calculations may be attributed to uncertainty
in the experimental initiator concentrations, if there were localized variations in the initiator concentrations [84]. Inefficiency may also be caused
by side reactions such as those with stabilizers present in the polymer.
The reaction kinetics of atactic PP (aPP) with DCP have been studied
by means of differential scanning calorimetry (DSC) [86]. In ethylenepropylene copolymers cross-linking and degradation reactions can occur
simultaneously. Different correlations between the number of broken bonds
compared with the number of new bonds depending on propylene content
have been reported [12,87].
( c) Processing. Peroxide-induced PP degradation processes have been
investigated in different processing equipment, such as laboratory batch
mixers, single screw extruders and twin-screw extruders with different screw
configurations [88-91]. When comparisons are made at the same temperature, peroxide level and residence time the greatest extent of degradation is
found in the twin screw extruder and the least in the single-screw extruder,
because of the rapid efficient melting and mixing in the twin screw extruder.
Screw configurations avoiding intensive shearing elements with rapid heating and premature peroxide decomposition were found to be most effective.
97
75r----------------------------.
60
45
~
"'C
.5 30
"ai
:::!:
15
OL-~~~~~--~~--~~--~~
0.00
0.02
0.04
0.06
0.08
Peroxide concentration (wt%)
0.10
Figure 2.7 The effect of peroxide concentration and temperature on the degradation of PP
(peroxide: Trigonox 101). Temperature: 0 = 250C; f:::, = 225C; 0 = 200C.
Figure 2.7 shows an example of the MFI increase of PP after extrusion

with DTBPH. Degradation at higher temperatures yields somewhat higher
MFI levels as a result of the increased PP chain scission rate.
Liquid peroxides or peroxide formulations in solvents or premixed with
the powder resin would yield a higher peroxide utilization efficiency owing to
faster homogeneous mixing in the polymer melt [89, 92]. Inhomogeneous
mixing of peroxide with the polymer causes loss of efficiency and localized
excessive degradation yielding a larger amount of low molecular weight
fragments from PP [93]. Broad or even bimodal MWD could be produced if
the peroxide decomposed before being uniformly mixed in the polymer [92].
Combination of a dialkyl peroxide (DTBP) and hydroperoxide, e.g.
t-butylhydroperoxide (TBHP), for PP degradation is claimed for a two-step
degradation at subsequently increased temperatures, first during pelletization, then during conversion into finished article [94]. Degradation of PP
with radical initiators other than organic peroxides has also been reported,
e.g. 2,3-dimethyl-2,3-diphenylbutane (DMDPB) and benzopinacol derivatives [95]. However, such C---C initiators are far too unreactive; DMDPB
has a halflife of 1 min at well above 300C. These systems have not gained
practical significance.
Thermal decomposition of DTBPH yields t-butyl alcohol and acetone as
main products, which can only be partly removed by venting of the extruder
[55]. Perketals such as 2,2-di(t-amylperoxy)propane and 3,6,6,9,9-pentamethyl-3-n-propyl-l,2,4,5-tetraoxacyclononane with shorter or longer halflives, respectively, than DTBPH do not release t-butylalcohol but are less
efficient than the common dialkylperoxides [96].
98
Stabilizer, antioxidants and other radical scavengers reduce the overall

degradation rate of PP. Phenolic antioxidants and organic phosphite
synergysts commonly used at levels below 0.1 % only slightly inhibit the
degradation.
(d) Summary. The controlled degradation of PP by organic peroxides is
widely applied in industrial practice today to produce CR-PP resins with a
narrow MWD and optimized processing properties. The modification is
commonly conducted by a melt process in twin screw extruders. A large
number of studies have been published concerning the effects of processing
conditions and the modelling of the degradation reactions.
There is a wide choice of peroxides, but only those with optimal reactivity
in the PP melt modification process are suited. If the peroxide is too fast it
will decompose during the polymer heating-up stage, but if too slow the
granulated product will contain undecomposed peroxides that continue to
degrade the polymer during further processing. In comparison with other
types of peroxides the dialkyl peroxides are relatively stable and yield upon
decomposition at the processing temperature of PP reactive t-butoxyl or
methyl radicals which are very efficient H-abstractors.
The choice of peroxides for CR-PP applications is severely restricted by
the recommendations of the German Bundesgesundheitsamt (BGA) and
American Food and Drug Administration (FDA) for food applications. The
BGA-allowed peroxides are DTBPH, DTBP and DTBPIB at levels restricted to max. 0.1 wt% [97]. In addition, the level of decomposition products
remaining in the modified PP is of importance. To comply with FDA food
approval, CR-PP materials have to be prepared with DTBPH and contain
maximally 100 ppm of t-butylalcohol [98].
2.3.2
Cross-linking of P P
The cross-linking of polyolefins such as PE and EVA and of EPM and

EPDM elastomers by using organic peroxides as cross-linking agents is
well-known [27,99-101]. Nojiri and Sawasaki gave a review of the crosslinking of PP by organic peroxides with coagents, azides, radiation crosslinking, silane cross-linking and by other methods [102]. In a more recent
paper the cross-linking modification of PP with organic peroxides, siloxane,
triazo compounds and by radiation and salt cross-linking was reviewed by
Shu [103]. Chodak [104] reviewed the properties of cross-linked polyolefinbased materials, including cross-linked PP.
(a) Mechanism. The efficiency of PP cross-linking depends mainly on the
competition between two reactions of the macroradicals generated after H
abstraction by oxyl radicals. The rate of chain scission is influenced mostly
99
by temperature, and the rate of recombination depends on initiator concentration and on the rate of its decay [105]. Chodak and Lazar [106J showed
that the cross-linking of PP as measured by the insoluble gel in boiling
xylene closely correlated with the decomposition rates of various initiators
tested. A higher initiation rate, causing an increased radical concentration
and stationary level of macro radicals, resulted in a rise of the recombination
rate in PP [105,107]. An increase of disproportionation at the expense of
recombination when going from primary to secondary and tertiary alkyl
radicals may be expressed by the ratio 1: 5: 25 [101]. Greater reactivity of
radicals can increase the cross-linking efficiency as a result of smaller
selectivity of the attack of the PP chain. This can lead to larger local
concentrations of secondary and primary macroradicals which give more
recombination reactions than disproportionation reactions (section 2.2.3).
The terminal chain fragment radical being formed after the chain scission
reaction may also combine with the primary macro radical formed after H
abstraction and thus form branched polymer structures [70,107]. Combination of cross-linking and degradation of PP by using low-temperature
decomposing peroxides and dialkyl peroxides giving PP with free-end
long-chain branching was reported to improve strain hardening elongational viscosity [108J. Generally, the activation energy for fragmentation is
much higher than for recombination of radicals, so the efficiency of crosslinking is greatly influenced by temperature [105,106]. Higher amounts of
gel are reached at about 165C-170C, approximately the melting temperature of PP. Decreased concentration of cross-links was observed at increasing temperatures, attributed to the increase of fragmentation reactions with
respect to recombination reactions.
Very high levels of peroxide are reported to cross-link PP [106, 107, 109,
110]. The efficiency of cross-linking is reported to be also very dependent
on the type of peroxide [106, 107, 111J (Figure 2.8). The cross-linking of
unstabilized iPP at 170C in closed ampoules under nitrogen was higher for
TBPB and dibenzoyl peroxide (BPO) than for DCP. Dilauroyl peroxide
(LPO) and DTBP gave no cross-linking. BPO is less efficient than TBPB
because of the greater induced decomposition at high radical concentrations. The higher halflife of DCP results in too Iowa radical concentration.
LPO yields upon decomposition and decarboxylation inefficient alkyl radicals. The low cross-linking efficiency observed with DTBP is probably
because of its high volatility, which under the test conditions used causes the
DTBP to decompose in the vapor phase.
Atactic PP was also cross-linked by using BPO, DIPP and 2,2-azobis
(isobutyronitrile) (AIBN) in various solvents at high concentrations up to
15 wt% on PP [110]. In ethylene-propylene copolymers with higher
ethylene contents the cross-linking reaction increases with respect to the
degradation reaction [12,87].
100
1oo.------------------------------,
~0)
50
0~~~~~~0~.4~--~0~.6~--~0~.8~--~1~.0~
i (mol/kg)
Figure 2.8 Gel formation (g) in PP as a function of concentration (i) of various peroxides.
o = BPO; = DCP; t) = TBPB; ~ = DTBPIB; 6. = DTBPH; \l = DTBPHY. Reproduced with permission from Chodak, I. and Lazar, M., Angew. Makrornol. Chern., 106,
153-160; published by Hiithig & Wepf Verlag, Heidelberg, 1982.
(b) Cross-linking coagents. Cross-linking reactions of PP induced by

organic peroxides can be effectively enhanced by the addition of polyfunctional monomers such as divinylbenzene (DVB), diethylene glycol dimethacrylate, diallyl maleate, unsaturated esters and ethers of pentaerythritol (e.g.
tetra-allylether) and triallyl cyanurate [111, 112]. The grafting of these
monomers to PP creates active sites for trapping other macroradicals and
for the formation of a cross-linked structure. With pentaerythritol tetraallylether as coagent in aPP a much higher gel content was found with DCP
than with DTBP and DTBPH [113].
Sulfur is an effective coagent of PP cross-linking initiated by peroxides
[114] suppressing the PP chain scission and forming polysulphidic bridges
in PP. An optimum of the formation of insuluble gel is reached with a DCP
to sulfur ratio close to 1: 1. Sulfur donors, such as thiourea and derivatives
of thiourea, also gave increased gel contents in PP in combination with
TBPB and BPO [115,116]. The cross-linked PP contained solely the
bonded sulfur and no nitrogen. A relatively steep dependence of gel yield on
the ratio of peroxide to thiourea was observed.
Coagents such as p-benzoquinone, hydroquinone and bisphenol are also
very effective in PP cross-linking [117]. The role of quinone as the coagent
of cross-linking can consist in the trapping of macroradicals and thus
101
bridging polymer fragments which lead to the formation of a polymer

network. With p-benzoquinone at 170C the highest cross-linking efficiencies were obtained in combination with TBPB. Other peroxides tested BPO, DCP, DTBPIB, DTBPH and DTBPHY - gave lower efficiencies. Gel
contents showed a strong maximum as a function of quinone concentration.
The density of cross-links in PP cross-linked with DTBPIB and p-benzoquinone was analysed by NMR to be a linear function of the quinone
concentration [118]. A cross-linking effect as indicated by an MFI decrease
and improved mechanical properties of the modified material was also
observed in reactive extrusion of iPP with p-benzoquinone in combination
with DTBPIB using a twin-screw extruder at 230C [112]. PP cross-linked
with TBPB and quinones also showed increased thermo-oxidative stability,
because the stabilizing quinones are bound to the polymer matrix and
cannot sublime from the polymer [119].
Cross-linking of PP by 1,3-benzene bis(sulfonazide) was combined with
degradation by DTBPH to obtain fibers with luster [120].
( c) Silane cross-linking. An alternative technique to obtain cross-linked
PP is via the grafting of unsaturated organosilanes and subsequent curing
by moisture [121-123] (section 2.3.4(c)). Hydrolysis of alkoxysilane groups
and rapid condensation of the resulting silanols yield siloxane cross-links.
The hydrolysis and condensation process is accelerated in the presence of a
catalyst, dibutyltin dilaurate. Silane-grafted polyolefins are, in the absence
of moisture, thermoplastic and processed to the finished article, mainly
continuously produced articles such as sheet [121, 124], cable [125] and
foam [126,127] (this is discussed in more detail in ch. 5).
(d) Summary. Cross-linking of PP with organic peroxides can be

achieved by using high peroxide concentrations. BPO represented a very
effective cross-linking peroxide. However, in general, low reaction temperatures have to be applied, below the melting temperature of iPP, in order to
avoid the otherwise predominant chain scission reaction. Homogeneous
mixing of the peroxides into the high melting PP can only be achieved by
impregnation or mixing with PP in solution and subsequent evaporation.
Decomposition products from the peroxides applied at high concentrations
will generate voids in the cross-linked PP. Although the cross-linking
efficiency of PP by organic peroxides can be improved by using polyfunctional co agents, the radical-induced chain scission reaction of PP is generally dominant at PP processing temperatures. The various practical
problems involved in such cross-linking processes of PP with organic
peroxides restrict their application in practice. The cross-linking of PP via
silane grafting and moisture curing also gained no practical importance.
102
2.3.3
Peroxidation of PP
It is well known that PP can be peroxidized by treatment with oxygen

and/or ozone [128-136]. Grafted peroxides are mainly tertiary hydroperoxides and dialkyl peroxides, as peroxide bridges between two chains [131,
132, 135, 137]. Post-treatment of ozonized PP by oxygen further increases
the total active oxygen content, with a relatively lower amount of hydroperoxide [138]. PP is also oxidized with a low level of hydroperoxidation
in the presence of atomic oxygen formed from UV photolysis of ozone
[139]. Irradiation of PP films or fibers with gamma-radiation in the
presence of air also leads to the formation of hydroperoxides [140-142]
which can further decay to dialkylperoxides and other oxidation products
[143, 144].
(a) Mechanism. In the first stage of the peroxidation reactions such as by

ozone preferably tertiary hydrogen atoms of the polymer are abstracted and
the alkyl radical R* produced reacts with oxygen (Figure 2.9, routes A and
B). As alkyl radicals recombine with oxygen at a considerable rate under the
applied conditions, they are not present in detectable amounts. Subsequently, propagation reactions C and D may follow, intramolecular or intermolecular H abstraction produces hydro peroxide during this period [133].
In the initial stage of iPP oxidation at 130 C at a low oxygen pressure of
D
pp"""",~,..",
A
103
"""".~"""'"
""""~'"''''''
8
~ """"'~""""
c 1 R-H
8
""""~""""
8H + R*
""""'IItI""",
Figure 2.9 Peroxidation reactions of PP by ozone.
103
10.6 kPa a marked shift towards higher molecular weight with simultaneous
broadening of MWD curves to lower molecular weights is observed. The
molecular weight increase is ascribed to radical intermolecular recombinations of alkoxyl radicals [145]. After chain scissions due to high-energy
radiation or mechanical shear, secondary or primary macroalkyl hydroperoxides may also be formed at chain ends [61]. In the final stage,
termination reactions occur producing several kinds of non-radical products, particularly carbonyl and hydroxyl groups [133].
If peroxidation is carried out at room temperature, a steady concentration of the hydroperoxides is reached quickly and their relative concentrations with respect to dialkyl peroxides formed decrease as the time of
ozonization increases [131]. Above 90 C, peroxides undergo thermal decomposition and the radicals formed may initiate autoxidation processes
and PP chain scission [146]. At higher oxygen pressures and longer
oxidation times molecular scission resulting in decrease in molecular weight
dominates [145].
Melt rheology measurements of ozonized PP after peroxide decomposition at 190 C under nitrogen indicated that the number of chain scissions
agreed with the number of peroxides per chain, proving that peroxides
grafted onto PP were isolated and not in sequences [131]. Grafted peroxide
decomposition has been studied with a spin trapping technique in ESR and
with DSC [146,147].
D
(b) Use of organic peroxides. Radical initiators such as (in)organic peroxides are reported to provide control over the extent of (hydro)peroxidation
of PP [148-155]. By using TBHP in aqueous solution under oxygen
pressure, PP films with a higher ratio of dialkylperoxide to hydroperoxide
could be obtained than by oxidation without peroxide [154]. The initiator
shortens the time necessary for obtaining a critical concentration of grafted
peroxide, after which any further oxidation proceeds as self-accelerating
autoxidation. In a similar process in an autoclave PP was treated in water
with TBPP or BPO and oxygen at 75 C for 2 h [153]. PP swollen in
n-heptane or cumene containing cumene hydroperoxide was peroxidized in
air at 60 C [150]. PP was peroxidized at 90 C in air with the aid of minute
amounts of DTBP in vapor form as initiator [148]. Oxidation of amorphous or isotactic PP in benzene at lOODC-130 DC using DTBP yields only
about 40% hydroperoxides on the total absorbed oxygen, which are mainly
present in low molecular weight PP fragments [151]. The (per)oxidation
rate increased with initiator concentration. At relatively short reaction times
of 300 min at 120DC a large amount of initiator still remained. A combination of organic peroxides have been used for the peroxidation of PP in the
form of powder or granules in a high-speed mixer at 70C-120DC [155].
Peroxides with a halflife < 30 min at 100C are combined with peroxides
having a halflife ~ 30 s at 200C, e.g. LPO and DTBPH. Peroxidation of PP
D
104
has also been reported in an aqueous slurry using oxygen and inorganic
peroxides, e.g. potassium persulfate [152].
The use of hydroperoxidic derivatives of crystalline and amorphous
poly-alfa-olefins as macromolecular initiators was reported by Natta, Beati
and Severini in 1959 [128]. Grafting of monomers on PP can be achieved
by reacting with peroxidized PP at elevated temperatures or at a low
temperature using a redox reaction [129, 130, 132, 134, 152, 153, 155-157].
( c) Summary. Peroxidation of PP by ozone or combined irradiation and

oxygen methods yields a mixture of grafted hydro peroxide and dialkylperoxide groups, of which the amount and the ratio are difficult to control.
By the use of organic peroxides in the presence of air or oxygen the
peroxidation is accelerated. However, the practical application of
peroxidation techniques is restricted owing to various disadvantages such as
the occurrence of oxidation side products, degradation and cross-linking
reactions.
When peroxidized PP is used as a precursor for the grafting of monomers, grafting is initiated by radicals created from the decomposition of the
more stable dialkyl type peroxide of the polymer [129, 158], whereas the
polymer hydroperoxide initiates homopolymerization reactions without
grafting [159].
2.3.4 Grafting of PP with reactive monomers
The lack of reactive groups in the polymer structure of polyolefins limits
many of their end-uses, particularly those in which adhesion, dyeability,
paintability or reactivity with other polymers is needed. Also, the olefinic
character of the semi-crystalline PP and its thermal and mechanical properties cause limitations in higher temperature applications and in blending
with other polymers (section 2.3.5). Reviews have appeared in the literature
on functionalization of polyolefins [160], graft reactions of various monomers on polymers by reactive extrusion [161], the graft copolymerization of
vinyl monomers onto PP [17] and surface grafting onto PP [162].
The modification of PP with various monomers by special Ziegler-Natta
or metallocene copolymerization methods, by grafting after hydroperoxidation or halogenation, and by photografting, radiation-induced grafting,
plasma grafting or mechanochemical grafting has been reviewed by Xu and
Lin [18]. Very little attention has been paid, however, to aspects of
functionalization and graft-copolymerization of PP with organic peroxide
initiators.
Maleic anhydride or acrylic acid functionalized PP are used primarily for
two reasons. The first is to promote interfacial filler-polymer reactions with
the aim of achieving adhesion in composites, e.g. glass fiber- PP reinforcement [163, 164]. Maleic-anhydride-grafted PP was reported to be a more
105
efficient coupling agent for glass fibers than acrylic-acid-grafted PP [164].

The second is to achieve coupling reactions with other functional polymers
and promote compatibilization of immiscible polymer blends and alloys, e.g.
with polyamides, PA (this is discussed in detail in ch. 3) or poly(vinyl
chloride), PVC [62, 165, 166]. Functionalized PP is also used in anticorrosion coatings on steel pipe [167J, in metal/plastic laminates [168J and to
improve dyeability of fibers and the printability and metallization of films
[169]. Ionic cross-linking of maleated PP is achieved by kneading with zinc
acetate or sodium acetate [170]. Anhydride or acid-modified aPP can also
be used as hot melt adhesive [171]. Modified PP resins that show good
adhesion and related properties in practical applications require about
0.1 %-0.2% of grafted maleic anhydride [59]. Removal of unreacted maleic
anhydride by heat treatment improves the adhesion [172]. The graftcopolymerization of silanes to polyolefins is generally employed to obtain
materials which are cross-linkable in the presence of water or moisture
(section 2.3.2(c)). The polyolefins are commonly grafted with about 2 wt%
of polyfunctional organosilanes having a polymerizable group and an easily
hydrolyzable functionality. Properties and uses of functionalized PPs have
been reviewed by Xu and Lin [18].
The properties of PP-polystyrene (PS) graft-copolymers (PP-g-PS) allow the targeting of the materials as potential replacements for acrylonitrilebutadiene-styrene terpolymer (ABS) or alternatives for toughened reinforced
PA or PA/poly(phenylene oxide) (PPE) blends, as compatibilizers for
PP-based blends such as PPIPS and PP/PPE blends [173]. Melt strength
and low sagging properties were improved by preparing PP with branches
of copolymers of styrene and methacrylate monomers [174]. Grafting of PP
with butyl acrylate leads to a PP with higher elasticity and adhesive
properties, useful for adhesive resin applications [175]. Alloys prepared by
reactive processing of PP and acrylic and/or other monomers are also
claimed as paper-substitute material [176].
(a) Monomers. Grafting of monomers onto PP is described in many
studies and in industrial practice it is mostly performed using organic
peroxides as radical initiators. Modifications with various functional monomers have been reported: maleic acid, itaconic acid, crotonic acid, and
related anhydrides and esters, alkenyl succinic anhydrides, fumaric acid
[177-80J, acrylic acid, methacroylic acid [163J, glycidyl methacrylate [181J,
and with vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane
and 3-methacroyloxypropyltrimethoxysilane [123]. Such modifications are
generally aimed at obtaining single monomer grafts or short length grafts
which substantially change the polymer's chemical or reactive properties but
not the mechanical properties. In the case of PP, graft-copolymerizations
with polymerizable monomers containing no functional groups such as
methyl, ethyl, butyl and isobutyl (meth)acrylate [182-5J, styrene [182,
106
186-9], vinylacetate and vinylchloride [190, 191] mostly lead to long-chain

segment extensions and/or side chains, with the main purpose of
modification of the polymer's physical or mechanical properties.
In order to reduce side reactions of monomers, Diels-Alder adducts of
conjugated dienes such as norbornene, cyc10pentadiene or furan, with
acrylic acid and maleic anhydride may be used as precursors, releasing and
grafting the monomer by the retro-Diels-Alder reaction using an organic
peroxide [192]. Increased grafting efficiency of maleic anhydride was found
when using Diels-Alder adduct precursors [193]. Maleic anhydride may
also be activated by substitution of one of the H atoms on the double bond
by a polar atom such as bromine [194].
In many studies and patents mixtures of monomers are applied,
e.g. mixtures of maleic anhydride and styrene [110,195] or triallyl cyanurate [196], styrene and acrylic acid [188] or triallyl cyanurate [197],
vinyl acetate and vinyl chloride [191] and vinyl acetate, propylene and
isobutylene [110]. Mostly, combinations of monomers were used with the
aim of achieving increased grafting levels. In some cases grafting of monomers is carried out on PP during blending with other polymers (section
2.3.5).
(b) Mechanism. Figure 2.10 presents schematically the possible reaction

routes of the grafting of PP with (functional) monomers. Depending on the
type of monomer employed, homopolymerization may compete with grafting. With homopolymerizable monomers the chain length of the resulting
grafts is usually long enough to yield a graft-copolymer with altered physical
properties.
R-O--O-R'
pp
.......
---+
R-O *
*O-R'
~........
B1 R-Q*
......
~......
c!
. . . )J.+
+ R-QH
M . .
nM
---+
......
~, .....
(M}n
nM
---+
..
.....
~(M}n
Figure 2.10 Scheme of grafting reactions of monomers onto PP.
107
The mechanism of grafting of functional monomers onto PP has been

studied most extensively with maleic anhydride. The reactivity and the
grafting yield of maleic anhydride onto PP is typically low [60] owing to
the low free-radical reactivity of maleic anhydride as a consequence of its
structural characteristics. Extensive studies by Russell et al. [42, 43, 46] on
the grafting reactions of maleic anhydride on hydrocarbon models using the
peroxides BPO or DTBPHY as free-radical initiators have led to the
conclusion that, first, MA grafting is favored over homopolymerization, and,
second, that the grafts comprise mainly single succinic anhydride units [42]
(see ch. 1, section 1.5.2(a) for a fuller discussion).
It is generally accepted that the grafting of maleic anhydride onto PP
occurs to the secondary PP macroradical (route E) which is generated by
chain scission of the polymer [164, 180, 198]. Constable and Adur [164]
postulated that the maleic anhydride and acrylic acid are grafted as single
units or, in the case of acrylic acid, grafted as short polymer chains to PP
chain ends. However, suppression of chain scission at high initial maleic
anhydride concentrations has been attributed to direct grafting of maleic
anhydride to the tertiary C radical of PP (route D) [198, 199]. Petruj and
Kolar [200] proposed a cumulation of maleic anhydride groups along the
PP chains via an intramolecular process proceeding along the main chain
via a hexagonal 'backbiting' mechanism. However, this was suggested to be
negligible by Roover et al. [180]. The grafting of several maleic anhydride
units to the polymer chain end has also been proposed [180,201]. De
Roover et al. [180] carried out an extensive characterization of maleicanhydride-functionalized PP prepared in the melt using DTBPIB at 190C.
They concluded that maleic anhydride is grafted to the terminal PP
macroradical after chain scission. The molecular weight of the grafted PP
depended only on the organic peroxide content used, but not on the maleic
anhydride concentration. The investigators also found that poly(maleic
anhydride) chain ends and non-grafted poly(maleic anhydride) are formed.
Colored products formed during the grafting reactions are also generally
ascribed to oligomeric products of maleic anhydride with conjugated
unsaturated groups [202]. Termination of the succinic anhydride adduct
radical, besides via intramolecular or intermolecular H abstraction, was
shown also to occur via addition of methyl radicals derived from the
initiator. Termination reactions producing unsaturated products appeared
not to be important [42]. Grafted poly(maleic anhydride) was shown to
depolymerize at 300C. Various other reaction possibilities, such as grafting
of maleic anhydride onto a primary PP macroradical and an ene-reaction
between isopropenyl chain ends of PP (after chain scission) and maleic
anhydride were excluded by De Roover et al. [180].
Gaylord and Mishra proposed an additional initiation step in which an
excited maleic anhydride dimer abstracts hydrogen from the polymer [178];
the excited dimer then adds to the polymer radicals formed. Subsequent
108
reactions lead to the attachment of a single succinic anhydride adduct.

However, a conventional radical mechanism involving initiation, propagation and termination steps appears to have a more general application [46].
The incorporation of maleic anhydride onto PP may be increased by
addition of an electron-donating monomer such as styrene, forming a charge
transfer complex with maleic anhydride (this is discussed in more detail in
ch. 1). A correspondence of the grafting yield with the maleic anhydride/
monomer interaction has been demonstrated [203]. Gaylord and Mishra
[178] have described efficient grafting of maleic anhydride onto PP without
significant PP degradation in the presence of dimethylformamide or
dimethylacetamide, attributed to the inhibition of the homo polymerization
of maleic anhydride which would participate in the PP degradation reactions. The use of N,N-dialkylethanolamines or N,N-dialkylaminoethyl
(meth)acrylates at levels lower than 0.2% have been claimed to improve the
grafting efficiency of maleic anhydride and styrene onto PP in the molten
state [204].
The mechanisms of grafting of easily polymerizable monomers such as
styrene, methacrylates and vinyl acetate onto PP using organic peroxides as
initiator have been studied to a limited extent in the literature. It was
suggested that the styrene graft-copolymers on PP were formed by initiation
of styrene polymerization by a PP macro radical rather than by termination
of a growing PS homopolymer with PP macro radicals [182].
Results from the grafting of ethyl acrylate on aPP in xylene at 80C by
BPO suggested that at low conversions ( < 15%) predominantly homopolymerization took place, and that graft-copolymerization occurred at higher
conversions, when H-abstraction reactions from the polymer generating
initiating macro radicals became significant when part of the ethyl acrylate
was consumed [184].
Besides the reactivity and decomposition rate of the radical initiator, the
solubility and diffusion of radicals and monomers in the PP /monomer
two-phase system are also critical parameters [182, 186-189, 205]. Using
t-butylperoxy-2-ethylhexanoate (TBPEH) as initiator at 90C-110C, the
rate of graft-copolymerization was shown to be increased in the presence of
the PP matrix as a result of a Trommsdorff- Norrish effect and diffusionlimited propagation [189]. A maximum grafting yield of methyl methacrylate on aPP depending on the weight fraction of benzene as solvent
indicated that the propagation and termination reactions and the occurrence of a gel effect in the graft-copolymerization of methyl methacrylate
vary with swelling of the PP and grafted copolymer [206]. In the graftcopolymerization of styrene onto PP using TBPEH no PP degradation or
cross-linking side reactions of PP were observed [189]. However, using
acrylic acid as co-monomer of styrene and BPO as initiator, an increased
gel content was observed [188].
MODIFICAnON OF POLYPROPYLENE BY ORGANIC PEROXIDES
109
( c) Reaction systems of monomer grafting. Various processes for the

grafting of monomers on polyolefins using organic peroxides have been
published. Reaction systems can be separated into those with the polymer
in the solid state, in solutions or suspensions or in the melt phase. The
reaction conditions are quite different for the different reaction systems:
reaction medium, temperature, reaction time, dosing conditions, premixing
of reactants, added chemicals (catalysts, inhibitors of homopolymerization),
etc. Therefore, a great variety of organic peroxides with different reactivities
are applied as radical initiators in such processes.
Grafting onto PP in the solid state. Examples of the use of organic

peroxides for grafting reactions onto PP in the solid phase are reported with
various monomers, e.g. maleic anhydride [179, 196, 207-211], itaconic
anhydride [212], acrylic acid [174, 213], and styrene [186-189, 210, 214].
In various reports combinations of monomers are also applied [174, 179,
188, 196, 197]. In most cases an inert atmosphere is created to avoid
oxidation side reactions.
At low initiator concentrations (BPO < 0.5%) and low temperature
( < 100C) no grafting on iPP was observed [209]. Relatively high maleic
anhydride and peroxide concentrations of several wt% on PP are reported
to be needed to ensure high conversion [211]. With increasing peroxide
concentrations the amount of grafted maleic anhydride increased, and the
molecular weight decreased, but less when also more maleic anhydride was
used [179]. Kinetic studies show that the reaction is first-order, the H
abstraction from PP probably being the rate-determining step. In grafting
experiments with TBPB the liberated benzoic acid indicates that under the
conditions used the H-abstraction from PP is faster than the decarboxylation of the perbenzoate radical [179]. Considerable gel formation indicating
a cross-linking side reaction was found after grafting of itaconic acid and
acrylic acid or mixtures of maleic anhydride with these monomers onto PP
in the solid phase using TBPB [179]. A combination of two radical
initiators with different decomposition temperatures can be used to graft
unsaturated acids onto PP. Polypropylene was heated at two different
temperatures with itaconic acid in the presence of LPO and DTBPIB
consecutively at 70C and 100C [212]. Probably, the latter peroxide was
hardly decomposed at 100C but reacted during the subsequent extrusion
with glass fibers.
In grafting processes of styrene onto PP in the solid phase, the (apolar)
styrene monomer diffuses in the amorphous part of PP until saturation
swelling, excess monomer remaining in liquid phase outside the PP particles.
The grafting efficiency is therefore decreased at higher styrene concentrations (Figure 2. l1(a. The rate of graft-copolymerization was shown to be
increased in the presence of the PP matrix as a result of a Trommsdorff-
110
l100
>0
c::
Q)
80
:=
Q)
Ol
c::
60
Ol
(;
c::
0
.~
e:0
Q)
40
20
00
40
60
100
80
Styrene fraction (%)
(a)
100
;e
20
100
80
80
c::
of!0 60
~
c::
~
c::
Q)
:=
Q)
/,.. -~-------~------------------++
+
, +
40
40
Ol
c::
e
(!l
20
20
0
(b)
60
;e
0
10 20 30 40 50 60 70 80 90
Time (min)
Figure 2.11 (a) Conversion (e) and grafting efficiency (.A.) of styrene onto PP as a function of
styrene fraction (110C, peroxide: Trigonox 21), and (b) conversion (e = 70 wt% PP;
o = without PP) and grafting efficiency (+) of styrene onto PP as a function of time.
Temperature = 110C; peroxide = Trigonox 21. Source: Beenen, W., van der Wal, D.J.,
Janssen, L.P.B.M. et al., Macromol. Symp., 102, 255, 1996.
Norrish effect and diffusion-limited propagation (Figure 2.11(b)) [187,189].

The grafting efficiency increased in the course of the graft-copolymerization
to a plateau level at higher conversion.
Experiments with PP particles of different sizes suggested that the
polymerization of a mixture of styrene and acrylic acid by BPO at 90C
predominantly occurred in the polymer matrix [188]. The final depth of
penetration of the monomer into the polymer will be determined by the
relative rates of diffusion and polymerization [186]. Depending on PP
geometry and the reaction conditions, part of the polymer material may
remain unmodified. Homogeneous graft-copolymerization will be favored
111
by a higher porosity of the PP but impaired by a higher crystallinity. Also,

in combination with other monomers, e.g. acrylic monomers which give a
poor swelling of PP, styrene probably has an important function as swelling
solvent [174,182]. Swelling of the PP by vinyl acetate increased as a
function of the temperature [190]. The amount of graft-copolymer linearly
increased with the reaction time, related to an increased swelling of the PP
by vinyl acetate when more vinyl acetate is grafted. The grafting efficiency
decreased with higher initial monomer concentration.
Solvents such as toluene were added to swell the PP to promote the
surface reaction [208]. High levels of grafted maleic anhydride up to 9%
were obtained by using a low amount of solvent and triallyl (iso)cyanurate
as co-monomer, and relatively high amounts of initiator (> 12.5% BPO)
[196, 210, 215].
Grafting onto PP in aqueous suspensions. Suspension processes for
modification of PP with radical initiators have been reported with different
monomers, e.g. with maleic anhydride and (meth)acrylates [216-218],
glycidyl methacrylate [219, 220], styrene [217, 221-225], vinyl acetate and
vinyl chloride [190, 191], and vinylpyridin [226].
The PP polymer particles may also be impregnated with the styrene
monomer or mixtures of styrene with other monomers in an aqueous
suspension, followed by heating at 90C-120C with peresters such as
TBPB, TBPEH, t-amylperoxy-ethylhexanoate, t-butyl- or t-amylperoxy
isobutyrate to polymerize the monomer within and on the surface of the
polymer particles [222, 226]. The impregnation may be improved by using
porous PP particles [223].
The grafting efficiency of acrylate monomers was enhanced by swelling of
the PP in the suspension with chi oro benzene, with monomer and BPO as
initiator, and a subsequent reaction temperature > 85C [218]. Also, a
two-step graft-copolymerization at different temperatures may be carried
out by using a combination of radical initiators. Styrene was grafted onto
PP in aqueous suspension by using a BPO-DCP mixture at 85C for 7 h
and at 140C for 4 h, followed by impregnation with blowing agents to give
expandable beads [224, 225].
Grafting onto P P in solution. Grafting of monomers onto PP carried
out in solution using different types of initiators has been reported with
maleic anhydride and acrylic acid [110, 177, 183, 227-230], Diels-Aldermaleic anhydride adducts [231], maleic anhydride, ethyl and butyl acrylate
[182-185, 206, 232], maleic anhydride, hydroxyethyl methacrylate or mixtures of methracrylate monomers [233, 234], vinyl acetate [235] and styrene
[182, 222, 236].
Minoura et al. [177] found DCP provided a much higher grafting
efficiency in maleic-anhydride-grafting onto atactic PP (aPP) in benzene
112
than did DTBP, BPO or AIBN, attributed to differences in the Habstraction capability of the radicals produced. In a degradation study of
diluted PP in solutions in o-dichlorobenzene at 150C DTBPIB was found
to be, on weight basis, more effective than DTBPH, DCP and DTBP [229].
Grafting efficiency of methyl methacrylate onto aPP was much influenced
by the solubility of the grafted poly (methyl methacrylate) (PMMA) in the
solvent used, but it was hardly at all dependent on the concentration of the
initiator used [182]. The grafting efficiency of methyl methacrylate in
swollen aPP increased with an increase in temperature, monomer concentration and with increase in molecular weight of the PP polymer. The
grafting efficiency was highest in a good solvent for all components. Grafting
efficiency was much lower in n-heptane, a poor solvent for PMMA but a
good swelling solvent for PP, suggesting that macroradical transfer reactions with PP playa role in the grafting reaction [182]. The grafting of
maleic anhydride and methyl methacrylate onto aPP in various solvents
(n-hexane, cyc1ohexane, benzene and cumene) varied with the chain transfer
constants of the solvent-graft-copolymer radicals [110, 183]. For styrene,
grafting efficiency was increased at higher temperatures favoring radical
transfer reactions to the basic polymer. Grafting efficiency was not much
influenced by initiator concentration, even decreasing at higher concentration. The solvents used did not influence the grafting efficiency, indicating
the low importance of radical chain transfer from the growing PS chain to
the aPP.
In some cases a solution copolymerization process was preceded or
followed by another modification process using other reaction systems.
Polypropylene degraded by extrusion with a dialkyl peroxide contains an
increased amount of isopropenyl end groups which may have a favorable
effect on the grafting of monomers. PP degraded with DTBPH to a low
molecular weight was treated in chlorobenzene with maleic anhydride and
DTBP at 125C [227].
aPP-ethyl acrylate graft-copolymer emulsions were made by grafting
acrylic acid onto aPP in the presence of BPO in xylene solution, followed
by solv~nt evaporation and further ethyl acrylate emulsion polymerization
in water with a water-soluble initiator system [232].
Vinyl-aromatic UV-absorbing monomers, e.g. 2(2-hydroxy-5-vinyl)2Hbenzotriazole, were grafted onto aPP in chlorobenzene at 150C-160C
using DTBP as initiator [237].
Grafting onto PP in the melt state. A high-temperature grafting process
above 300C in the absence of oxygen or initiator is reported to effect high
grafting levels of maleic anhydride onto amorphous PP [238]. The reaction
is effected by thermally generated PP radicals. The preparation of polyolefin
waxes by thermal degradation of higher molecular weight polyolefins in an
113
autoclave in the presence of organic acids and anhydrides, e.g. maleic

anhydride has been patented [239].
The majority of studies on functionalization of PP with various monomers have been conducted with PP in the molten phase using organic
peroxides as initiator. The most important monomers used were maleic
anhydride or maleic esters [72, 163, 165, 166, 170, 178, 180, 193, 198, 200,
201, 205, 211, 240-248], acrylic acid [163, 230, 249-252], metal complexes
of acrylic acid [253], glycidyl methacrylate or hydroxyethyl methacrylate
[181,254,255], styrene [256-259], silanes [121, 124, 127,260-263], allylic
monomers [264], vinyl acetate [265], N-vinylpyrrolidone [266] and an
unsaturated isocyanate [267]. Glycidyl-group-containing monomers other
than glycidyl methacrylate reported for grafting onto PP are, e.g. N-{4-(2,3epoxypropoxy)phenyl}maleimide [268] and n-{ (4-glycidyloxy-3,5-dimethylphenyl)methyl}acrylamide [269]. Also, mixtures of styrene with other
monomers such as glycidyl methacrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate were used using DCP in reactive extrusion [195].
Typical levels of grafted acrylic acid monomer in isotactic PP (iPP) can
be 9% with acrylic acid homopolymer less than 30% of the grafted product
[161]. In the case of glycidyl methacrylate grafting, the major part of
non-grafted glycidyl methacrylate remained in the free monomeric form
[181]. In the grafting of an unsaturated isocyanate (1l(,Il(-dimethyl metaisopropenyl benzyl isocyanate) on PP, DTBPH was more efficient at higher
temperature (210C) than TBPB. A large excess of initiator compensates for
the poor grafting efficiency of the monomer, but also considerably degrades
the PP. Grafting levels could also be increased by using an acrylic comonomer [267].
The grafting of monomers onto PP using organic peroxides is almost
always accompanied by degradation of the polymer as a result of chain
scission [251]. Peroxides which have the best grafting efficiency have
commonly also the greatest effect on the melt flow of PP [243]. On a
peroxide equivalent basis, the efficiency increased in the order DTBPH <
DCP < DTBPIB < DTBPHY. Although in another study it was found that
BPO and DCP gave similar acrylic acid grafting levels, higher than those
achieved with AIBN and LPO, PP degradation was more pronounced with
DCP than with BPO [163]. It has been reported that the PP degradation
was greater in the presence of maleic anhydride (5 wt%) and peroxide
(0.5 wt% DCP or DTBP) than in the presence of peroxide alone [178]. This
is attributed to the homo polymerization of maleic anhydride influencing the
PP degradation. However, it was also found that the extent of the PP
degradation is solely determined by the peroxide concentration and not by
the concentration of maleic anhydride [180, 198] (Figure 2.12).
Peroxides which have a short halflife at 180C, e.g. TBPP and
isononanoyl peroxide, were reported to be preferred for grafting of mono-
114
0.4
2000
1500 "2
-0 0.3
'E
()':
~
1000 a.
:::i: 0.2
"0
CI>
.t:
~
c:l 0.1
0.0
0.0
u:::
0
500
0.2
0.4
0.6
0.8
:::i:
0
1.0
Peroxide concentration (wt%)
Figure 2.12 Grafted maleic anhydride (MA) (0) and melt flow index (MFI) of PP as a
function of peroxide (Perkadox 14) concentration; MFI of modified PP with (6) and without
( + ) MA. MA concentration = 2 wt%. Source: Hogt, A.H., Antec '88, conference proceedings;
published by Society of Plastics Engineers, 1988.
mers, in particular maleic anhydride, onto PP at about 180a C, thereby

giving less degradation of the molecular weight [270]. BPD and DCP
showed similar grafting efficiencies of maleic anhydride on PP at 185 a C, but
in contrast to DCP, BPO (having a lower t 1/2 ) caused no viscosity decrease
[170]. It may be that a higher concentration of radicals leads to more
grafting with less degradation.
A certain amount of degradation of PP was purposely intended during
grafting of unsaturated silanes onto PP at 220a C using a perketal (1,1-bis(tbutylperoxy)-3,3,5-trimethylcyclohexane), DCP or DTBPIB to decrease
extruder energy consumption (MFI from less than 0.7 to 25-70). The more
reactive BPO and chlorinated BPO (bis-2,4-dichlor-benzoyl-peroxide) gave
insufficient degradation of PP and were considered unsuitable [260]. Tbutylperoxy isopropylcarbonate (BPIC) was also reported as peroxide for
grafting of unsaturated silanes [271, 272]. A cross-linking side reaction was
reported in PP grafted by DCP with acrylic acid based on the occurrence
of a gel content in boiling xylene [250]. In the grafting of metal complexes
of acrylic acid by DCP onto PP, a copper acrylate complex showed higher
grafting efficiency than did the other complexes, and the PP degradation
was also reduced [253]. A very low grafting efficiency was obtained by melt
kneading of PP with styrene using TBPP at 200 a C [257].
Limited solubility of monomers is also observed to be an important
factor that controls the overall grafting [198, 203, 273]. The grafting
efficiency of maleic anhydride typically passes through an optimum with
increasing amount of maleic anhydride, the optimum depending on the
115
0.4
-';I.
1000
DTBPH
0.3
00(
::E
0.2
100
CD
CJ
.,...
at
lL
'Gi
~
-c
E
it
::E
0.1
0.0
10
)
Solubility parameter
Figure 2.13 Grafting of maleic anhydride (MA) and PP degradation in relation to solubility
parameters of the added peroxide initiator (abbreviations, see Appendix 2.A). Hatched
boxes = MA grafted; cross-hatched boxes = melt flow index. Source: Hogt, A.H., Advances in
Additives and Modifiers for Polymer Blends, conference proceedings; published by Executive
Conference Mangement, 1993.
amount of initiator used [245]. At excess maleic anhydride concentrations,

the formation of a polymer/maleic anhydride two-phase system causes loss
of initiator to the maleic anhydride phase, thereby lowering the effective
concentration in the polymer. When poor mixing conditions prevail, the
partition of peroxides over the PP and maleic anhydride phase was shown
to result in decreased grafting efficiencies, whereby the tendency to partition
to the maleic anhydride phase was related to the solubility parameter of the
peroxides [205]. Under these conditions, DTBPH was found to be most
soluble in PP giving the highest grafting efficiencies (Figure 2.13).
The evidence regarding the effects of antioxidants on grafting efficiency
are contradictory. Although the grafting efficiency of maleic anhydride onto
PP appeared not to be significantly affected by the presence of commonly
used phenolic and phosphite stabilizers [243], a higher grafting of maleic
anhydride onto unstabilized as opposed to stabilized PP has been reported
[240]. In the stabilized polymer, phenoxyl radicals generated by the phenolic stabilizer react with PP radicals and compete with the PP-maleic
anhydride adduct formation.
The grafting of PP with maleic anhydride by reactive extrusion was
studied using a statistically experimental design method, giving optimal
116
maleic anhydride and initiator concentrations [247]. Kotlar [181] carried

out a statistically controlled study on the grafting process of glycidyl
methacrylate onto PP in an extruder using TBPB as initiator. For glycidyl
methacrylate graft-copolymers on PP, NMR analysis was too insensitive to
determine branching and the chain length of the graft.
In several cases the reaction ingredients were homogenized with the PP
prior to extrusion. PP was mixed with acrylic acid and DCP, allowed to
stand for 2-3 h, and extruded at 190C-210C [250]. PP powder was
premixed with the acrylic acid and BPO dissolved in acetone, which was
thereafter evaporated, and extruded [252]. Various allyl compounds were
mixed in chloroform solution followed by evaporation of the solvent before
grafting by DCP to aPP in the melt phase [264]. The grafting efficiency of
glycidyl methacrylate was also related to mixing effects and dispersion of the
peroxide and not only to glycidyl methacrylate concentration [274]. The
MFI was positively correlated to the peroxide concentration and the
downward position of the glycidyl methacrylate injection. The monomer
may also be polymerized first, e.g. in the case of styrene at 60C-85C, to
provide macromonomers with styryl groups at one end, which are then
grafted on a polyolefin in an extruder [275].
Using a brominated maleic anhydride, the thermally induced bromine
radicals also caused a change in the stereo regularity of PP which became
completely amorphous [194]. A polyolefin elastomer/PP thermoplastic
elastomer (TPE) mixture was grafted with glycidyl methacrylate or hydroxyethyl methacrylate in the presence of an organic peroxide, i.e.
DTBPIB, DTBPHY or DTBPH [276, 277]. PP may also be modified
during compounding with fillers using maleic anhydride and peroxide,
resulting in a compound with improved mechanical properties [241].
Various maleate, acrylic and methacrylic ester and amide derivatives of
hindered amines were reacted with PP in order to obtain polymer-bound
light stabilizers [278-280]. Modification of PP with bis-acryloyl-hindered
amines by DCP gave initially a cross-linked product which broke down
under conditions of high shear and high temperature to give a homogeneous
gel-free modified polymer. Monoacrylates and acrylamides and bis-methacryloyl-hindered amines bind to PP to a much lower extent, which was
related to their higher tendency to homopolymerize.
(d) Summary. In contrast to processes in which ozonization or irradiation procedures are used for the grafting of monomers, processes in which
organic peroxides are used as radical initiators consist of only one step and
can be carried out in common reactors or extruders. Depending on the
reaction conditions, homo polymerization and graft-copolymerization are in
most cases competing processes. Advantages of grafting maleic anhydride to
PP in the solid phase below the melting temperature is the possibility of
grafting relatively high amounts of maleic anhydride with a lower PP
117
degradation side reaction and an easier removal of the non-grafted maleic

anhydride by vacuum, solvent rinse or neutralization and water rinse.
In most studies on graft-copolymerization in solution aPP was used,
which dissolves much better in various solvents than does iPP. In a
comparative qualitative study of the reaction between PP and maleic
anhydride in solution in xylene and in the molten state with DCP, the same
levels of grafted maleic anhydride were obtained [247]. Because of the good
mixing conditions, the melt phase seems a suitable medium for graftcopolymerization. However, the ability to polymerize and graft monomers
to high conversion by reactive extrusion is limited by the high temperatures
and short residence times inherent in melt extrusion processes.
Reaction temperatures employed in modifications of PP in the solid
phase or in aqueous suspensions range from 60C to 140C, mostly around
lOOC, with reaction times from 1-6 h. Peroxides most reported are BPO
and TBPB. In some cases two-step graft-copolymerizations at different
temperatures are performed with a dialkyl peroxide, DTBPIB or DCP as
second initiator. In solution graft-copolymerizations mostly the use of BPO
is reported. Organic peroxides commonly applied in melt modifications of
PP at temperatures greater than 180C are dialkyl-type peroxides, e.g. DCP,
DTBPIB, DTBPH and DTBPHY; in some studies BPO and TBPB were
also used. In general, it is difficult to relate grafting efficiencies of organic
peroxides to their structure, because the type of radicals generated as well
as the decomposition rate varies simultaneously for peroxides with different
molecular structures. When employing relatively fast peroxides, homogeneous premixing with the PP or dosing together with the monomer or diluted
in a solvent is critical to ensure an efficient reaction. Such procedures often
used in laboratory experiments are mostly not feasible for practical processing conditions.
Variable results from different studies on grafting of maleic anhydride
onto PP in the melt phase may be attributed to the relative insolubility of
maleic anhydride in molten PP and the influence of the maleic anhydride
concentration and the mixing conditions on the formation of a separated
liquid maleic anhydride phase. Often it is not clear in the extruder where
the polymer, monomer and peroxide are mixed when the peroxide begins to
decompose. In the modification of PP with (functional) monomers or
graft-copolymers, the use of solvents facilitates, in general, the mixing of the
reactants, but is also disadvantageous because side reactions can occur and
recovery and recycling are needed.
2.3.5
Reactive blending of PP
To improve the interfacial adhesion and to stabilize phase morphology in

polymer blends different methods have been developed in the past. Mostly
they are based on in situ formation of graft and block copolymers in the
118
polymerization or processing step. In some cases, addition of a third

(polymer) component with multifunctional reactive groups has been used to
improve the interaction between blend components.
Block and graft copolymers have been applied as interfacial agents [281].
A review on in situ formation of block-graft copolymers via reactive
blending for improved 'compatibilization' has been given by Xanthos and
Dagli [282].
(a) Mechanism. The thermomechanically induced formation of polymer
radicals at processing under high temperature and shear are well known
[283]. Their use in recombination reactions and generation of graft and
block copolymers has been reported for the example of PE/PA-6 [284]. The
use of free-radical-generating compounds, e.g. organic peroxide, to improve
the blend properties has been described for the early stage of polymer blend
development on the same blend [285].
Various efforts have been made to develop further this approach. Terms
such as interfacial free-radical grafting or cross-linking [286], interphase
cross-linking [287] and peroxide modification or compatibilization [288,
289] have been used. In some cases, to improve the interfacial grafting, a
cross-linking agent or monomers have been added [290-292]. The importance of the peroxide solubility in the blend components on the interfacial
grafting has been shown [205]. To highlight the possibilities and opportunities of organic peroxide in the polymer blending area several examples will
be discussed based on PP as one of the blend components.
(b) PP/thermoplast blends
PP/PE blends. Blending or compatibilization in the presence of organic
peroxide has been investigated mainly on the PP/PE blend [293-296]. PP
chain scission and PE cross-linking occurs at the same time. A reactive
extrusion on PP/LLDPE (50: 50 wt: wt) blend has been performed by
injection of free-radical initiator (DTBPHY) into the feed port of the
extruder [293]. A high degree of dispersion of one polymer in another is
required so that when reaction occurs at the phase interface enough
graftlinks (combinations of polymer radicals) should be formed. For this
reason the extruder temperature has been set as cool as possible and a static
mixer attached to the single-screw extruder has been set to an elevated
temperature. Most of the initiator has been decomposed in the static mixer.
Addition of initiator during melt blending of PP /LLDPE caused an increase
in elongation at yield but a decrease in the impact strength and yield
strength. Blend characterization showed that, in the presence of peroxide,
degradation of PP occurred and chain extension and/or branching occurred
in the PE phase. At a higher initiator concentration of about 0.2 wt%
cross-linking products were present. The maximum size of the dispersed
119
phase decreased from 4 microns to less than 2 microns by addition of

peroxide, but the copolymer formation could not be detected with sizeexclusion chromatography, temperature rising elution chromatography or
differential scanning calorimetry.
A PP-Iow-density-PE (LDPE) blend was investigated through the whole
concentration range by mixing components in a co-rotating twin-screw
extruder and injecting diluted DTBPH (0.1 and 1 wt%) downstream [294].
The injection molded samples show a higher tensile strength at break over
the entire range of the reacted blend composition, but only the LDPE-rich
blends showed a satisfactory overall balance of mechanical properties.
With hydro quinone as the cross-linking agent and peroxide (DTBPHY:
1-3 wt%) in higher concentration, extensive cross-linking in the PP/LDPE
blend occurs [287]. The gel content in the PP/LDPE blend does not depend
on the PP portion and the impact properties are significantly improved by
cross-linking. Cross-linking leads to increased interaction on the interphase
owing to formation of interlinks between PE and PP. Bringing together the
dissimilar rheological properties of polymer components in the PP/LDPE
blend with DTBPH resulted in improved dispersive mixing and finer and
more uniform blend morphology [295]. In addition, the PP/PE ratio, type
of PE, amount of peroxide and processing conditions influenced the crystallinity, interfacial adhesion, blend morphology and rheology of PP/PE
blends.
Mixed plastics (waste). Blends of several virgin plastics have been used
to investigate the influence of peroxide in compatibilization of multicomponent polymer blends with potential application in plastic waste recycling.
The use of relatively high levels of peroxide (DTBPH: 0.5-2 wt%) improved
the mechanical properties of simulated mixed plastic waste [289]. The
influence of up to 20 wt% of PP in different types of PE has been examined
in the presence of several conventional compatibilizers and peroxides [288].
Increase in breaking strain could be achieved by addition of 0.1 wt% of
DCP. Reaction of a blend of PP-based polymers representing a recycled
automobile dashboard with DTBPH resulted in a material with improved
processing properties but reduced impact strength [297].
Polypropylene/polyamide blends. From the introduction of the reactive
compatibilization for polyolefin/polyamide (PA) blends with peroxide
[285], especially the PP/PA blend, gained the most attention from many
researchers. Improved compatibilization can be achieved, e.g. with maleicanhydride-grafted PP [298], acrylic-acid-functionalized PP and other
monomer combinations [62]. The grafted monomer on the PP reacts with
the amide or amine end group of P A, forming a graft copolymer.
Compatibilization of PP and PA-6 in one processing step with enhanced
interfacial reaction has been achieved by addition of maleic anhydride and
120
different peroxides (DTBPH, DTBPHY, DTBPIB and DCP) by blending

the polymer mixture [286, 299]. The importance of the final molecular
weight of PP on blend properties has been demonstrated and should be kept
in mind when reactive processing PP with peroxide.
(c) Polypropylene/elastomer blends
Thermoplastic elastomer vulcanizates. In the early stage of the development of elastomeric blends based on curable rubber and thermoplastics it
was recognized that the peroxide which dynamically (under shear conditions) cures the rubber was also involved in interfacial grafting reactions
between rubber and PP [300, 301].
An overview of different rubber/thermoplast (PP) blends cured, among
others, with peroxide has been made [302] (this is discussed in ch. 9).
Besides rubber cross-linking, PP chain scission occurs, which adversely
affects the mechanical properties of the TPE vulcanizate. To prevent this,
very often coagents are added such as bismaleimide and triallyl cyan urate
[303]. The coagent increases the cross-link density in the rubbery phase and
improves the grafting between PP and rubber. Figure 2.14 shows the
properties of different rubber/PP (60: 40 wt: wt) blends cured with a
bismaleimide/DCP system [303].
The increase of the interpolymers (graft-links) in natural rubber (NR)/PP
10
9
8
rn
a..
C/l
C/l
~ 6
~
4
2
3
c
2
~
U;
'iii
1
00
50
100
150
200
Tensile strain (%) Figure 2.14 Stress-strain behavior of different elastomer-thermoplast combinations, Elastomer-Thermoplast = 60%: 40% wt: wt; dynamic cured with BMI/DCP. Curve 1 = NBR/PP;
curve 2 = EPDM/PP; curve 3 = NR/PP; curve 4 = BR/PP; curve 5 = SBR/PP. For abbreviations, see Appendix 2.A. Reproduced with permission from Radusch, H.-J., Luepke, T.,
Poltersdorf, S. and Laemmer, E., Kautsch. Gummi, Kunstst., 43, 767; published by Hiithig,
Heidelberg, 1990.
121
(60: 40 wt: wt) blends by addition of peroxide has been followed by an

extraction method and estimation of non-soluble PP phase [304]. The
formation of graft-links between thermoplast and rubber in the presence of
peroxide has been shown [305]. Tensile properties and morphology of
EPDM/PP/HDPE ternary blend has been examined by the addition of
DCP [306]. Depending on the processing conditions and amount of DCP,
in the range 0.3-1.4 wt%, a decrease in the crystallinity of PP and highdensity PE (HDPE), mechanochemical degradation of PP and cross-linking
of EPDM occurs.
Impact modification of P P. Improvement of impact properties of PP
can be achieved by incorporation of 5-20 wt% elastomer to PP by blending
it in the melt phase. To suppress the degradation of PP by blending it in
the presence of a peroxide a preblend/masterbatch has been prepared with
50-75 wt% EPDM in PP. This masterbatch was subsequently mixed with
PP to the desired rubber content in PP [307]. Peroxide and co agent have
been used in blending NR and PP. Figure 2.15 shows the improvement of
impact and yield strength of the NR/PP blend (10: 90 wt: wt) with peroxide
content [308].
(d) Summary. Organic peroxides can be used as a low molecular weight
compatibilizer in thermoplast/thermoplast and thermoplast/rubber blends.
In a few cases they have been tested in application as a coupling agent in a
composite/thermoplast system [309, 310]. The function of peroxides as
compatibilizers is often related to their effect of leveling off dissimilar
220
40
%~. <f'Eu
'I
30
E
u
E
u 20
~ 10
-Sc:::
'Iii
t5
as
a.
!!!
.-0/
/.
_.--"
--......
210
-Sc:::
205
(a)
",..,.0
-",0
/0
!!!
'Iii 200
"0
Qj
>= 195
190~~~~~-L--~--~
2L..-..~~~~-L---~"""""'"
0.00 0.01 0.02 0.03 0.04 0.05

Peroxide content (wt%)
215
(b)
0.00 0.01 0.02 0.03 0.04 0.05

Peroxide content (phr)
Figure 2.1S (a) Impact, and (b) yield strength of NR/PP (10%: 90% wt: wt) blend versus
peroxide content (DTBPIB), with 0.6 phr trimethylol-propanetriacrylate. Part (a): 0 = 25C,
= - 20C. Reproduced with permission from Yoon, L.K., Choi, C.H. and Kim, B.K., J. Appl.
Polym. Sci., 56, 239; published by John Wiley, New York, 1995. 1995, John Wiley.
122
rheological properties of the blend components by inducing simultaneously

degradation and/or chain extension reactions. In situ block copolymer
formation, based on cross-interfacial polymer reactions in the presence of
peroxide, also plays a role in polymer blending. Polymers bearing peroxy
groups [311] may be used to promote interfacial adhesion between two
polymer phases through reaction in phase boundaries without causing
major changes in the dispersed and matrix polymers.
2.4 Future trends
Polyolefins, in particular PP, are moving from commodity resins to highperformance resins. The properties of PP resins are increasingly tailored to
specific applications by new catalyst technologies in the polymerization
[1,2] and by modification techniques of the final polymer. Reactive extrusion will be one of the most attractive techniques for such modifications. The
free-radical polymerizations of non-olefinic monomers on PP in solid
porous polymers are also promising developments [312]. In most of these
modifications, organic peroxides play a key role as initiators of radical
reactions. Modifications of PP by organic peroxides will in the future be an
interesting area of activity for the polymer producer, compounder and
producer of end-use articles. Continuous efforts are directed at the development of new organic peroxides or adaptations of peroxide formulations for
(new) applications in the modification of polyolefins, whereby the major aim
is to create polymers with unique structures and performance which are not
attainable by existing polymerization technologies. In addition, new peroxides are desired with increased efficiency, subsequently better cost-performance and a lower amount of decomposition products, allowing better
organoleptic properties in the modified polymer and acceptability for
food-contact applications.
Special groups of peroxides are being developed which are highly effective
or have a specific performance. These include multifunctional peroxides such
as peroxides with unsaturated groups [313-315], hydroxyl- [316], acid[23] or silane- [317] functional peroxides. In the cross-linking of polyolefins
by 1-(2-t-butyl peroxy isopropyl)-3-isopropenyl benzene, the aromatic part
of the peroxide is chemically bound to the polymer chain and the amount
of aromatic decomposition products was therefore substantially reduced
[313]. t-Butylmonoperoxymaleate is an example of a multifunctional peroxide capable of directly incorporating acid and anhydride groups in polymers
[23]. With vinyltris(t-butylperoxy)silane-modified polyolefins improved adhesion to metals was obtained [317]. In particular cases, functional groups
can be incorporated in the polymer after an induced decomposition reaction
and subsequent rearrangement of multifunctional peroxides. Allylic peroxides have been shown to give epoxide functionality in polyolefins in this way
123
[315]. When functional peroxides are used the degree of incorporation of

the functional groups can be very efficient without the need to remove
unreacted monomer. The majority of reports on multifunctional peroxides
concerns modifications of polyolefins such as PE or EP(D)M rubbers. For
modifications of PP such multifunctional peroxides could also be a promising group of peroxides.
The use of peroxides incorporated in a polymer is a recent development.
Such peroxides can be a part of the backbone, but can also be pendent
groups. In most cases peroxides with unsaturated groups are used to
prepare polymers with perester side groups [311]. However, because of their
short halflife, such polymeric peroxides are difficult to apply in a melt
modification process of PP.
An interesting application of modification of PP by grafting reactions is
the preparation of polymer bound additives, such as UV absorbers [237J,
antioxidants [61J or hindered amine light stabilizers [278, 279, 318].
A major problem in the development of chemical modification processes
of PP is often the lack of knowledge of the effects of process variables and
reaction conditions on the composition and properties of the material
obtained. Better insight into the chemical processes, in particular the radical
chemistry related to the use of organic peroxides, will contribute to the
development of new and improved methods for modifications of PP.
Acknowledgements
The contributions of university student trainees and many collegues of Akzo

Nobel Central Research who took part in our research projects and those
who helped with the preparation of this paper are gratefully acknowledged.
Appendix 2.A
2.A.i.i
Polymers
ABS
aPP
CR-PP
EPDM
EPM
EVA
HDPE
iPP
LDPE
LLDPE
NR
PA
PE
PMMA
PP
PPE
PP-g-PS
PS
PVC
TPE
Acrylonitrile-butadiene-styrene terpolymer
Atactic polypropylene
Controlled-rheology PP
Ethylene-propylene-diene monomer terpolymer
Ethylene-propylene copolymer
Ethylene-vinylacetate copolymer
Isotactic polypropylene
Natural rubber
Polyamide, nylon
Polyethylene
Poly(methyl methacrylate)
Polypropylene
Poly(phenylene oxide)
Polypropylene-polystyrene graft-copolymer
Polystyrene
Poly(vinyl chloride)
Thermoplastic elastomer
2.A.i.2 Peroxides!
AIBN
BPIC
BPO
DCP
DMDPB
DTBP
DTBPH
DTBPHY
DTBPIB
EHP
2,2-Azobis(isobutyronitrile) (Perkadox AIBN)

t-Butylperoxy isopropylcarbonate (Trigonox BPIC)
Dibenzoyl peroxide (Lucidol)
Dicumyl peroxide (Perkadox BC)
2,3-Dimethyl-2,3-diphenylbutane (Perkadox 30)
Di-t-butyl peroxide (Trigonox B)
2,5-Bis( t-butylperoxy)-2,5-dimethylhexane (Trigonox 101)
2,5-Bis( t-butylperoxy)-2,5-dimethylhexyne (Trigonox 145)
Bis(t-butylperoxyisopropyl)benzene (Perkadox 14)
Bis(2-ethylhexyl) peroxydicarbonate (Trigonox EPH)
1 Perkadox, Trigonox and Lucidol are tradenames of peroxides of Akzo Nobel Chemicals
[36].
LPO
TBCP
TBHP
TBPB
TBPEH
TBPP
125
Dilauroyl peroxide (Laurox)

t-Butylcumyl peroxide (Trigonox T)
t-Butyl hydro peroxide (Trigonox A)
t-Butyl peroxybenzoate (Trigonox C)
t-Butylperoxy-2-ethylhexanoate (Trigonox 21)
t-Butyl peroxypivalate (Trigonox 25)
2.A.I.3 Miscellaneous
BGA
DSC
DVB
ESR
FDA
GC
MFI
MWD
NMR
UV
Bundesgesundheitsamt
Differential scanning calorimetry
Divinylbenzene
Electron spin resonance spectroscopy
Food and Drug Administration
Gas chromatography
Melt flow index
Molecular weight distribution
Ultraviolet radiation
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Sanchez, 1. and Baron, A.L. (1990) European patent 381 135.
Berg, A.L. and Endstra, W.C. (1977) G.A.K., 30, 280.
Ligner, G. and Avar, L. (1994) ACS Meeting, Chicago, 34, 160.
Blends of poly ami des and maleic-anhydridecontaining polymers: interfacial chemistry

and properties
M. VAN DUIN and R.J.M. BORGGREVE
3.1
3.1.1
Introduction
(In situ) compatibilization of polymer blends
Mixing two or more polymers usually results in phase separated systems,

although molecularly miscible polymer blends are known too, some of them
having economic importance. Blends of immiscible polymers offer attractive
opportunities for achieving unique property combinations, minimizing weak
properties and/or obtaining optimum cost/benefit ratios. The performance
of multiphase blends depends critically on their phase morphology and the
nature of the interface between the phases. Quite often immiscible polymer
blends have poor mechanical properties relative to their components and
the phase morphology is strongly dependent on the details of the processing
history.
In practice, polymer blends are produced by melt mixing rather than by
blending in solution. Unfavourable interactions between the molecular
segments of the components result in a high, interfacial tension in the melt,
which makes it difficult to disperse the components properly during mixing.
It brings about phase rearrangements under low stress or quiescent conditions, which result in variation of properties. Moreover, poor interfacial
adhesion in the solid state causes premature, mechanical failure and brittle
behaviour, as weak interfaces may act as catastrophic defects. The way to
overcome most of these problems is compatibilization. The addition of
appropriate block or graft copolymers that act as interfacial agents has been
shown to be effective [1-4]. However, the route of compatibilization by
means of preformed copolymers is not used much in practice as there seems
to be a lack of economically viable and practical methods for synthesizing
such additives for blends that are of interest. Besides, addition of preformed
compatibilizers is often accompanied by problems such as long times of
diffusion to the interface or micelle formation, so that considerable amounts
of compatibilizer are required.
An attractive alternative to preformed compatibilizers is the in situ
formation of block or graft copolymers during melt blending via interfacial,
chemical reactions of the (functionalized) polymeric components. This is a
Chapman & Hall 1997
134
very effective way of compatibilization, as the copolymers are formed at the

site where they are needed: at the interface. In general, both polymers have
to be functionalized with chemical groups which show reactivity towards
each other. However, in situ compatibilization of polyamides (PAs) requires
functionalization of the second blend component only: the amine and
carboxylic acid end groups and/or the amide chain functions of PA may
serve as reactive sites for, for instance, acid- or anhydride-containing
polymers. It was recognized early that interfacial chemical reactions upon
melt blending of PAs with functionalized polymers result in fine and stable
morphologies. A British patent issued in 1965 [5] described that PA-6.6
may be toughened by the incorporation of ethylene- (meth)acrylic acid
copolymers as a dispersed phase in the form of particles with diameters less
than 5 .urn. It was observed that the melt viscosity of the blend was
substantially higher than that of either component, which was interpreted
as an indication that chemical reactions had taken place between the PA
and the acid-containing copolymer.
3.1.2
Blends of polyamides and maleic-anhydride-containing polymers
PAs have been used for numerous engineering applications, since they
became available as moulding and extrusion materials. Some of their
favourable properties are high strength and modulus, good chemical and
abrasion resistance, high melting point, low coefficient of friction and
toughness. However, under certain circumstances, such as low temperature
and in the presence of sharp notches, PAs are brittle. Since the 1960s
numerous efforts have resulted in hundreds of patents describing PA
compositions with improved ductility. An overview of important patents on
toughened PAs has been given by Keskkula and Paul [6]. They conclude
that the most far-reaching patent in this field, with 168 examples and 55
claims, was issued to Epstein [7] in 1979. In this patent it is claimed
that melt blending of acid- and anhydride-containing elastomers with
a PA results in super-tough materials, provided that the rubber is dispersed
into particles measuring between 0.01-1.um and adhering to the PA
matrix. Nowadays, most PA producers have a rubber-toughened grade,
including a maleic-anhydride-(MA)-modifed rubber as compatibilizer in
their product assortment. Ethylene-propylene-diene terpolymer (EPDM),
hydrogenated styrene-butadiene-styrene terpolymer (SEBS) and butadiene
rubber (BR) are the rubbers that have been studied and patented most
widely.
PAs can also be combined with a number of engineering polymers to
yield polymer blends for applications requiring a high heat deformation
temperature, less moisture sensitivity, attractive surface appearance of
fabricated parts or reduced cost. Again, one principal point becomes
apparent when examining the patent literature: the non-PA blend component contains a functional group capable of reacting with PA and very often
BLENDS OF POLYAMIDES AND MA-CONTAINING POLYMERS
135
Table 3.1 Selected patents involving the use of maleic-anhydride-modified polymers for
polyamide-blend compatibilization. For abbreviatons, see Appendix 3.A
Blend
PA/rubber
PA/PP
PA/ABS
PA/PPE
Patent No.
US
US
EP
EP
US
US
US
US
4174 358
4346194
0194705
0261748
4713 415
4987 185
4681 915
4888 397
Year
1979
1982
1986
1988
1987
1991
1987
1989
Company
Du Pont
Du Pont
DSM
Shell
Monsanto
Monsanto Kasei Co.
General Electric
General Electric
this functional group is MA. Examples of MA-functionalized polymers

(MA-f-pol) that have been incorporated into PA and of which the PA
blends are commercially available at present are poly(dimethyl phenylene
oxide) [8-11], polypropylene (PP) [12, 13] and acrylonitril-butadienestyrene terpolymer (ABS) [14-18]. In addition, a large variety of blends of
PA with the copolymer of styrene and MA (SMA) and a third blend
component (polystyrene (PS), poly(styrene-co-acrylonitril) (SAN), ABS,
poly(methylmethacrylate) (PMMA) and PPE) have been studied.
The utilization of anhydride- or acid-functionalized polymers (f-pol) in
the compatibilization of blends containing PP has attracted both academic
and industrial interest. Table 3.1 shows some important patents for the use
of MA-f-pol to improve the properties of PA-containing blends.
The MA-f-pols are usually produced by radical or thermal grafting of
MA onto polymers, especially polyolefins, or by copolymerization of MA
with suitable co-monomers such as styrene. Other functional groups can be
incorporated in a polymer for reactive compatibilization with PAs, such as
(meth)acrylic acid, oxazolines and epoxides, but MA is the most widely
used. A major advantage of MA is its susceptibility for radical grafting or
copolymerization and the lack of homopolymerization [19]. As a result,
only short MA grafts are present in graft copolymers and MA monomers
are isolated in the backbones of copolymers. This results in effective use of
MA. Furthermore, as no free MA homopolymer is formed, only residual
MA monomer has to be removed after grafting [20]. Finally, the resulting
succinic anhydride moiety shows reactivity for a variety of functional
groups, such as amines, epoxides, oxazolines, isocyanates and under some
circumstances alcohols, and it is relatively inexpensive (about $1000 per
1000 kg).
3.1.3 Scope o/review

The goal of this review is twofold. First, published data on PA/MA-f-pol
blends will be summarized, with the emphasis on scientific papers of the past
136
Chemical and physical structure

of blend components
Blend composition
Processing conditions
(Im)miscibility
Interface
Rheology
Chemistry
Morphology
mutually and
continuously
interacting
Properties
Figure 3.1 Structure-properties relationships in in situ compatibilized polymer blends.
decade; patents are not included. Second, an attempt is made to develop

structure-properties relationships, correlating the various phenomena in
these blends (Figure 3.1).
In polymer blends compatibilized by addition of a preformed, block or
graft copolymer the final morphology and thus the properties are more or
less independently determined by the blend composition (volume ratio of
blend components, amount and nature of compatibilizer, etc.), the physical
properties of the polymers (glass transition and melt temperature, interfacial
tension, etc.) and the rheology of the blend (absolute viscosities and viscosity
ratio). In addition, the processing conditions (equipment, screw design,
temperature, residence time, etc.) are of importance. In in situ compatibilized
blends the compatibilizer is formed during melt mixing and structureproperties relationships are more complex, as chemistry, rheology and
morphology interact continuously as long as reactive groups are present. As
a result, variations in processing may result in changes in morphology and
properties. As long as chemical reactions are still taking place, additional
processing steps or recycling may also result in a change of properties.
137
3.2 Interdependence of chemistry, rheology and morphology - interface

3.2.1
Chemistry in blends of polyamides and maleic-anhydride-containing

polymers
( a) Reactions of amines, amides and polyamides with low molecular weight

anhydrides
Reactions with amines. P A chains contain two functionalities that might
be reactive towards anhydride groups, namely, the amine end groups and
the amide chain groups. Note that in this review anhydride and imide refer
to the five-membered cyclic structures only, that is, succinic anhydride and
succinimide, respectively, unless a special adjective such as linear is used.
Low molecular, aliphatic, primary amines (1) are reactive at room temperature towards anhydrides (II) (Scheme 3.1) [21]. The nitrogen of the amine
attacks an anhydride carbonyl resulting in ring opening and formation of
an amic acid III, (I + II --t III). The high reactivity of these amines, for
instance in comparison with alcohols, is explained by the high nucleophilicity of the nitrogen. Even in solution at room temperature the
reaction of these amines with anhydrides is almost instantaneous. Amide
acid formation is a reversible reaction: at elevated temperatures the amine
and anhydride are re-formed (III --t II + I). For primary amines this reverse
reaction competes with ring closure to imide (IV) at 100C-150C
(III --t IV + H 2 0).
If an excess of aliphatic amine is present the carboxylic acid function of
the amic acid is neutralized to the corresponding ammonium salt (V), which
usually has a lower solubility (I + III --t V). As the temperature is increased
up to 170C this salt may dehydrate and the diamide (VI) may be formed
(V --t VI + H 2 0) [22]. Upon heating above 200C the diamide is converted
to the imide with formation of an amine (VI --t IV + I). In the presence of
special, dehydrating agents, such as acetic anydride [23] or N,N'-dicyclohexylcarbodiimide [24], the iso-imide (VII) may be formed from the amic
acid too, which is thermally unstable at room temperature and converts to
imide (VII --t IV). In principle, the imide is sensitive towards hydrolysis
(IV + H 2 0 --t III), but in a neutral environment the imide is a stable
product until at elevated temperature pyrolysis occurs. Under extreme
conditions the imide may react with an excess of amine, yielding the imide
imine (VIII).
Reactions of anhydrides with amides. In contrast to reactions of low
molecular weight anhydrides with amines only a few studies have been
reported for those with amides (IX) [21, 22, 25]. Owing to the low
nucleophilicity of aliphatic amides their reactivity towards anhydrides is
C:>
.. .
o
e
H3N-R
(tl
NH-R
III
R-NH-LR,
l
JX
NH-R
XI
~JLR'
0
R~OH
OH
VI
H-R
NH-R
-R-NH!
..
VII
~
-R-NH-L R,
OH
-H20
- H2O
C;a
o IV
c}~
-H2O
RNH2
VIII
cr
....R
N
Scheme 3.1 (a) Reactions of low molecular weight, five-membered, cyclic anhydrides with amines and amides.
IX
!R-NH2
OH
-~
C::::-H--R ..
~o l~~'
: R: I -R:JL
II
R-NH---U..-R' _0_
H201-R~OH
R-NH 2
N/
R-NH,
139
+===:t:
- H,O
Scheme 3.1 (b) Amidation-hydrolysis and transamidation equilibria.
several orders of magnitude lower than that of corresponding amines (a pKa

of 15 compared with 4). At temperatures above 140C the amide is degraded
in the presence of an anhydride: the amine part is combined with the
anhydride and an imide is formed, whereas the carbonyl residue results in a
carboxylic acid (Scheme 3.1) (IX + II ~ IV + R'-COOH). Acids and water
are effective catalysts [25]. As for intermediates, the linear imide-acid (X:
analogue of the amic acid of the amine) has not been demonstrated
(IX + II ~ [X]) [21,22]. However, Tessier and Marechal showed that in the
temperature range 150 to 200C, minor amounts of the amide-linear-imide
(XI) are formed (2 IX + II ~ XI + R'-COOH) [22]. At temperatures above
200C it has not been possible to demonstrate the presence of this species, XI
[21]. The formation of the amide-linear-imide (XI) suggests a direct reaction
between anhydride and amide. However, there is sufficient evidence for
PA/MA-f-pol blends that the reaction proceeds indirectly via hydrolysis of
the amide (vide infra). Finally, it has to be noted that amides themselves are
not inert. They are moisture sensitive (amidation-hydrolysis equilibrium)
and may participate in transamidation reactions (Scheme 3.1(b)).
Polymer analogous reactions. Chemical characterization of the reaction products of PAs with low molecular weight anhydrides at temperatures
above 200C demonstrates the formation of amide-linear-imide (XI),
imide (IV) and additional carboxylic acid only [21, 22, 26]. This shows
that, although amine end groups are preferentially converted (I + II ~
IV + H 2 0), PA amide groups are also involved in reactions, resulting in PA
chain scission (IX + II ~ IV + R'-COOH). The actual degree of PA chain
scission is determined by the initial anhydride: amine molar ratio. It has
recently been shown that PA-6 can be recycled by kneading with large
amounts of trimellitic anhydride, resulting in useful monomers for polycondensation polymers [27].
The gradual, but substantial decrease of the torque during melt mixing
of PAs with low molecular weight anhydrides is evidence of the occurrence
ofPA chain scission (Figure 3.2(a)) [26,28,29]. Two mechanisms have been
proposed: a slow reaction of the anhydride with the PA amide, resulting in
direct chain scission (Scheme 3.1(a): IX + II ~ IV + R'-COOH); or fast
amine end group capping (Scheme 3.1(a): I + II ~ IV + H 2 0) followed by
140
(b)
----(a)
Time
Figure 3.2 Torque development upon addition of a mono- and a dianhydride to a polyamide
melt (indicated by arrow); (a) PA-6/phthalic anhydride, and (b) PAmXD.6/pyromellitic
dianhydride. For abbreviations, see Appendix 3.A. Curve (a) redrawn from Park, I., Barlow,
J.W. and Paul, D.R., in J. Pol. Sci., Phys., BJO, 1021 (1992); curve (b) redrawn from De Roover,
B., Etude des melanges constitues de poly(m-xylyime adipamide) et de polypropyleneJonctionnalise
par l'anhydride maleique, PhD thesis, Universite Catholique de Louvain (1994).
a slow PA amidation-hydrolysis equilibration (Scheme 3.1(b, resulting in

indirect chain scission and formation of new carboxylic acid and amine end
groups. From simple numerical calculations it follows that the nature and
the molecular weight of the reaction products are identical for both routes
[30]: the overall reaction equations are identical.
Addition of a stoichiometric amount of pyromellitic dianhydride to poly(m-xylylene adipamide) (PAmXD.6) results in an immediate increase of the
melt torque, followed by a gradual decrease to a constant level [30] (Figure
3.2(b. This indicates that, first, amine end groups react with the dianhydride,
resulting in an increase of molecular weight (chain extension). This is followed
by re-equilibration until a new amidation-hydrolysis equilibrium is reached.
This latter equilibration is rate determining. De Roover reviewed kinetic data
for the two mechanisms discussed above and showed that, even when the high
amide: amine ratio of PAs ( 1) is taken into account, the reaction of amines
is favoured [30]. However, it has been shown that extrapolation of data from
low to high molecular weight systems is not straightforward, owing to local
environment effects in the case of polymers [31].
Polymer analogous reactions have been carried out using various MA-fpols and a low molecular weight amine [21, 22, 32-35]. Amic acid
(ammonium salt) [III(V)], diamide (VI), imide (IV) and iso-imide (VII) were
demonstrated and the relative amounts were shown to vary with the
reaction conditions (temperature, stoichiometry and catalyst) as shown in
Scheme 3.1(a).
141
(b) Reactions in blends of polyamides and maleic-anhydride-containing

polymers
Evidence for coupling of polyamide to maleic-anhydride-containing polymer. Selective extraction of one of the two components of PA/MA-f-pol
blends has frequently been used to study grafting of PA to MA-f-pol.
However, this should be done with caution, as extraction of the dispersed
MA-f-pol phase out of a semi-crystalline PA matrix or extraction of the
continuous phase out of a PA/MA-f-pol blend with occlusions in the
dispersed phase provides only qualitative information on the degree of
grafting [29]. After isolation of the residue (using filtration or (ultra)centrifugation), various techniques such as differential scanning calorimetry
(DSC), Infra red (IR) spectroscopy (Figure 3.3(b)) or elemental analysis
have been used to determine the chemical composition, thus demonstrating
the formation of graft copolymer.
If PA is the continuous phase, extractions are usually performed with
formic acid. The occurrence of a stable, white, colloidal suspension is
interpreted as evidence for block copolymer formation (Molau test [36]).
Insufficient compatibilization results in flocculation, whereas co-continuous
morphologies result in a coarse, milky solution [26]. For instance, Triacca
et aZ. showed that for 60: 40 (wt: wt) blends of PA-6 with ABS, PA-6 grafts
were formed upon addition of SMA (25 wt% MA) as compatibilizer and
that increasing the amount of SMA in the blends from 0 wt% to 10 wt%
resulted in enhanced graft formation: the amount of un extractable PA-6 of
the original PA-6 increases from 0% to 11 % [14].
Quantitative extraction can also be performed if the non-PA phase is
continuous. Ide and Hasegawa [37] used PA-6/PP and PA-6/PP-g-MA
(20: 80 wt: wt) blends and showed that when un grafted PP was used in the
blend, extraction of the PP with xylene yielded 20 wt% residue, which
corresponds to the original amount of PA-6 used in the blend. Further
confirmation for the exclusive presence of PA-6 in this residue was demonstrated from DSC results. When PP-g-MA was used in the blend instead,
the yield of the residue increased from 20 wt% to 30 wt% and DSC
measurements showed the presence of both PA-6 and PP in this residue. In
the latter case, the amount of PP linked to PA-6 was shown to increase with
increasing the anhydride-to-amine molar ratio from 0 to 1.0.
Repeated extractions with various solvents, i.e. coacervation, allows the
fractionation of PA/MA-f-pol blend [34], and sometimes the actual isolation of the PA/MA-f-pol graft-copolymer [28]. In the case of 80: 16 (wt: wt)
PA-6/PS blends, compatibilized by 4 wt% PS containing terminal anhydride
groups (obtained by anionic polymerization and end capping with trimellitic
anhydride chloride), not all the functionalized PS was shown to be involved
in the grafting reaction [28]. Surprisingly, the degree of interfacial reaction
142
anh.
c:
o
iii
e
!II
!II
c:
I"CI
t!:
4000
3200
2400 2000
1600
1200
800
400
Wave number (em l )
Figure 3.3 Infra red spectra ofa 50:50 (wt:wt) blend of PA-6 and SMA (28wt% MA): (a) as
such, (b) after formic acid extraction, and (c) after hydrochloric acid treatment; the main
anhydride (anh.) amide and the combined imide-carboxylic acid peaks are labelled. For
abbrevations, see Appendix 3.A. Reproduced from van Duin, M., Aussems, M.A. and Borggreve, R.J.M., J. Pol. Sci., Pol. Chern. Ed. (submitted).
143
seems to be more or less independent of the molecular weight and the

anhydride content of the functionalized PS.
Chemistry of coupling polyamide to maleic-anhydride-containing polymer.
Blends of PAs with MA-f-pol are usually obtained via melt blending at
temperatures above 200C. As a result, the amic acid (ammonium salt) (III
and V) and the diamide (VI) will only be intermediates. The iso-imide (VII)
will not be formed at all, owing to the elevated temperature, but also
because dehydrating agents are not applied in PA/MA-f-pol blends. Imide
imines (VIII) have been suggested to explain cross-linking phenomena when
converting polyamic acids to polyimides, but if traces of water are present,
as is usually the case in PAs, the imines will be quickly hydrolyzed. At
temperatures above 200C the imide (IV) probably is the only species
formed. As discussed in subsection 3.2.1(a) and exemplified for PA/MA-f-pol
blends below, amide (IX) does not react directly with anhydride (II), but
indirectly via amine end groups (I) followed by re-equilibration. As a result,
Scheme 3.1 is simplified to Scheme 3.2 for PA/MA-f-pol melt blending.
Direct evidence for the conversion of anhydride into imide in PA/MA-fpol blends is hard to provide owing to insufficient signal-to-noise ratio
and/or overlap with intense amide peaks in IR (Figure 3.3a) or nuclear
magnetic resonance spectra. Marechal [26] was able to subtract the IR
spectrum of PAmXD.6 from spectra of PAmXD.6EPM-g-MA blends.
Spectral curve fitting of the residual IR spectra allowed quantification of the
conversion of anhydride to imide. For batch melt mixing the conversion was
time dependent for low screw speeds only, indicating that chemical reactions
in the blends occur mainly in the early stage of mixing. This was confirmed
by titrations: at high screw speeds no further reduction of the amount of
amine end groups was observed after 30 s of mixing [26]. Using IR
spectroscopy De Roover [30] showed that in the formic acid extraction
residue of PAmXD.6/PP-g-MA blends (90 to 75 wt% PA) the grafted MA
of PP-g-MA is completely converted.
R- NH
--1LR,
IX
H2O
0
-R:...JL OH
cia
R-NH 2
-H 2O
II
R-N~
0
IV
Scheme 3.2 Reactions of polyamides with maleic-anhydride-containing polymers in the melt.
144
MA-f-pol
PA
~I
HOOC
o H~
"
Scheme 3.3 Artist's impression of imide formation and polyamide chain scission at the interface
in blends of polyamides and maleic-anhydride-containing polymers.
Indirect evidence for imide formation and quantification of MA conversion is possible via hydrochloric acid hydrolysis of PA/MA-f-pol blends [29,
34, 38]. Via reference samples, it has been shown that amide functions of
both the free and the grafted PA are degraded [29, 34]. However, the last
monomer of PA, bound to MA-f-pol via an imide function, is not removed.
IR spectroscopy of a 50:50 (wt:wt) blend of PA-6 or PA-6.6 and SMA
(28 wt% MA) after hydrochloric acid treatment demonstrates a conversion
of MA from 28 wt% to about 22 wt% and the presence of an imide peak
[29]. For hydrolyzed PA-6/MA-f-pol blends the imide peak overlaps with a
carboxylic acid peak corresponding to amino caproic acid bound as an imide
via the amine group (Figure 3.3(c)).
For PA/MA-f-pol blends the difference in reactivity of PA amine end
group versus amide chain functionality towards MA-f-pol has been a topic
of discussion and different opinions have been expressed. The various,
seemingly contradictory, observations can be brought into agreement by
taking the anhydride: amine molar ratio into account. If this ratio is below
1.0 PA will be linked to MA-f-pol via a direct reaction of the amine end
groups. For instance Ide and Hasegawa [37] showed that upon increase of
the anhydride: amine ratio from 0 to 1.0 the amount of grafted PP-g-MA
in 20: 80 (wt: wt) PA-6/PP-g-MA blends increases from 0 wt% to 10 wt%,
but then levels off. Consequently, the amount of amine end groups decreases
to 0 and this was supported by an increased difficulty of dyeing the PA
phase with an acid dye. Lawson et al. [34] showed that in a 80: 20 (wt: wt)
PA-6/hBR-g-MA blend with an anhydride: amine molar ratio of about 0.3,
the experimental amount of PA graft equals that calculated from the
amount of MA graft and the PA molecular weight. It was assumed that only
amine end groups and no amide groups react. In addition, the solution
viscosity of free PA-6 extracted from a variety of PA-6/rubber-g-MA blends
145
was more or less equal to that of the original PA-6. These findings support
the assumption that for anhydride: amine molar ratios lower than 1.0 the
higher intrinsic reactivity of the amine groups dominates that of the amide
groups and PAs are linked via the amine end groups to MA-f-pol.
It has been shown that at anhydride: amine molar ratios above 1.0
chemical reactions still occur, so amides have to be involved. It has been
discussed above that the imide formation proceeds via reaction of the amine
end group followed by PA hydrolysis, which is supposed to be rate
determining. PA chain scission occurs and new amine and carboxylic acid
end groups are formed. For instance, upon 1 h melt kneading the MA
content of SMA in blends with PA-6 or PA-6.6 (50:50wt:wt) decreases
from 28 wt% to 16 wt%, which is only possible if the average number of
chain scissions is about 20 per PA chain [29]. The solution viscosity of free
PA extracted from PA/MA-f-pol blends decreases when the amount of
MA-f-pol increases [26]. For a 50: 50 (wt: wt) PA-6.6/SMA (28 wt% MA)
blend, a reduction up to 50% of the weight average molecular weight of the
PA matrix was determined [29].
Length of polyamide graft. Several studies have shown that the number
average molecular weight of the PA grafts is smaller than that of the matrix
PA chains and decreases with increasing MA content of the MA-f-pol
(content of MA-f-pol itself or of the mixing temperature or mixing time [26,
29, 30, 38]). For instance, PA-6/EPDM-g-MA blends have been extracted
and the nitrogen content and MA conversion of the residues determined
[38]. The number average molecular weight of the PA-6 grafts in the residue
was calculated and was shown to be smaller than that of the free PA-6
matrix.
Various explanations have been put forward, which do not necessarily
exclude each other. Marechal [26] suggested that the concentration of
amine end groups in the PA layer close to the interface is relatively high.
This is most probable for low molecular weight PA, which prefers the
interface for entropic reasons. Therefore, low molecular weight PA will react
selectively, resulting in short PA grafts.
De Roover [30] has suggested that because the reaction between amine
and anhydride in the melt is very fast the grafting process is probably
diffusion controlled. The selectivity of grafting of low molecular weight PA
is then explained by its relatively high rate of diffusion.
Another explanation might be that the PA chains, once grafted to
MA-f-pol, will undergo selective hydrolysis at the interface [29] (Figure 3.4).
PA grafts will exhibit random coil configurations thus preventing other PA
chains from reaching the interface and reacting further. Upon imide formation a molecule of water is formed, which may hydrolyze a neighbouring
amide to an amine, which can subsequently react to form an imide. As a
result of this continuing reaction, the amount of the grafted PA (on a weight
146
Figure 3.4 Transmission electron micrographs of 50: 50 (wt: wt) blends of (a) PA-6/SMA, and
(b) PA-6.6/SMA (SMA: 28 wt% MA) (PA phases in coupes were stained with osmium
tetraoxide). For abbreviations, see Appendix 3.A. Reproduced from van Duin, M., Aussems,
M.A. and Borggreve, RJ.M., J. Pol. Sci., Pol. Chern. Ed. (submitted).
basis) does not vary, and this was shown experimentally in a 20: 80 (wt : wt)
PA-6/PP-g-MA blend [37] and in 50:50 (wt:wt) PA/MA-f-pol blends
(PA = PA-6 or PA-6.6; MA-f-pol = EPDM-g-MA or SMA containing
1.5 wt% or 28 wt% MA, respectively) [29]. However, the length of the PA
grafts decreases and the number increases. This explanation is supported by
the fact that in mixtures of PA-ll and a low molecular weight anhydride
which were heated to 205C for 20 h, the PA-ll grafts consisted of
monomers, dimers and trimers only [22]. For 50:50(wt:wt) PA-6.6/SMA
blends it has been shown that about 60% of the cross-links (vide infra)
consists of 1,6-hexanediamine monomer [29].
In principle one might expect that as a result of transamidation reactions the length of the PA grafts would eventually become equal to
that of the matrix PA chains. However, owing to loss of entropy as
148
dissolve in chloroform, indicating that it was cross-linked [42]. Increasing

the amount of SMA added to PA-mXD.6 was shown further to result in
insoluble material when the anhydride: amine ratio exceeds 1 [43]. Moreover, extraction of the free PA-6.6 from a 50: 50 (wt: wt) PA-6.6/SMA blend
revealed that 97 wt% of the SMA was present as a gel, which did not
dissolve in methyl ethyl ketone [29].
( c) Effects of chemistry on rheology. Rheological measurements on PAl
MA-f-pol blends have usually been limited to the determination of the
torque during melt blending (constant level after several minutes) or of the
melt index of the final blend. For a variety of PA/MA-f-pol blends, the melt
viscosity of the blend was shown to be higher than the viscosity of either of
the blend components [14, 26, 28, 30, 37,43]. An increase in the MA content
of MA-f-pol or a decrease of the MA-f-pol molecular weight results in
enhancement of the melt viscosity increase. These phenomena are usually
interpreted as evidence for the occurrence of grafting. However, one has to
be careful not to overinterpret these data, as melt viscosity increases also
occur for blends without in situ compatibilization as a result of the influence
of dispersion on rheology [30] (subsection 3.2.2(b)).
In this respect dynamic mechanical spectrometry (DMS) provides more
unambiguous information. DMS measurements of 50: 50 (wt: wt) PA/MA-fpol blends (MA-f-pol is EPDM-g-MA or SMA with 1.5 wt% or 28 wt%
MA, respectively) has demonstrated that an increase of the MA content of
MA-f-pol results in a decreased dynamic viscosity and, especially at low
frequencies, an increased loss angle [29]. These findings agree with enhanced
PA chain scission and shorter P A grafts as a result of the increased MA
content of the MA-f-pol (subsection 3.2.1(b)). For PA-6.6/MA-f-pol blends,
however, it was shown that log(dynamic viscosity) divided by log(frequency)
is close to -1.0 and the loss angle is small (frequency = 10- 1 rad s -1; loss
angle < 10). This is additional evidence of the phenomenon of cross-linking
when symmetric PAs are applied (subsection 3.2. 1(b)).
(d) Effects of chemistry on morphology. It should be noted that the

various phenomena related to morphology, such as the size and the shape
of the dispersed phase, the interfacial thickness and crystallinity, are not
determined by chemistry only. They are also affected by the composition of
the blend, the compatibility-interfacial tension of the polymers, the viscosity
ratio and the details of the processing procedure, as will be discussed in
subsection 3.2.2(a).
Coupling of PA to MA-f-pol results in graft copolymer formation,
whereby the interfacial tension is reduced and coalescence is prevented. This
explains the general observation of decreased particle size of the dispersed
phase by scanning or transmission electron microscopy (SEM or TEM,
respectively); sometimes a decrease of one or two orders of magnitude, upon
147
Figure 3.4 (Continued)
a result of coupling to the interface, relatively short grafts are most likely
maintained.
Asymmetric versus symmetric polyamides: coupling versus cross-linking. Paul et al. [39- 41] were the first to note the distinct difference in
chemistry between symmetric (PA-x,y) and asymmetric (PA-x) PAs. The
former are prepared from dicarboxylic acids and diamines and can be
viewed partly as high molecular weight diamines or as a potential source of
low molecular weight diamines. After sufficient conversion they may induce
cross-linking of the MA-f-pol. The latter PAs are obtained from IY.,Waminocarboxylic acids or the corresponding lactams and are high molecular
weight monoamines and result in coupling of PA to MA-f-pol only.
Cross-linking is frequently observed for blends of symmetric PAs with
MA-f-pols. Analysis of a commercial, tough, PA-6.6/ EPDM-g-MA blend
showed that after removal of PA, a large part of the isolated rubber did not
149
addition of MA-f-pol to PA blends. In fact, a decreased particle size is

usually interpreted as indirect evidence for the chemical process of coupling
of PA to MA-f-pol, i.e. for in situ compatibilization. In contrast to 80: 20
(wt:wt) PA-6/PS blends, annealing of PA-6/PS/PS-g-MA blends does not
result in a coarser morphology, which is evidence for prevention of coalescence due to PA/MA-f-pol compatibilizer formation [28]. Variations of the
MA content of the MA-f-pol and of the content and/or the molecular weight
of the MA-f-pol usually have a pronounced effect on the particle size.
For low MA content of MA-f-pol, the compatibilization reactions are
completed within a few minutes. As a result, the composition at which phase
inversion occurs and the dimension of the dispersed phase of PAmXD.6/PPg-MA blends do not vary after this time, although the blend torque changes
most likely due to PA degradation [30]. For high MA content of MA-f-pol,
chemical reactions may proceed for tens of minutes. For a 50: 50 (wt: wt)
PA-6/SMA (28 wt% MA) blend the particle size of the SMA dispersion
continuously decreases; after 1 h the particles are so small that they cannot
be visualized by TEM any more [29].
In the case of asymmetric PAs only coupling occurs, which allows a very
fine (0.05-1I1m), uniform and spherical dispersion (Figure 3.4(a. For
symmetric PAs cross-linking is possible, which explains the coarse ( 1 11m)
and often more complex morphology, varying from irregularly shaped
droplets to dendritic or cauliflower structures (Figure 3.4(b [29, 39-41,
44-46]. It is thought that the process of blend dispersion is interrupted by
cross-linking and that an intermediate, non-equilibrium morphology is
fixated. The presence of occlusions in the dispersed phase is a common,
although not exclusive, phenomenon for blends containing symmetric PAs
[29, 44, 46].
SEM on fractured samples shows smooth surfaces in the case of PA-6/
EPDM blends [47]. Upon addition of EPDM-g-MA the fracture surface
becomes rough, indicating increased interfacial adhesion. This phenomenon
was also observed in PA-6/SMA blends [48]. Only a few papers deal with
the actual presence of graft copolymers in the interface of PA/MA-f-pol
blends. An elegant extraction-encapsulation-TEM method has been developed by Nishio et al. [49] for determining the thickness of the PA graft layer
surrounding PP particles in PA-6/PP/PP-g-MA blends. An increase in the
PP-g-MA content resulted in an increase of the thickness of the PA graft
layer. Yukioka and Inoue [50] applied ellipsometry, an optical method for
determining the interfacial thickness, for bilayers of an amorphous PA and
SMA. At temperatures above 200C the interface is realized almost instantaneously and its thickness is not time dependent. The interfacial layer of
about 20nm is thicker than that of a non-reactive PA/SAN bilayer,
indicating that the graft copolymer is indeed located at the interface. Entire
graft copolymer chains are drawn into the interface to generate a very
smooth concentration gradient.
150
TEM micrographs of PA/MA-f-pol blends usually demonstrate the

presence of crystalline lamellae in the PA phase. It has been shown that the
size of the PA spherulites decreases upon reduction of the thickness of the
PA ligament separating rubber particles, induced either by simply blending
with more rubber or by addition of rubber-g-MA [47, 51]. The most
probable explanation is increased nucleation at the PA/rubber interface.
DSC of 50:50 (wt:wt) blends of PA-6 or PA-6.6 with EPDM-g-MA
(1.5 wt% MA) or SMA (28 wt% MA) showed that only for the PA-6/SMA
blend the heat of melting was reduced [29]. The decreased crystallinity is
probably not directly related to graft copolymer formation, but indirectly a
result of the physical hindrance of crystallite growth in the very thin PA
ligaments (1-20 nm) in between the SMA dispersion. Upon continued
kneading of a PA-6/SMA blend for 1 h the crystallinity was actually lost
[29]. In supertough PA no spherulites are observed at all [52]. Moon et al.
[53] showed that in a 30:70 (wt:wt) PA-6/PP blend with PP-g-MA as
compatibilizer the PA phase is disperse. An increase in the PP-g-MA
content results not only in a decreased particle size, but also in a decrease
of the PA melting temperature (undercooling) until it approaches that of
PP.
The effects of chemistry on morphology and interface have been discussed, but it is clear that there is a pronounced, reciprocal influence, as the
interface is actually the reaction zone. Man')chal [26] showed a good
correlation between the conversion of MA (in EPM-g-MA) in PAmXD.6/
EPM-g-MA blends and the interfacial volume, using an interfacial thickness
of 40 nm. An increase of the screw speed reduced the particle size of the
dispersed EPM-g-MA phase, resulting in an increase of the interfacial area
and enhanced MA conversion.
3.2.2
Morphology and rheology of blends of polyamides and maleicanhydride-containing polymers
(a) Morphology development. The morphology of an immiscible polymer

blend can best be regarded as an emulsion in which one liquid is dispersed
in another. When the fraction of the dispersed phase exceeds a critical value,
a region of compositions may exist where the blend exhibits phase cocontinuity. This co-continuous morphology can be considered as the intermediate structure at which phase inversion occurs and the dispersed phase
becomes the matrix and vice versa. It is generally accepted that the
composition of the polymer blend and the ratio of the viscosities of the
components determine the blend morphology [54]. The midpoint of the
phase inversion region can be expressed by [55]:
11]2=1
2 1]1
'
151
in which 171 and 172 represent the melt viscosities of the pure components,
and 1 and 2 are the volume fractions of the components at phase
inversion.
It was found that for an in situ compatibilization the amount of graft
copolymer formed at the interface does not affect the composition at which
phase inversion occurs [30]. De Roover showed that during reactive
blending of PAmXD.6 and PP-g-MA the only parameter that determines
the phase inversion composition is the viscosity ratio of the components at
the first stage of the mixing process. The location of the phase inversion is
fixed early during the blending process and does not seem to be influenced
by either further modification of the viscosity ratio versus the mixing time
or the amount of graft copolymer formed.
A more dynamic type of phase inversion may occur when two polymers
with different melting or flowing temperatures are melt blended. When two
polymers are melt blended in an extruder the polymer with the lowest
melting or flowing temperature forms, in the first instance, the matrix. After
the second polymer has melted, phase inversion may occur, depending on
the viscosity ratio and the composition. In the case of blends of PA and
MA-f-pol, PA usually has the highest melting point so that this kind of
phase inversion occurs in the melting zone of the extruder when PA is the
major component, such as in rubber-toughened PA.
Commercial, immiscible polymer blends are usually characterized by a
dispersed phase in a continuous matrix. In order to obtain optimum
properties, the dispersion should be very fine, i.e. particle sizes below 1 J1.m.
It has been recognized that the stage at which the polymeric solids are
molten may already have a considerable influence on the final particle size,
as this process involves locally very high shear stresses [56, 57]. The
dispersion process during melt mixing of immiscible polymers involves
processes such as fluid drop stretching into threads, break-up of the threads
into small droplets and coalescence of droplets into larger ones. The balance
of these competing processes determines the final particle size, which is
captured upon solidification of the blend. Droplet stretching and the
break-up of threads have been modelled for polymeric fluids [58,59] as well
as the process of coalescence [60, 61]. Parameters controlling these processes are the viscosities of the major and minor phases, the viscosity ratio,
local shear rates and shear stresses, mobility of the interface and the
interfacial tension. A low interfacial tension promotes stretching of even very
small droplets so that a very fine morphology can be obtained. Graft
copolymer formed at the interface as a result of a chemical reaction will
lower the interfacial tension. Moreover, owing to the presence of a graft
copolymer the interface may assume a so-called immobile character, which
slows down the coalescence rate [62]. The compatibilizer formed in situ is
able to stabilize the morphology not only during blend preparation but also
in further processing steps.
152
In a pragmatic approach, Wu [63] obtained a master curve which related

the blending shear rate (y), the matrix and dispersed phase viscosities ('1< and
'1d' respectively), the interfacial tension (v) and the viscosity ratio (A) to the
EPM rubber domain size (d) in compatibilized blends with PA-6.6:
d = 4v
1'1<
AO.S4
'
for A = '1d > 1.

'1<
Scott and Macosko [64] used this relationship to describe the dispersion
process of EPM-g-MA in PA-6.6 and found that this rather crude approach,
although neglecting various, possibly occurring phenomena, gave reasonable results.
As discussed in subsection 3.2.1(d) the interfacial reaction between
MA-f-pol and PA is responsible for a fine dispersion. Borggreve and
Gaymans [38] showed that in the case of PA-6/EPDM (90: 10) blends, the
modification of EPDM with some MA has a dramatic effect on particle size.
By introducing a reactive site on the rubber, a graft copolymer may be
formed at the interface, which lowers the interfacial tension and hinders
coalescence and thus reduces the final particle size. However, increasing the
MA content of the rubber from 0.13 wt% to 0.89 wt% had no significant
effect on the morphology. These results were confirmed by Scott and
Macosko for PA-6.6/EPM-g-MA (80:20) blends [64].
Majumdar et al. [40,41] showed that there is a fundamental difference
in the morphology generated when asymmetric PAs and symmetric PAs are
blended with a maleated elastomer (subsections 3.2.1b and 3.2.1d). The
one-point attachment for the asymmetric PAs results in very small rubber
particles, with no effect of the amide content of the PA (Figure 3.5). It was
concluded that the prevention of coalescence is the main function of the
graft copolymers formed in situ. The symmetric PAs on the other hand yield
much larger and more complex shaped particles, whose size steadily
decreases with decreasing amide content. This has been attributed to
increasing physical interactions between the two phases as the methylene
content in the PA repeat unit is increased that brings about an increase in
the extent of reaction with the maleated rubber [40]. Another explanation
might be that with increasing methylene content the amount of potential
cross-linking units decreases and as a result the dispersion process is
stopped at a later stage. By preblending PA-6 with a symmetric PA such as
PA-6.6 some cross-linking in the PA/rubber-g-MA may be introduced,
which results in a larger, final rubber particle size [39]. This procedure can
be used as a strategy to arrive at an optimum particle size.
Takeda and Paul [65] observed a much finer dispersion of SAN in PA-6
when SMA was used as a compatibilizer. The particle size reduction is
largest if the SMA and SAN are fully miscible with each other. For particle
size reduction there seems to be an optimum MA content of the SMA
2:
153
0.8
.J
0.4
(12,12)
11
12
CH 2 :NHCO molar ratio
Figure 3.5 Rubber particle diameter, dw , for blends of 20 wt% SEBS-g-MA with various
polyamides. For abbreviations, see Appendix 3.A. Reprinted from Polymer, 35, Majumdar, B.,
Keskkula, H. and Paul, D.R., Morphology development in toughened aliphalic polyamides, p.
1386, Copyright 1994, with kind permission from Butterworth-Heinemann journals, Elsevier
Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK.
copolymer (6 wt%), when applied in the presence of SAN with a corresponding AN content. At lower MA content insufficient graft copolymer is
formed and compatibilization is not optimum. When the MA content is too
high, the SAN particles become enlarged and complex in shape and it
appears as though the styrenic phase tends to become co-continuous with
the PA-6 phase.
(b) Blend rheology. The melt viscosity of polymer blends depends on the
melt viscosities of the components and the composition of the blend. If the
size of the dispersed phase is above a critical value, so that it may be
deformed in the flow field, the blend viscosity can be lower than the weight
average viscosity of its components [66]. However, compatibilized blends
usually consist of a small dispersed particles that hardly deforms in either
shear or elongational flow. In that case, the blend viscosity is higher than
the weight average viscosity of its components. This general view has been
confirmed for PA-6.6/PP blends [11]. Uncompatibilized blends (large
particle size) have a lower melt viscosity in a broad range of compositions
than the weight average viscosity of its components. After adding PP-g-MA
during blend preparation, the melt viscosity of the blend (now with a finely
dispersed phase) is higher than the weight average viscosity.
For compatibilized blends of immiscible polymers with a small dispersed
phase, the classical approach is to describe the melt viscosity with Einstein's
law:
I] = 1]0
(1
+ 2.5),
154
in which 11 is the viscosity of the blend, '10 is the viscosity of the matrix and
<p the volume fraction of the dispersed phase. This law was proposed for
spherical particles, which do not interact and adhere perfectly to the matrix.
De Roover [30] established that neither Einstein's law, nor Shima's adapted
version were able to describe the melt viscosity (as measured by the mixing
torque of a Brabender mixer) of PAmX-D.6/PP-g-MA blends as a function
of composition. A good correlation was found between the melt viscosity of
the compatibilized blends and the total interfacial area per unit volume. It
was suggested that this is related to the immobilized graft copolymer
concentration at the interface (immobile interface).
3.3
Relationships between morphology-interface and blend properties
The mechanical properties of PA/MA-f-pol blends have been thoroughly

studied. Especially, investigations on PA/rubber, PA/ABS and PA/PPE
blends have resulted in important insights into structure-properties relationships of PA/MA-f-pol blends in particular and of polymer blends in
general. Studies on other PA/MA-f-pol blends, such as the economically
important PA/PP blends, have not yielded additional, scientific understandIng.
3.3.1
Rubber-toughened polyamides
The toughening mechanism of rubber-modified PAs has attracted considerable interest for many years [67-69]. The present state of understanding is
that in order to be effective, small rubber particles have to cavitate easily
when the material is loaded, so that the triaxial tension in the deformation
zone, i.e. in the vicinity of a notch, can be relieved and a transition from
plane-strain to plane-stress can take place. This condition leads to easy
shear deformation and the crack propagation becomes stable owing to
repeated blunting and continued energy absorption. It was found that
rubbers with a low cavitation stress are the most effective impact modifiers
[70]. Besides the ability of the impact modifier to generate voids in a triaxial
stress field, the interparticle spacing was found to correlate strongly with the
impact toughness of a PA/rubber blend [67,68].
When the interparticle distance is decreased, the temperature at which the
transition from brittle to ductile fracture in an impact test occurs declines.
The interparticle distance or ligament thickness can be reduced either by
increasing the rubber concentration or by decreasing the rubber particle
size. The physical background of the critical ligament thickness between
cavitated rubber particles has been related to orientated crystalline lamellae
in the PA phase at the interface [71]. If the interparticle distance is smaller
the relative amount of orientated crystalline lamellae is higher, and this
80
C\I
-E
....,
155
60
~
""0
. 40
""0
Q)
.r::
-5 20
z
0.5
dw
1.0
1.5
(~m)
Figure 3.6 Notched Izod impact strengths at 20 C versus the weight average particle size, dw ,
of PA-6/EPM/EPM-g-MA blends (by courtesy of K. Dijkstra, DSM Research).
D
results in a lower local yield stress. However, if the rubber particle size is
smaller than 0.2,um, cavitation becomes more difficult, resulting in a
decrease in the impact strength of the blend (Figure 3.6).
In order to disperse the rubber sufficiently fine in the PA matrix, the
rubber is usually modified with MA (for the reasons mentioned above).
Although it is common knowledge that MA is essential for a fine dispersion,
Borggreve and Gaymans [38J found that neither the MA content of EPDMg-MA (0.13 to 0.89 wt%), nor the amount of PA coupled at the interface
after melt blending, had any influence on the impact toughness of PAl
EPDM blends if the morphology is not changed. As a result, it has been
questioned whether mechanical adhesion at the interface is required in
rubber-toughened PAs. It is hard to settle this debate, as it is difficult to
separate the effects of mechanical adhesion and particle size. However,
debonding of rubber particles has been shown to be an effective toughening
mechanism in polyvinylchloride (PVC) [72J and even holes have proven to
be effective impact modifiers in polycarbonate [73].
An intriguing result was reported by Marechal [26J, who found that the
addition of phthalic anhydride to a PA-6/EPM-g-MA blend (1 mol
equivalent phthalic anhydride relative to the amount of PA amine end
groups) significantly increased the impact toughness at room temperature.
It was suggested that the low molecular weight anhydride reacts preferentially with the low molecular weight PA in the interface, leaving the high
molecular weight PA to graft onto the EPM-g-MA, resulting in good
interfacial adhesion.
3.3.2
PolyamidelABS blends
Blends of PA-6 and ABS have a significant commercial importance because
156
of the relatively low cost of ABS and its contribution to the dimensional
stability of the blends, the ease of production and the good surface quality
of the mouldings. Majumdar et al. [16-18] have thoroughly investigated the
structural parameters that determine the properties of PAjABS blends. The
mechanical properties can be optimized by adjusting the PA: ABS ratio and
the concentration of compatibilizer. It was found that at least 15 wt% of
rubber is needed in a PA-6jABS blend in order to obtain ductile behaviour
in an Izod test at room temperature [16]. At higher rubber concentrations
(and thus higher ABS concentrations) the brittle-to-ductile transition temperature shifts to lower values. The level of impact toughness, however,
increases with increasing PA concentration. This brings about an optimum
PA: ABS ratio. Generally, a finer morphology gives a lower brittle-to-ductile
transition temperature and a better balance of mechanical properties.
Among other materials, such as imidized acrylics, MA-f-pols have been
used as reactive compatibilizers in this system [28, 74]. On the one hand,
the MA-f-pol should be miscible with the SAN matrix of ABS. On the other
hand, MA is able to react with the P A. It is known that SMA is miscible
with SAN if the MA and AN contents are more or less the same [75]. As
the AN content of SAN used in ABS is usually above 25 wt%, SMA with
an MA content of around 25 wt% should be an effective compatibilizer for
PA-6 and ABS. Indeed, such an SMA copolymer can effectively disperse
ABS domains in a PA matrix. However, blends compatibilized by this highly
funct:c'o alized polymer are brittle below room temperature [74]. Majumdar
et ai. tate that owing to a significant degree of interfacial reaction the
mole ular structure of SMA is modified to such an extent that it is no longer
miscible with SAN. In addition, the highly reactive SMA at the interface
may result in a high number of short PA grafts (section 3.2.1) [29]. When
the average molecular weight of the PA grafts is close to or below the critical
molecular weight for mechanical adhesion, insufficient adhesion will result.
It was suggested [18] that mechanical adhesion between the PA and SAN
phase is necessary in order to have a stress transfer so that the rubber
particles within the SAN phase are able to cavitate and relieve the triaxial
stress state.
Finally, it can be remarked that addition of SMA to PA-6 (glass
transitions higher than 100C and 50C, respectively) results in increased
heat distortion temperatures [48, 76].
3.3.3
Tough polyamidejpoly( dimethylphenylene oxide) blends
PPE is a glassy polymer with a high glass transition temperature (220C).

PPE is blended with PA-6.6 in order to reduce the moisture absorption of
the PA and to increase its heat deflection temperature and dimensional
stability. Applications of PAjPPE blends are, for example, exterior
automotive body parts, where the required, thermal properties are bound
up with the high temperatures that are used in the painting process.
157
The principal method of compatibilizing PA/PPE blends involves first

grafting of MA onto PPE in the melt at about 280C-300C [8]. Subsequently, PPE-g-MA and PA are reactively blended. Alternatively, PPE and
PA-6.6 can be compatibilized by melt blending the two polymers in the
presence of MA [77]. Also PPE may be chemically modified in a reactor to
have anhydride end groups for reaction with PAs [78]. Hobbs et al. [8-10]
have published several studies on the mechanical behaviour of rubber
toughened PA-6.6/PPE blends. Usually PA-6.6 forms the continuous phase
and a rubbery impact modifier is contained within the dispersed PPE
domains. The size and anisotropy of the dispersed PPE phase decreases with
increasing graft copolymer concentrations. The rubber is needed to obtain
sufficient toughness and is dispersed within the PPE phase in order to get
optimum rheological properties.
High notched Izod impact strengths at room temperature are obtained
only in those blends in which the PA and PPE phases are strongly coupled
and have rubber loadings above 10 wt%. If the graft copolymer concentration at the interface is fixed, the brittle-to-ductile transition shifts to lower
temperatures with increasing rubber concentration. It is suggested that the
increase in toughness in the blends appears to be the result of progressive
softening of the dispersed PPE phase through the addition of rubber. In
order to be effective in improving the impact strength of PA-6.6/PPE blends
an appreciable level of copolymer must be present. The graft copolymer
reduces the size of the dispersed phase, increases the interfacial adhesion
and retards the craze breakdown so that extensive shear flow can take
place. The mechanical adhesion between PA and PPE at the interface may
also be of importance to obtain sufficient stress transfer so that the rubber
within the PPE phase may cavitate and be operative, as discussed in section
3.3.1.
3.4 Overall model and future trends

The chemistry in PA/MA-f-pol blends (temperature> 200C) can be summarized as follows. PA reacts with MA-f-pol to yield imides. If the
anhydride: amine molar ratio is below 1.0 only amine end groups of PA
react. If the ratio is above 1.0, all the amines are converted first, but
consequently the amide groups are hydrolyzed resulting in PA chain
scission and the formation of carboxylic acid and amine end groups. The
latter then react with MA-f-pol and lead to the formation of imides. For
asymmetric PAs, coupling to MA-f-pol is the only reaction which occurs,
whereas for symmetric PAs cross-linking of MA-f-pol may also occur.
Grafting and chain scission affect the rheology of PA/MA-f-pol blends.
Grafting and cross-linking, on the other hand, has an effect on the morphology of the blends as well as their composition, the polymer interactions, and
the viscosity ratio. The chemistry, rheology and morphology of blends will
158
Chemical structure
chemical structure of backbone
- MA content of MA-f-pol
- NH2 end group content of PA
Physical structure
- molecular weight
branches
cross-links
Chemistry
PA chain scission
-grafting
cross-linking.
~
,
'InterfaCe
,
interfacial tension
- interfacial thickness
Morphology
disperse--continuous
particle size
- crystallinity
interfacial adhesion
Blend
composition
I I
Processing
conditions
Rheology
viscosity
viscosity ratio
Properties
- impact toughness
- heat distortion temperature
water sensitivity
- processability, etc.
Figure 3.7 Structure-properties relationships for blends of polyamides and maleic-anhydridecontaining polymers.
continously change and interact as long as there is unreacted anhydride

present in the system.
The understanding of the complex relationships between rheology and
morphology on the one hand and properties of polymer blends on the other
hand has grown over the past decade. However, for in situ compatibilized
blends as shown for PA/MA-f-pol blends, these relationships are even more
complex because of the continuous and reciprocal interaction between
chemistry, rheology and morphology. Figure 3.7 provides an overview of the
various, relevant parameters in in situ compatibilized blends and the way
they interact as discussed in Section 3.2. It is an extension of a similar
scheme proposed by Paul [79].
We believe that PA/MA-f-pol blends have been developed and commercialized over the past two decades in a rather empirical way. Insight has been
gained afterwards and is still not quite optimum for a more focused blend
development and optimization. The past ten years, however, have shown an
increase in scientific publications, and the lack of understanding is being
redressed. For future research emphasis should be placed on characterization
ofthe interface and quantification of the various relationships in Figure 3.7. In
addition, the influence of the processing conditions (type of melt mixer,
temperature, screw speed, etc.) and for ternary blends the sequence of polymer
addition should be studied in a systematic way and be quantified too.
159
We expect that the application of PA in integrated parts will grow. As a

result, adhesion of P A on a macroscopic level will become increasingly
important. The use of MA-f-pol as adhesion promoter is obvious and a
model similar to that in Figure 3.7 will be needed in order to achieve
optimum macroscopic adhesion. An advantage of the studies of adhesion
between macroscopic layers is that the 'morphology' is fixed, so that
correlation of, for instance, block lengths of block copolymers in the
interface and adhesion is more straightforward.
Appendix 3.A
3.A.l
3.A.I.I Polymers
ABS
BR
EPDM
EPM
hBR
MA-f-pol
PA
PAmXD.6
PMMA
PP
PPE
PP-g-MA
PS
PVC
SAN
SEBS
SMA
Acrylonitril-butadiene-styrene terpolymer
Polybutadiene; butadiene rubber
Ethylene-propylene-diene terpolymer
Poly(ethylene-eo-propylene); ethylene-propylene rubber
Hydrogenated BR
Maleic-anhydrid-functionalized polymer
Polyamide
Poly(m-xylylene adipamide)
Polypropylene
Poly(dimethylphenylene oxide)
Polypropylene-maleic anhydride graft-copolymer
Polystyrene
Polyvinylchloride
Poly(styrene-eo-acrylonitrile)
Hydrogenated styrene-butadiene-styrene block terpolymer
Poly(styrene-eo-maleic anhydride)
3.A.I.2 Miscellaneous
AN
DMS
DSC
IR
MA
SEM
TEM
Acrylonitril
Dynamic mechanical spectrometry
Infra red
Maleic anhydride
Scanning electron microscopy
Transmission electron microscopy
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Modification of polymer melts by oxazolines and

their use for interfacial coupling reactions
with other functional polymers
N.C. LIU and W.E. BAKER
4.1
Introduction
The blending of immiscible polymers offers attractive opportumhes for

developing new materials with useful combinations of properties [1-5].
However, most blends are immiscible and often have poor mechanical
properties and unstable morphologies. Compatibilization of such blends is
necessary. Preformed block or graft copolymers have been traditionally
added to polymer blends as compatibilizers [6,7]. However, owing to the
lack of economically viable routes for the synthesis of suitable copolymers
for important blend systems, compatibilization by preformed copolymers
has not been used as extensively as the potential utility might suggest. A
more proactive alternative is to generate these copolymers in situ during the
melt blending of suitably functionalized polymers [8,9]. In situ reactive
compatibilization has already been implemented in a number of commercial
products. One of the well-known examples is Du Pont's super tough nylons,
where maleic anhydride (MA) is first grafted onto poly(ethylene-co-propylene-co-diene) (EPDM) rubbers and then reacted with the terminal amine
groups of nylons. A number of other engineering polymers have followed
with similar compatibilization strategies.
Although there are a number of commercially available polymers containing acidic reactive groups, such as MA-grafted EPDM (Du Pont),
styrene-ethylene/butylene-styrene triblock copolymer (SEBS) (Shell), polypropylene (PP) (Himont) and carboxylic-acid-functionalized polyethylene
(PE) (Dow Chemical), PP (BP Performance Polymers), and poly(butadiene-co-acrilonitrile-co-acrylic acid) (NBR) (Novacor), few commercially
available polymers purposely functionalized with basic reactive groups have
been reported. This is, by and large, partly a result of the scarcity of suitable
basic reactive monomers because of their toxicities, difficulties in preparation and handling, instabilities, cost-effectiveness, etc. However, there have
been developmental polymers containing basic functionality. A well-known
example of these is poly(styrene-co-vinyl oxazoline) (OPS) introduced by
Dow Chemical [10]. OPS polymers are reactive copolymers of polystyrene
(PS) containing 1.0% or 1.7% oxazoline functionality. The introduction of
OPS started an interesting period of research on the utilization of oxazoline
Chapman & Hall 1997
164
functionality in the reactive compatibilization of polymer blends. Research

efforts have also been made on the functionalization of polymers with
oxazolines and their use in interfacial reaction with other functional polymers.
In this chapter, preparation and synthesis of reactive polymers containing
oxazoline groups are briefly reviewed. The various aspects of the interfacial
coupling reactions between oxazoline-containing polymers and other functional polymers and the properties of the resulting blends are discussed in
detail. Modification of polymer melts by small oxazoline molecules such as
bis-2-oxazolines, is also mentioned.
4.2 Preparation of oxazoline-functionalized polymers
4.2.1
Vinyl oxazoline monomers
Functionalized polymers containing oxazoline groups may be obtained by

the copolymerization of suitable oxazoline-containing monomers with other
monomers or by the melt grafting of suitable oxazoline-containing monomers onto preformed polymers. 2-isopropenyl-2-oxazoline, I (IPO; structure
1) is the most frequently used monomer both in copolymerization and in
melt grafting.
Two practical synthetic routes are often employed for the preparation of
IPO. One is through the reaction of methacrylonitriles with 2-aminoalcohols
[11]. A weak Lewis acid such as zinc chloride is necessary to catalyse the
reaction. Another is by the reaction between 2-ethyl-2-oxazolines and
paraformaldehyde [12], followed by dehydration of the resultant product
[13]. The Fourier transform infra red (FTIR) spectrum of IPO shows a
strong band at 1611 cm -1 characteristic of the double bond, and a weaker
band at 1659 cm -1 characteristic of the oxazoline ring structure [14].
4.2.2
Copolymerization
A useful method for preparation of oxazoline-containing polymers by

copolymerization is the well-known free-radical emulsion polymerization
technique [15, 16]. Most often used is the copolymerization of IPO with
styrene, which is reported in a plethora of patents to prepare reactive
165
MODIFICATION OF POLYMER MELTS BY OXAZOLINES
polymers for use in the reactive compatibilization of polymer blends. Dow

Chemical's OPS is a developmental product of copolymerized IPO with
styrene. Other functional monomers used include oxazolinylmethyl methacrylate [17]. In addition, IPO and styrene are grafted onto acrylonitrilebutadiene-styrene copolymer rubber [18].
4.2.3
Modification
(a) Melt grafting. Liu and Baker [14] grafted IPO onto a PP
homopolymer in the melt. The grafting was carried out at 190C on a Haake
Rheocord 600 batch mixer using a peroxide initiator. Grafting of IPO was
confirmed by use of FTIR spectroscopy [14]. The spectrum of IPO-grafted
PP (Figure 4.1) shows a band at 1658 cm -1 characteristic of the oxazoline
ring. The strong band at 1611 cm -1 characteristic of the double bond in the
monomer (Figure 4.2) disappeared from the spectrum of oxazoline-grafted
PP. 1H nuclear magnetic resonance (NMR) spectroscopy was used [14] to
determine quantitatively the percentage of grafting; this was done by
calculating the ratio of the integral of peaks at 3.55 ppm and 3.80 ppm (for
the four hydrogen atoms on the oxazoline ring) to the integral of peaks
between 0.5 ppm and 1.8 ppm (for the six hydrogen atoms of PP) (Figure
4.3). Melt grafting of IPO onto EPR [19] and styrenic polymers [20] using
free-radical initiators is reported in the patent literature.
1.0
(l)
u
c
0.8
-+-'
-+-'
E
rn
c
0
L.
0.6
f-
0.4
2000
1650
1300
950
600
Wavelength (cm- 1 )
Figure 4.1 Fourier transform infra red spectrum of oxazoline-grafted polypropylene. Reproduced from Liu, N.C. and Baker, W.E., Polymer, 35, 988, 1994.
166
1.0
Figure 4.2 Fourier transform infra red spectrum of 2-isopropenyl-2-oxazoline. Reproduced

from Liu, N.C. and Baker, W.E., Polymer, 35, 988, 1994.
X2
4.5
3.5
4.0
3.0
ppm
4.5
5.5
2.5
3.5
1 .5
0.5
ppm
Figure 4.3
1H
nuclear magnetic resonance spectrum of oxazoline-grafted PP. Reproduced from

Liu, N.C. and Baker, W.E., Polymer, 35, 988, 1994.

HO~OH + 2CHz= CH - CN NCCH2CH20~
167
NCCHzCH20~OCH2CH2CN
OCH2CH2CN + 2NH2CH2CH20 H _
Scheme 4.1
(b) Other modification. Reactive polyethers containing terminal oxazoline

groups have been reported by Chen, Pan and Yuan [21]. (Preparation
reaction details are given in Scheme 4.1.) The modified polyethers were
characterized using infra red (IR) spectroscopy. A reactive NBR rubber
containing pendent oxazoline groups has been prepared by reacting NBR
with ethanol amine in a solution modification process; the resulting
oxazolinated-NBR polymer was characterized by means of IR and NMR
spectroscopy (Edwards, P.D., Polysar Ltd, June 2,1989, personal communication).
4.3 Interfacial reactions with other functional polymers
4.3.1
Interfacial reactions
(a) Characterization. It is well known that small oxazoline molecules are

reactive towards a number of functional groups, e.g. acids, anhydrides,
hydroxyls and amines. Dow Chemical's OPS reportedly undergoes the same
types of reactions as small oxazoline molecules [10]. However, in the case
of polymer blends, characterization of interfacial reactions between the
blend components poses a number of practical problems, including difficulty
in the detection of very low concentrations (usually lower than 1%) of the
new chemical groups being formed as a result of the reactive melt blending.
Baker and Saleem [22] studied the reaction which occurs between
oxazoline groups in OPS and the carboxylic acid groups in poly(ethyleneco-acrylic acid) (CPE) (Scheme 4.2). An FTIR spectrum (Figure 4.4(a of
the insoluble fraction of a reactive OPS/CPE blend after one week of
Soxhlet extraction in xylene shows a broad stretching vibration at
Scheme 4.2
168
(a)
1800
1600
1500
Wavelength (cm-1)
Figure 4.4 Fourier transform infra red spectra of (a) the insoluble fraction of OPS/CPE alloy
after a one-week extraction, and (b) model compounds obtained by reacting 2-ethyl-2oxazoline with 2-ethyl-hexanoic acid. Reproduced from Baker, W.E. and Saleem, M., Polymer,
28, 2057, 1987.
1540 cm -1 and a sharp peak at 1652 cm -1, confirming the presence of

amide groups. A pronounced shoulder at 1734 cm - 1 from the c=o of the
ester linkage is present adjacent to the strong carbonyl stretching band of
the unreacted carboxylic acid of CPE at 1705 cm - 1. Comparison of this
spectrum with that of the product of a model reaction between 2-ethyl-2oxazoline and 2-ethyl-hexanoic acid reveals that the latter has very similar
band positions in the region 1500-1800 cm -1 (Figure 4.4(b)).
Reactive blending of polymers in the melt results in an increase in
molecular weight and melt viscosity, which is in turn expected to be
manifested by an increase in torque during mixing. Figure 4.5 shows the
torque-time relationship for various nonreactive and reactive blends. After
an initial melting and mixing period a slow increase in torque can be noticed
for the reactive blend, whereas a significant decline in torque is observed for
169
15
12
'-"
Q)
:::J
0-
L-
0
f--
CPE+OPS
3
0
12
18
24
3G
Time (min)
Figure 4.5 Torque-time relationships for various PS/PE blends with 10 wt% PE; processing
temperature = 225C; mixing speed = 100 rpm; CPE/OPS is a reactive blend. Reproduced
from Baker, W.E. and Saleem, M., Polymer, 28, 2057, 1987.
the two nonreactive blends (CPE/PS and PE/PS). Solubility characteristics

also indicate that an interfacial reaction does take place between OPS and
CPE; a reactive blend of OPS containing 10% CPE is soluble in toluene at
room temperature, whereas reactive blends with 20% and 30% CPE are
only partially soluble in toluene. With the increase of CPE content to 40%,
the reactive blend becomes insoluble in toluene. On the other hand, the PS
fraction of unreactive PS/PE blends of the same composition is soluble in
toluene and the PE fraction remains undissolved.
Liu et ai. [23J investigated the interfacial reaction between oxazoline
groups in OPS and PE-g-MA by using FTIR spectroscopy. The presence of
an absorbance at 3440 cm -1 (NH stretching of secondary amide) in the
spectrum of the OPS/PE-g-MA reactive blends and its absence in similar
but nonreactive blends confirmed the formation of amide groups during the
reactive melt blending. A new strong absorption peak at 1734 cm - 1 was also
formed (ascribed to the ester part of the interpolymer linkage) and constitutes further evidence for the interfacial reaction. Figure 4.6 shows that such
reactive blending leads to an increase in mixing torque but no such increase
was observed for the corresponding nonreactive blends which have no
functional groups in both components; this again, points to the occurrence
of an interfacial reaction.
170
25
20
~ 15
Q>
:::l
e-
t2
(b)
10
(a)
5
00
10
Time (min)
Figure 4.6 Torque~time relationships for (a) nonreactive blends of OPS with PE, and (b)
reactive blends of OPS with MA-grafted PE (70: 30). All blends prepared and 190C and 100
rpm. Reproduced from Liu, N.C., Baker, W.E. and Russell, K.E., J. Appl. Polym. Sci., 41, 2285,
1990.
Fowler and Baker [24] studied the behaviour of reactive blends of PS

with carboxylic-acid-functionalized NBR as a function of OPS concentration. A significant torque rise was observed after the initial melting (Figure
4.7) and the melt flow indices of these blends decreased from 2.5 dg min ~ 1
in blends without OPS in the PS phase to less than 0.1 dg min ~ 1 at 40%
OPS in the PS phase (Figure 4.8). Both observations indicate substantial
amounts of interfacial reaction and molecular weight increase, particularly
when high matrix phase oxazoline concentrations are used.
Liu and Pan [25] reported the interfacial reaction between poly(propylene oxide) with terminal oxazoline groups and poly(vinyl chloride) (Scheme
40
E
~
Q>
:::l
e-
t2
30
20
Rubber
addition
(a)
10
00
(b)
Time (min)
Figure 4.7 Typical torque~time curves for a reactive blend (20% NBR, 40% OPS, 40% PS) at
100 rpm and 185C: (a) melt blended for 5 min, and (b) rubber sequentially added to PS phase.
Reproduced from Fowler, M.W. and Baker, W.E., Polym. Eng. Sci., 28, 1427, 1988.
171
2.4
f 2.0~
~
t 1.6 \
"C
~ 1.2
O.Br0.4
""-0
"""----:-- m
0.0 L-..---L--"--...L....I..-L-~!...==::====!:==
o 10 20 30 40 50 60 70 BO
OPS (%)
Figure 4.8 Melt flow index (MFI) of reactive PS/NBR blends as a function of OPS concentration. Reproduced from Fowler, M.W. and Baker, W.E., Polym. Eng. Sci., 28, 1427, 1988.
Scheme 4.3
4.3). The reaction was characterized by a solvent extraction procedure, IR

spectroscopy, and molecular weight increases.
(b) Kinetics. There is no easy method for evaluating the kinetics of
interfacial reactions between blend components. When the torque in a batch
mixer reaches a steady state it may be assumed that the interfacial reaction
has gone to completion. Baker and Saleem [26] reported that the interfacial
reaction between oxazoline groups in OPS and carboxylic groups in CPE
is rather slow. They chose a reactive blend system with 40% CPE for
studying the kinetics of the reaction as maximum reaction occurs in this
system, as indicated by torque rises during blending (Figure 4.9), with
minimum and maximum torque values, Tmin and Tmax , respectively (Figure
4.10). Differential scanning calorimetry (DSC) thermograms (Figure 4.11)
show that mixing reactive OPS/CPE blends (60:40) for 0 min (dry blend),
6 min, and 16 min gives rise to characteristics of an immiscible, twocomponent system, with a marked melting peak and glass transition regions.
Increasing the mixing time, however, led to a reduction in the sharpness of
the melting peak and only after 30 min of mixing does the glass transition
temperature (associated with OPS) disappear, possibly because of the
completion of the interfacial reaction. When the reactive blend system was
mixed at temperatures of 180C, 225C and 250C, their DSC thermograms
172
E
~
c:
.: 3
x
S'"
20
40
60
80
100
CPE (wt%)
Figure 4.9 Torque changes versus reactive OPS/CPE blend composition. All blends were
prepared at 225C and 100 rpm. Reproduced from Baker, W.E. and Saleem, M., Polym. Eng.
Sci. 27, 1634, 1987.
were identical, suggesting that the interfacial reaction is not limited by

chemical kinetics but rather by mass transfer considerations (i.e., degree of
mixing). This statement is also supported by the torque-time curves shown
in Figure 4.10. At a mixing speed of 50 rpm the torque continues to increase
even at 30 min, whereas the torque was stabilized at 25 min at a mixing
speed of 100 rpm. When the blend was mixed at 150 rpm, the torque levelled
off at about 15 min, indicating the completion of the interfacial reaction. To
reduce the reaction time, Lewis acids may be used as catalysts. The reaction
15
12
E
~
150 rpm
':;'--::::::>-0::::::::::== 1150
00 rpm
rpm
Q)
"
:::>
50 rpm
3
0
12
18
24
30
Time (min)
Figure 4.10 Torque-time relationships for reactive OPS/CPE (60: 40) blends at different
mixing speeds. Processing temperature was 22SOC for all blends. Reproduced from Baker, W.E.
and Saleem, M., Polym. Eng. Sci., 27, 1634, 1987.
173
'E
Qj
"C
r:::
340
360
380
400
420
440
460
Temperature (K)
Figure 4.11 Differential scanning calorimetry thermograms of 0 PSjCPE (60: 40) blends mixed
for the times indicated on the thermograms. Reproduced from Baker, W.E. and Saleem, M.,
Polym. Eng. Sci., 27, 1634, 1987.
time is reduced from over 30 min to about 10 min for OPS/CPE (90: 10)
blends when 0.1 % zinc chloride is used [27] (Figure 4.12).
In contrast to the above results, the interfacial reaction between oxazoline groups in OPS and carboxylic groups in NBR was reported to be
much faster. The reaction reached equilibrium in about 3 min at 185C and
100 rpm as indicated in Figure 4.7 [24,28]. The torque evidence was
reinforced by data on the impact energies of blend samples obtained at
different mixing times but at the same processing temperature and mixing
speed [28]. Fowler [28] found that the impact energies of the blends
reached a constant value after about 5 min. It was also reported that, as
expected, the reaction was faster at a higher processing temperature and
mixing speed.
The interfacial reaction between oxazoline groups in OPS and MAgrafted PE is fast, as reported by Liu, Baker and Russell [23]. Such a
reaction could be over in 3 min at 190C and 100 rpm, as indicated by the
torque-time curves during melt blending (Figure 4.6). This was corroborated by studying the scanning electron microscope (SEM) micrographs of
174
20 t16
E
~
12
Q)
::J
0-
8
4
\.
_-------(b)
~_
I
(a)
12
18
Time (min)
24
30
Figure 4.12 Mixing torque- time curves for OPS/CPE (90: 10) blends showing the effect of zinc
chloride as a catalyst: (a) without catalyst. and (b) with 0.1 wt% catalyst. All blends were
prepared at 235C and 100 rpm. Reproduced from Baker. W.E. and Saleem, M., J. Appl. Polym.
Eng. Sci., 39, 655, 1990.
the blends mixed for only 3 min: no significant difference was observed
between these blends and those which were mixed for 15 min.
( c) Extent of reaction. It is difficult to determine quantitatively the extent
of interfacial reaction between blend components in the melt because, in
most cases, the concentration of the reactive groups is very low. Curry and
Anderson [29] have developed an indirect method to determine the extent
of the interfacial reaction in OPSjCPE blends by using FTIR spectroscopy.
They calculated the extent of reaction and the concentration of interpolymer
linkage from the depletion of carboxylic acid groups during melt blending
(Table 4.1). The molar ratio between oxazoline and carboxylic acid groups
was fixed at 1: 6 for all blend samples; this was achieved by varying the
Table 4.1 Extent of interfacial reaction in OPS/CPE blends
OPS:CPE:PS
(wt :wt)
Acid
reacted
(groups/
cm 3 x 10- 2 )
Oxazoline
available
(groups/
cm 3 x 10- 2 )
Extent of
reaction
(%)
Torque
at 12 min
(Nm)
Cross-link
density
(wt%)
60:40:0
45:30:25
30:20:50
0.58
0.29
0.09
0.56
0.42
0.28
100
69
32
13.25
8.35
6.90
1.2
0.8
0.6
For abbreviations, see Appendix 4.A.

Source: Curry, 1. and Anderson, P., Adv. Polym. Technol., 11, 3, 1990/91.
175
blend composition. The amount of reacted acid was determined by the

difference between residual concentration after blending and the initial
concentration. The extent of interfacial reaction decreased from 100%, with
60% OPS in the blend, to only 32%, with 30% OPS in the blend. The
calculated density of interfacial linkage correlates well with the mixing
torque, which further confirms that mixing limits the interfacial reaction.
The amount of interfacial reaction is therefore reflected by torque changes
and the interfacial reaction may be assumed to go to completion when the
mixing torque reaches a steady state.
(d) Reactivity comparison with other basic groups. Melt functionalization
of polymers with basic (in most cases nucleophilic) reactive groups has
attracted increasing interest recently. In addition to the melt functionalization with vinyl oxazolines other reactive monomers have been used for
polymer functionalization, e.g. melt grafting of GMA onto PP [30,31] and
linear low-density PE (LLDPE) [32] (ch. 1), dimethylaminoethylmethacrylate (DMAEMA) and t-butylaminoethylmethacrylate (TBAEMA) onto
LLDPE [33-36] and hydroxyethylmethacrylate (HEMA) and 2-hydroxypropylmethacrylate (HPMA) onto PP [37]. The question of the effectiveness of oxazoline groups compared with that of other basic reactive groups
in the reactive compatibilization of polymer blends has been addressed. Liu,
Xie and Baker [37] studied the reactive toughening of PPjNBR blends with
different basic functionalized PP and NBR containing carboxylic acid. They
found that oxazoline and glycidyl functionalities are effective in toughening
the blends as indicated by the greatly reduced particle sizes and the
dramatically improved impact properties (Figure 4.13 and Figure 4.14).
Oxazoline functionality is more effective than glycidyl functionality. However, there are no significant improvements in the morphologies and impact
properties of PPjNBR blends when various hydroxyl (e.g. HPMA, HEMA)
and amino (e.g. DMAEMA, TBAEMA) functionalized PP are introduced
in the PP matrix. Although the concentrations of functional groups of all
species were not identical, the results indicate, indirectly, that oxazoline and
glycidyl groups in the PP matrix are reactive towards the carboxylic acid
functionality in the NBR rubber phase whereas the secondary and tertiary
amino groups and hydroxyl groups are less reactive.
Some condensation polymers may have both acidic and basic functionalities. For example, PA-6 may have both carboxylic acid and amine
groups at the chain ends. Therefore, both basic and acidic functionalities
may be effective in the reactive compatibilization of PA-6 blends. Triacca
et al. [38, 39] reported that the oxazoline group is less reactive with
PA-6 than MA, as indicated by rheological and morphological evidence.
They suggested that the oxazoline groups in OPS react with the carboxylic
acid chain ends of PA-6. Akkapeddi and Van Buskirk [40] reported
176
25
20
,....
--,
15
0'
....
Ql
W
+'
c
a. 10
:=
0
12
=-----:--:
o:::::::ii
.A.
24
18
30
Percentage of Fu netio na lized PP in Matrix
HPMA
HEMA
GMA
.A.
TBAEMA
IPO
.6-
DMAEMA
Figure 4.13 Effects of different basic functionalized PP on the impact energy of PPjNBR
blends. = HPMA; = GMA; ... = TBAEMA; 0 = HEMA; 0 = IPO; f::" = DMAEMA.
For abbreviations, see Appendix 4.A. Reproduced from Liu, N.C., Xie, H.Q. and Baker, W.E.,
Polymer, 34, 4680, 1993.
that PS with less than 2% oxazoline functionality is not reactive with

poly(ethyleneterephthalate) (PET) in an extruder whereas styrene copolymers with 3%-5% glycidyl methacrylate showed sufficient reactivity.
4.3.2
Properties of blends with oxazoline-modijied interfaces
(a) Morphology and interfacial adhesion. Morphology and interfacial adhesion are two important factors in determining the mechanical properties
177
2.0
.......
z
0/
L-
'-"
1.0
--l
E
::J
E
x
::i!:
1.5
0
0
0
-c
a
~o
0.5
0.0
.:,g:=---.
---=:
::::::=--=-
12
_---/2:: ~
24
18
30
Percentage of Fun-::tionalized PP in Matrix

o
HPMA
GMA
HEMA
o IPQ
TBAEMA
A.
DMAEMA
Figure 4.14 Effects of different basic functionalized PP on the peak force during impact for
PPfNBR blends. = HPMA; = GMA; ... = TBAEMA; 0 = HEM A; 0 = IPO;
D. = DMAEMA. For abbreviations, see Appendix 4.A. Reproduced from Liu, N.C., Xie, H.Q.
and Baker, W.E., Polymer, 34, 4680, 1993.
of polymer blends. The introduction of graft or block copolymers at blend

interfaces affects blend morphology by lowering the interfacial tension,
resulting in finer morphology during blending and stabilizing the blend
morphology in subsequent processing.
Takeda and Paul [39] studied the morphology of PA-6jOPS blends.
They found that the introduction of interfacial reactions involving oxazoline
functionality resulted in much finer morphology. For unfunctionalized PS,
178
REACTIVE MODIFffiRS FOR POLYMERS
2:
11)
OL--L__~~__~~~-L__L-~__~~
PS
20
40
60
Composition (wt%)
80
100
OPS or SMA2
Figure 4.15 Weight average particle size, ilw, for 75% PA with 25% of OPSjPS mixtures and
SMAnjPS mixtures as a function of composition of the styrenic phase. The reaction was in a
Brabender mixer; temperature = 240C; reaction time = 10 min; mixing speed = 60 rpm.
0= PSjOPS; = PSjSMA2. Reprinted with permission from Takeda, Y. and Paul, D.R., J.
Polym. Sci. Polym. Phys. Ed., 30, 1273, published by John Wiley & Sons, 1992.
the average particle diameter in PA-6/PS blends was 3.5 pm, whereas for
pure OPS the average particle diameter in PA-6/0PS blends was reduced
to 0.9 f1.m (Figure 4.15). Mixtures of PS and OPS showed a monotonic
drop in particle diameter as a function of the percentage of OPS in the PS
phase.
Liu and Baker [41] studied the effect of oxazoline concentration on the
average particle size of reactive PSjNBR blends at different processing
conditions indicated by Pp in Figure 4.16. They found that the average
particle size decreased by a factor of four with the introduction of less than
0.15% oxazoline functionality in the PS matrix. A further increase in
oxazoline functionality did not significantly reduce the NBR particle size
owing to the greater resistance to the deformation of smaller particles.
Similar results have also been reported by Liu and Baker [14] in a reactive
PPjNBR blend system as shown in Figure 4.17. The NBR particle size
decreased by a factor of three with the introduction of less than 0.025 wt%
of oxazoline groups in the PP matrix.
Baker and Saleem [27] studied the morphology of OPS/CPE blends. It
was shown that increasing the amount of reactive components leads to a
179
1.0
0.8
2;
Q)
'iii
Q)
0.6
13
:;::::
tii
c..
0.4
0.2
0.0 L-..-'-_L-..--'----'_--'---'-_....I.-----I._....I.---'
0.0
0.1
0.2
0.3
0.4
0.5
Oxazoline functionality in PS (wt%)
Figure 4.16 Effect of interfacial reaction on the rubber particle size of reactive PSjNBR blends
prepared at identical processing conditions (one processing condition for each curve; a larger
processing parameter, Pp, indicates more intensive mixing). Pp: /:::, = 4.3; V = 12.1; 0 = 34.6.
Reproduced from Liu, N.C. and Baker, W.E., Polym. Eng. Sci., 32, 1695, 1992.
gradual decrease in the dispersed phase size. At 50% replacement of PE with

reactive CPE, the blend morphology became very fine.
There is no known satisfactory method for measuring the interfacial
adhesion between blend phases within blends. However, relative measures
of interfacial adhesion may be provided by using a variety of testing
methods, such as peel tests. Liu and Baker [41] attempted to evaluate the
interfacial adhesion in PS/NBR blends by peeling an NBR rubber strip from
a rigid PS adherent which had been bonded at 180 a C and 20 MPa for 12
min. The adhesive peel strength for nonreactive PS was 600 N m - 1. With
the introduction of 0.03% oxazoline functionality in the PS adherent, the
adhesive peel strength increased to 6.9 kN m - 1. This clearly indicates the
dramatic effect of interfacial reactions in improving interfacial adhesion.
(b) Tensile properties. Saleem and Baker [27] have studied the tensile
properties of reactive OPS/CPE blends at a fixed composition of 80: 20 and
a fixed ratio of OPS: CPE at 3: 2 in all blends. They found that there was
a gradual increase in tensile strength with increasing amount of reactive
components; the tensile strength did not change significantly after 50%
180
2.0
~---r----r--'--"----'---r---r----,
1.5
~
Q)
'w 1.0
Q)
(j
Q.
0.5
0.00.00
0.03
0.06
0.09
0.12
Oxazoline in PP (wt"lo)
Figure 4.17 Influence of oxazoline concentration on the rubber particle size of reactive
PPjNBR blends prepared at identical processing conditions (one processing condition for each
curve; a larger processing parameter, P p, indicates more intensive mixing). Pp: = 50;
= 140. Reproduced from Liu, N.C. and Baker, W.E., Polymer, 35, 988, 1994.
replacement of nonreactive components with their corresponding reactive

components (Figure 4.18). They further estimated the mol percentage of
reactive pairs that were available for interfacial reaction. They found that
the improvement in tensile strength of OPS/CPE blends increases with
increasing mol percentage of reactive pairs and levels off in the range of
0.15%-0.25% reactive pairs (Figure 4.19).
Triacca et al. [38] reported much improved tensile properties in PA-6/
SAN blends when an oxazoline containing SAN (R-SAN) was used in place
of SAN. Nonreactive PA-6/SAN blends were brittle and did not show a
yield point during tensile testing (Figure 4.20). On the other hand, reactive
PA-6/R-SAN blends showed yielding behaviour and a much improved
tensile strength over nonreactive analogues.
( c) Impact properties. Improvement in impact properties is the most
important reason for blending [1]. The impact properties of various reactive
blends involving oxazoline functionality have been studied. Liu and Baker
[41] reported that the impact improvement in reactive PSjNBR blends
initially increased with oxazoline concentration in the PS matrix and went
181
40
.--..
0
a...
......., 30
~
..c
+'
(jl
C
Q)
L....
+'
(fJ
Q)
Ul
20
Q)
t-
10
20
40
80
60
wt% CPE replacing PE

Figure 4.18 Changes in tensile strength of PSjPE (80: 20) blends with the replacement of PE
with CPE and PS with OPS; the ratio OPS: CPE is 3: 2. Reproduced from Saleem, M. and
Baker, W.E., J. Appl. Polym. Sci., 39, 655, 1990.
75,------------------------------------.
O~-----L------L-----~------~----~--~
~1
Estimated mol% of reactive pairs
Figure 4.19 Percentage improvement in tensile strength as a function of the concentration of

reactive pairs used in OPSjCPE blends. Reproduced from Saleem, M. and Baker, W.E., J. Appl.
Polym. Sci., 39, 655, 1990.
182
80
.-------------------------------,12
PA_6/R-SAN (75:25)
::==="1 .-/}
~~~~~~F~==~-AA-6
PA_6/SAN (75:25)
4
20
o!=---'-__:-':----'__-:'-:--I l-~--L-~=__-'-----:'" 0
o
10
20
150
200
250
Strain (%)
Figure 4.20 Stress strain diagrams for PA6, PA6/SAN and PA6/R-SAN blends at 5.08 mm
min-I. Reprinted from Polymer, 32, Triacca, V.I., Ziaee, S., Barlow, J.W., Keskkula, H. and
Paul, D.R., Reactive compatibilization of blends of N-6 and ABS materials, p. 1401, copyright,
1991, with kind permission from Butterworth-Heinemann journals, Elsevier Science Ltd, The
Boulevard, Langford Lane, Kidlington OX5 1GB, UK.
12
VJ
a..
IQ)
>
0
Ul
'U
Q)
CD
.....
0
+'
C
Q)
E
Q)
>
0
l-
e..
+'
U
e..
0.0
0.2
0.4
0.6
Oxazoline Functionality in PS (mol.%)
Figure 4.21 Effect of oxazoline concentration on the notched impact improvement of reactive
PSjNBR blends. Reproduced from Liu, N.C. and Baker, W.E., Polym. Eng. Sci., 32, 1695, 1992.
183
>-
15
1.0
0'1
L
Q)
t:
12
0.8
......
u
Q..
t:
0.6
E
-0
Q)
()
r+
r+
'<
...
E
L
0.4
:J
0.
eD
0.2
0
0.00
0.02
0.0
0.06
0.04
Oxazoline wt% in pp
Figure 4.22 Effect of oxazoline concentration on the notched impact improvement and ductility
index of reactive PPjNBR blends. Reproduced from Liu, N.C. and Baker, W.E., Polymer, 35,
988, 1994.
250r------.------.-------.-----~
200
150
o
u. 100
50
(b)
(c)
OL-------~------~------~------~
0.0
0.5
1.0
1.5
2.0
Displacement (cm)
Figure 4.23 Instrumented notched impact curves for (a) PP, (b) non-reactive PPjNBR blends,
and for reactive blends with (c) 0.010% oxazoline functionality, (d) 0.025% oxazoline functionality, and (e) 0.051 % oxazoline functionality. Reproduced from Liu, N.C. and Baker, W.E.,
Polymer, 35, 988, 1994.
184
through a maximum at higher concentrations (Figure 4.21). This seems to

be because the rubber particles were too small to terminate cracks during
impact when the oxazoline concentration is high. Liu and Baker [14] also
studied the impact properties of reactive PPjNBR blends. Without any
interfacial reaction, the impact energies of PP jNBR blends were about the
same as that of pure PP. With increasing oxazoline concentration in the PP
matrix, PPjNBR blends went through a brittle-ductile transition at about
0.02% oxazoline concentration, as shown in Figures 4.22 and 4.23. The
ductility index is the ratio of the impact energy absorbed after the maximum
force to the total energy absorbed during an impact event. The dramatic
improvement in impact energy and ductility of PP jNBR blends suggests a
change of failure mechanism.
Fowler and Baker [24] studied the impact properties of high-impact
polystyrene (HIPS)/OPSjNBR blends. The blending of HIPS with NBR
rubber (having carboxylic acid functionality) resulted in a 35% loss of
impact energy. However, with the addition of a small amount of OPS into
the HIPS phase the blends show an increase in impact strength of up to 90%
over that for pure HIPS (Table 4.2). The increase in impact strength is a
result of increased ductility rather than an increase in the peak load. The
optimum improvement in impact strength is achieved with an oxazoline
concentration between 0.1 % and 0.2% in the HIPS phase.
(d) Miscellaneous properties. The utilization of oxazoline functionality in
the reactive compatibilization of polymer blends has attracted much attention not only from academic researchers but also from industrialists. Table
4.3 lists some of the recent patents involving the utilization of oxazoline
functionality in improving polymer blend properties.
Most of the common engineering and commodity polymers are involved
in the blend systems, including poly(butylene terephthalate) (PBT), PET,
Table 4.2 Charpy impact results of HIPSjOPSjNBR blends.

NBR (wt%)
HIPS (wt%)
PS (wt%)
OPS (wt%)
Impact
energy (J)
Peak load
(N)
0
20
20
20
20
20
20
20
20
100
80
75
60
75
60
70
60
60
0
0
5
20
0
15
0
10
0
0
0
0
0
5
5
10
10
20
4.9
3.2
3.2
3.1
9.6
9.7
7.7
9.4
4.1
2060
1490
1540
1730
1800
1950
1870
1950
1990

Source: Fowler, M.W. and Baker, W.E., Polym. Eng. Sci., 28, 1427, 1988.
185
Table 4.3 Selected recent patents involving the use of oxazoline functionality in blend
compatibilization, The polymers with oxazoline functionality are copolymers of IPO with
styrene, except in the following patent: 1 IPO grafted PS; 10 oxazoline-modified expoxy resin;
15 copolymer of IPO, styrene and acrylonitrile; 16 oxazoline terminated PS; 17 IPO-grafted
ABS,
No,
Patent No,
Year
Blend
composition
Co-reactive
group
Properties
improved
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
JP05, 287, 193

JP05, 222, 276
JP05, 98, 139
JP05,98,103
JP05, 70, 660
JP05, 51, 502
EP523,259
EP523,258
JP04, 335, 057
JP04, 120, 165
JP04, 114, 169
JP04, 81, 459
JP04, 81,458
JP04, 45, 932
JP04, 07, 355
US4, 895, 897
US4, 886, 856
NL8,603, 112
EP257,692
JP63, 08, 450
JP62, 252, 437
EP205,145
US4, 590, 241
1993
1993
1993
1993
1993
1993
1993
1993
1992
1992
1992
1992
1992
1992
1992
1990
1989
1988
1988
1988
1987
1986
1985
PPE/PA
PBT/PP
PBT/HIPS
PSjEPR
PC/HIPS
PBT/PP
PC/HIPS
PPE/HIPS
POM/PET
PC/PP
PET/St-BA
PC/PA
PC/PA
PS/PA-PI
PC/PA
PC/EPR/PS
St-AA/PS
PBT/PPE
PBT/PS
SBR/NBR
EPR/PP/PS
PS/PE
PE/PS
Anhydride
Acid
Acid
Anhydride
HDT, impact
HDT, impact
Shrkinkage
Weatherability
Impact
Adhesion
Gloss
Gloss
Impact
Impact
Binder
Abrasion
Impact
Antistatic
Appearance
Impact
Impact
Impact
Adhesion
Mechanical
Foam
Adhesion
Mechanical
Anhydride
Acid
Anhydride
Hydroxyl
Anhydride
Acid
Hydroxyl
Hydroxyl
Acid
Hydroxyl
Anhydride
Acid
Acid
Acid
Acid
Acid
Acid
Acid
polycarbonate (PC), PPE, polyamide (PA), poly(oxymethylene) (POM),

HIPS, PS, PE, PP, poly(ethylene-co-propylene) elastomer (EPR), etc. The
range of properties improved is wide, including impact, heat distortion
temperature, processability, tensile stength, solvent resistance, adhesion,
shrinkage, weatherability, appearance, etc.
Table 4.4 Effectiveness comparison of pre-made and in situ formed compatibilizer with the
same amount of OPS and CPE in the blends,
PS:OPS:CPE:PE
(wt ratios)
47,5: 22,5: 15: 15
47,5: 22,5 : 15: 15
65:15:10:10
65: 15: 10: 10
Blending sequence
Tensile
strength (MPa)
Elongation
at break (%)
OPS/CPE preblended
Mixed all together (in situ)
OPS/CPE preblended
Mixed all together (in situ)
21.6
24,6
30,6
36.4
2,0
2,0
2,1
2,5

Source: Saleem, M, and Baker, W,E" J, Appl, Polym, Sci" 39, 655, 1990,
186
( e) Effect of blending sequence on blend properties. Saleem and Baker [27]

compared the effectiveness of a pre-made OPSjCPE compatibilizer with that
of an in situ formed one on the tensile properties of OPSjCPE blends. They
prepared a 60:40 OPSjCPE blend and added it to various PSjPE blends as
a compatibilizer. They found that the premade OPSjCPE compatibilizer
was effective in the compatibilization of PSjPE blends, with PS being the
major component, as shown by improved morphological and tensile properties. They also prepared in situ reactive OPSjCPE blends with identical
compositions. The blends with in situ compatibilizers had higher tensile
strengths than their corresponding blends with the pre-made compatibilizer
but the same overall composition (Table 4.4). The higher tensile properties
was attributed to a better distribution of the OPSjCPE graft polymer at the
interface in the case of in situ compatibilized blends.
0\
0.17 wt%
(J)
a..
en
'C
c:
.0.08wt%
(I)
:c
'0
0
>-
E'
(I)
c:
(I)
0.31 wt%
CIl
0.
.0.03wt:%
OL---~----~----~----------~
0.3
0.5
3
Particle size (~m)
Figure 4.24 Effect of rubber particle size on the notched impact improvement of PSfNBR
blends. The curve for reactive blends was obtained by varying the amount of oxazoline
functionality in PS (indicated on the curve) under an identical set of processing conditions. The
curve for nonreactive blends was obtained at varying processing conditions. = Reactive
blends; <> = non-reactive blends. Reproduced from Liu, N.C. and Baker, W.E., Polym. Eng. Sci.,
32, 1695, 1992.
4.3.3
187
The separate roles of interfacial reaction and rubber particle size in

toughening polymers
Rubber particle size and rubber-matrix adhesion are two important factors
determining the properties of rubber-toughened polymers. These two factors, however, are usually interrelated. It is difficult to alter the rubber
particle size without simultaneously altering blend composition, the amount
of interfacial reaction, and the viscosity characteristics of blend components,
etc. The question is, therefore, whether the interfacial reaction will specifically increase the impact properties. By using oxazoline functionalized
polymers in model systems for reactive toughening, Liu and Baker [14, 41]
have separated the individual effects of interfacial reaction from those of
rubber particle size.
In studying a model system of toughened brittle polymers (PSjNBR) Liu
and Baker concluded that high levels of interfacial reaction are required for
6r--------.---.----,--------,
5
(J)
a..
en
"0
cQ)
:0
a
0
>~
Q)
Q)
~a.
E
O~------~----L-----~------~
0.1
0.3
0.5
Particle size (101m)
Figure 4.25 The role of interfacial reaction in rubber-(NBR)-toughening of PS (notched impact

tests). Oxazoline functionality: 0 = 0.19 mol%; V = 0.08 mol%; 0 = 0.03 mol%; /::,. =
0.00 mol%. Reproduced from Liu, N.C. and Baker, W.E., Polym. Eng. Sci., 32, 1695, 1992.
188

10.-------~--~----._------_,
.()- .
rJl
"0
CD
:0
c:
en
8
Q.
.. /l.
/l.
15
Ii.
>.
~
.13El
CD
c:
CD
r1
?_9-
~a.
. 2f-
_-"i/
O~------~----~----L-------~
0.1
0.3
0.5
Particle size (!.1m)
Figure 4.26 The role of interfacial reaction in rubber-toughening of PS (unnotched

impact tests). Oxazoline functionality: 0 = 0.36 mol%; f::, = 0.19 mol%; 0 = 0.06 mol%;
\l = 0.03 mol%; 0 = 0.00 mol%. Reproduced from Liu, N.C. and Baker, W.E., Polym. Eng.
Sci., 32, 1695, 1992.
the effective toughening of PS (Figure 4.24) and, more importantly, that the
notched impact energy of a PSjNBR blend increases with increasing amount
of interfacial reaction with the same rubber particle size (Figure 4.25). In
Figure 4.24 the curve for reactive blends was obtained by changing the
amount of oxazoline functionality in the PS matrix at an identical set of
processing conditions, and the one for nonreactive blends was obtained
varying the processing conditions. With the same rubber particle size,
impact improvement for reactive blends is as high as four times that for
nonreactive blends. The extent of interfacial reaction increases with increasing molar concentration of oxazoline used in the PS phase. The increase in
the slope of curves in Figure 4.25 with increasing oxazoline concentration
indicates that the optimum particle size for toughening is greater for blends
with lower amounts of interfacial reaction. Unnotched impact testing
showed similar results except that the impact improvement is much greater
by almost tenfold (Figure 4.26).
In studying the model system for pseudoductile polymers (PPjNBR), Liu
and Baker [41] concluded that an interfacial reaction is required for a
189
15,-----,--------.,------------,
12
>~
Q)
Q)
~c..
.S
"0
.~ 6
n;
(;
-.--
o~----~------~
0.3
0.5
____________
Particle size
(~m)
Figure 4.27 Effect of interfacial reaction and particle size on the impact improvement in impact
energy of notched PP/NBR blends. The curve for reactive blends was obtained by varying the
amount of oxazoline functionality in PP (indicated on the curve) at an identical set of
processing conditions. The curve for nonreactive blends was obtained at varying processing
conditions . = Reactive blends; = non-reactive blends. Reproduced from Liu, N.C. and
Baker, W.E., Polymer, 35, 988, 1994.
transition from a brittle to a ductile failure to occur in toughened PP. Blends

without any interfacial reaction showed no improvement in impact properties whereas up to 13-fold improvement in notched impact energy was
observed for reactive blends above the brittle-ductile transition (Figure
4.27). Interfacial reactions not only help greatly in reducing the rubber
particle size but also play a further direct role in improving the impact
properties of PP jNBR blends. These conclusions are reinforced by the fact
that brittle-ductile transitions of PP /NBR blends occur at different rubber
particle sizes but only when the oxazoline functionality in the PP matrix
reaches relatively high levels (Figure 4.28).
Liu [42J further estimated the level of interfacial bonding required
for effective toughening at about 5 x 10- 7 mol/m 2 for notched PPjNBR
blends (Figure 4.29). This estimated value of critical interfacial bonding is
only moderately higher than literature results obtained by a very different
study in which pre-made block copolymers were used as compatibilizers [43].
190
15
>-
e>
CJ)
cCJ)
t5
10
C1l
0..
.S
"0
CJ)
.~
<il
0
0.2
0.3
0.5
Particle size (11m)
1.0
0.8
xCJ)
"0
.~
0.6
~
U
0.4
::::l
0
0.2
0.0
0.2
0.3
0.5
Particle size (11m)
...
Figure 4.28 Role of interfacial reaction and particle size in the brittle-ductile transition of
notched PP/NBR blends (each curve obtained at an identical processing condition by varying
amounts of interfacial reaction). The processing parameter was a measure of mixing intensity
and obtained by dividing the specific energy input during mixing by the torque ratio between
the rubber phase and the matrix. Processing parameter:. = 15; .... = 50;. = 140. Reproduced
from Liu, N.C. and Baker, W.E., Polymer, 35, 988, 1994.
4.4
Modification of polymer melts by bis-2-oxazolines
Before ending the chapter, it is worth touching briefly on the subject of

polymer melt modification by small molecule 2-oxazolines such as various
bis-2-oxazolines and tris- or mono-2-oxazolines. There are many patents
concerning the use of bis-2-oxazolines as chain extenders of polymers such
as PET and as coupling agents for polymer blends. Table 4.5 lists some of
191
12,----,----.----,----,----,----,
50
0.3
0.6
0.9
1.2
140
1.5
1.8
Interfacial bonding (~mol/m2)
Figure 4.29 Critical levels of interfacial bonding (per unit area of particle surface) in the
brittle-ductile transition of notched PPjNBR blends (each curve obtained at an identical
processing condition). The processing parameter, Pp , in the figure was a measure of mixing
intensity and obtained by dividing the specific energy input during mixing by the torque ratio
between the rubber phase and the matrix. Reproduced from Liu, N.C., Toughening of Brittle
and Pseudo-ductile Polymers via Reactive Blending - The Role of Interfacial Chemical Bonding;
PhD thesis, Queen's University, Kingston, Ont., Canada, 1992.
Table 4.5 Selected recent patents on the modification of polymer melts by bis-2-oxazolines
Patent No.
Year
Composition
EP583,807
JP05, 311, 055
JP03, 294, 354
JP03,247,652
EP400,936
EP384,190
EP371,444
JP02, 199, 157
JP02, 75, 655
JPOl, 289, 860
JPOl, 06, 054
EP282,263
JP63, 264, 661
JP63, 234, 058
JP62, 201, 963
1994
1993
1991
1991
1990
1990
1990
1990
1990
1989
1989
1988
1988
1988
1987
PET
PET
PC/PAr
PET/Phenoxy
PBT
PPS/PET
PC
PBT
PPE/PA
PA/PPE
PET/PPE
PET
PET
PC
PET/PA
Advantages
Recycling
Fluidity
Impact
Mechanical properties
Flammability
Appearance
Viscosity
Solvent resistance
HDT
Flammability
HDT
Tensile strength
Permeability
the recent patents on the subject. The polymer blend systems mainly have
polymers such as PET, PBT, PC, polyacrylate (PAr), poly(phenylene ether)
(PPE), poly(phenylene sulphide) (PPS), phenoxy, etc. A wide range of
properties are generally improved by the modification. Mono-oxazolines,
such as 2-ethyl-2-oxazoline, have been used to modify PET melt to reduce
its acidity by end capping [44].
192
Although less common there have also been publications in the literature
on the modification of polymer melts by 2-oxazolines. Cardi et al. [45]
studied the chain extension of recycled PET, and Inata and Matsumura [46]
studied the chain extension of PET with bis-2-oxazolines.
4.5 Conclusions
Interfacial reactions between polymers reactively functionalized with an

oxazoline group and other functional polymers having co-reactive groups
are effective in the compatibilization of polymer blends. Such co-reactive
groups include carboxylic acids, anhydrides, hydroxy Is, and amines, etc.
Oxazoline functionalized polymers can be prepared by the copolymerization
of vinyl oxazolines with other co-monomers and by the modification of
preformed polymers by melt grafting. The reactivity of oxazoline groups is
high. The interfacial reaction involving oxazoline functionalities is reasonably fast and, in most cases, diffusion controlled. Interfacial melt reactions
can improve a wide range of blend properties, including impact, heat
distortion temperature, process ability, tensile strength, etc. Oxazoline functionality is a suitable choice for model studies on the structure-property
relationships in compatibilized polymer blends. Small oxazoline molecules,
particularly bis-2-oxazolines, are useful in improving the properties of most
engineering polymers, such as PET, PBT, PA, PC, PPE, PAr and their
blends and in the recycling of such polymers.
4.6 Future trends
Blending is an economic method for improving the impact and tensile

properties and the chemical and solvent resistance, or to enhance the
process ability, abrasion resistance, flame retardancy, etc. Polymer alloys and
blends technology is progressing toward greater sophistication. The key for
success is blend compatibilization, including the generation and stabilization
of blend morphology and the improvement of reproducibility of blend
performance. Reactive compatibilization of polymer blends has been attracting increasing attention both from the academic and the industrial communities. Reactive polymers containing oxazoline functionality should play an
important role in the development of new high-performance materials as
well as in the optimization of existing blends. There is an increasing need
for the recycling of industrial and consumer polymers in response to
environmental concerns. Bis-2-oxazolines will play a role in recycling
polymers such as PET, PBT, PA, PC, PPE, etc.
Although studies on the control of the blend interface and morphology
and their effects on the performance of polymer blends have made significant
193
progress, more fundamental studies on the stabilization of blend morphology, the control of interfacial bonding and the structure-property relationships in polymer blends are important. Oxazoline functionality can be used
in model studies to evaluate the effects of interfacial reactions on the
development and stabilization of morphology and on blend properties and
to evaluate the critical requirement for interfacial bonding. The effectiveness
of grafted functionalities compared with that of copolymerized functionalities, the effect of the closeness of functional groups to the polymer
backbone, the exact amount of interfacial reaction, and so on, may also be
evaluated by using oxazoline-functionalized model systems. The wide commercialization of oxazoline-functionalized copolymers as reactive compatibilizers awaits the wider availability of vinyl oxazoline monomers.
Appendix 4.A
4.A.l
CPE
DMAEMA
DSC
EPDM
EPR
FTIR
GMA
HDT
HEMA
HPMA
HIPS
IPO
LLDPE
MA
NBR
NMR
OPS
PA
PA-PI
PAr
PBT
PC
PE
PET
POM
PP
PPE
PPS
PS
SBR
SEBS
SEM
SMAn
St-AA
St-BA
TBAEMA
Poly(ethylene-co-acrylic acid)
Dimeth ylaminoeth yImethacrylate
Pol y( eth ylene-co-propylene-co-diene)
Poly(ethylene-co-propylene) elastomer
Fourier transform infra red spectroscopy
Heat distortion temperature
Hydroxyethylmethacrylate
2-Hydroxypropy Imethacrylate
High-impact polystyrene
2-isopropenyl-2-oxazoline
Maleic anhydride
Poly(butadiene-co-acrylonitrile-co-acrylic acid)
Poly(styrene-co-vinyloxazoline)
Polyamide
Poly( amide-co-imide)
Polyarylate
Poly(butylene terephthalate)
Polycarbonate
Polyethylene
Poly(ethylene terephthalate)
Poly( oxymethylene)
Polypropylene
Poly(phenylene ether)
Poly(phenylene sulphide)
Polystyrene
Poly( styrene-co-butadiene) elastomer
Styrene-ethylene/butylene-styrene triblock copolymer
Pol y( styrene-co-maleic anhydride)
Poly(styrene-co-acrylic acid)
Poly(styrene-co-butyl acrylate)
t -Buty laminoeth yImethacry late
195
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5. Paul, D.R. and Newman, S. (1978) Polymer Blends, Academic Press, New York.
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Queen's University, Kingston, Ont., Canada.
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31. Sun, YJ. (1994) Etude de la Compatibilization des Melanges Polyolefine/Polyester en une
Seule Etape d'Extrusion Reactive, PhD thesis, Universite Louis Pasteur, Strasbourg,
France.
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Moisture cross-linkable silane-modified polyolefins

D. MUNTEANU
5.1
Introduction
Polyolefins (POs) are the largest-volume family of commercially important

high-tonnage thermoplastic polymers (about 60% share in thermoplastics in
1995). Polyethylene (PE) forms the major tonnage of plastics material
worldwide whereas polypropylene (PP) enjoys the fastest growing rates of
production. The emerging catalysts and technologies extend the properties
and application limits of POs beyond those traditionally accepted for these
resins to compete with other commodity thermoplastics, elastomers and
engineering resins.
The large number of PO grades available on the market for most of the
different applications may be regarded as:
physically functional materials, where the tailoring of polymer structure
and properties is performed during polymerisation; developments in
initiators and catalysts, engineering of the polymerisation processes and
an understanding of polymerisation kinetics allow today the most important features of POs to be tailored, such as molecular weight distribution,
branching type and distribution, crystallinity and stereoregularity;
homopolymers, random and block copolymers and even reactor-made
polymer blends are thus obtained;
chemically functional materials, where the use of different functional
monomers and different chemical reactions allows some useful properties
of the POs to be enhanced or new properties to be brought to them which
extend their applications. These modified polyolefins are obtained by two
basic approaches:
in-reactor modification - mainly the random copolymerisation of ethylene with functional co-monomers such as vinyl acetate, acrylic acid
and esters;
post-reactor modification - graft copolymerisation of functional monomers onto polyolefins, controlled degradation of polyolefins (polyethylene waxes, controlled-rheology polypropylenes) and subjecting POs to
different chemical reactions (controlled oxidation, chlorination, sulphochlorination and surface-fluorination).
Whereas the vast majority of the physically functional PO grades are
cheap commodity resins with large markets most of the chemically modified
Chapman & Hall 1997
MOISTURE CROSS-LINKABLE SILANE-MODIFIED POLYOLEFINS
197
polyolefins are speciality resins, more expensive, or even 'exotic' resins, often
tailored for very specific end uses and niche markets.
The conversion of the more or less linear structure of the PO chains into
a three-dimensional structure achieved by cross-linking not only drastically
improves a large number of properties such as high temperature properties,
mechanical properties and chemical and stress cracking resistance but also
imparts to POs new useful properties such as shape memory.
The first commercial cross-linked products were produced from lowdensity polyethylene (LDPE) in the middle of the 1950s by radiation
processes, and a few years later by peroxide processes. The applications of
these materials were initially in the cable area but developments in the
cross-linking processes and the use of other POs such as high-density
polyethylene (HDPE) have resulted in applications in other areas, such as
rotational moulded containers and pipes for transport of hot water or
chemically aggressive media.
In the late 1960s a third cross-linking technique was developed based on
silane chemistry. Unsaturated hydrolysable alkoxysilanes such as vinyltrimethoxysilane have been grafted onto POs, yielding moisture crosslinkable products because the pendent alkoxy groups attached to the PO
chains by grafting were capable of linking the chains into a three-dimensional network via the formation of siloxane bonds in the presence of trace
amounts of water.
In the late 1980s a new range of silane cross-linkable POs was introduced, this time by the in-reactor modification approach, i.e., by addition of
the organofunctional silanes to the high-pressure reactors used for the
production of LDPE.
This chapter is concerned with the moisture cross-linkable POs obtained
by both random and graft copolymerisation of silanes. This new crosslinking technique not only eliminated some disadvantages of the traditional
methods but also extended the properties and application limits of POs
cross-linked by irradiation and peroxides. Moreover, the silane cross-linking
method may be successfully used for other thermoplastics too.
5.2 Processes for cross-linking polyolefins
Cross-linking is the general term meaning the process of forming covalent

bonds or relatively short sequences of chemical bonds joining two polymer
chains together. Although the term 'cure' is used particularly to refer to the
cross-linking of unsaturated polyester and epoxy resins and 'vulcanisation'
for rubbers [1] both terms are often used for POs too, especially in the
technical literature.
The behaviour of POs to the reaction of free radicals is very dependent
on the PO structure. Thus, in PE the free radicals generate macroalkyl
198
radicals which combine to form larger molecules. However, POs with

tertiary bonded carbon atoms such as PP and poly(butene-1) are normally
decomposed by radicals, e.g. the PP degradation by p-scission of the chains
and can be cross-linked only by indirect means such as random
copolymerisation or grafting of suitable cross-linking co-monomers.
Irradiation- and peroxide-initiated cross-linking reactions have been
made effectively to increase the molecular mass of PE with corresponding
improvements in some properties. In the semicrystalline structure, consisting
of crystalline regions with amorphous parts in between, the amorphous
regions are weak from a mechanical point of view, with few interlamellar
links [2]. A three-dimensional network is formed by cross-linking with
chemical covalent bonds linking the crystalline and amorphous domains.
This drastically improves a large number of low-, room- and especially
high-temperature properties such as heat deformation, abrasion, viscous
deformation, chemical and stress-cracking resistance, impact and tensile
strength and also adds new useful properties such as shape memory.
Although this chapter is aimed only at silane cross-linking techniques a
short presentation of the irradiation and peroxide cross-linking processes
seems to be necessary for a better understanding of the merits and perspectives of silane cross-linking methods. The early history of PO cross-linking
was presented by Dole [3,4]. The state of the art of moisture cross-linkable
silane-grafted POs has been covered elsewhere [5]. Sultan and Palmlof
[6,7] reviewed the advances in cross-linking technology. Chodok has
recently reviewed [7a] the properties of cross-linked polyolefin-based
materials.
5.2.1
Irradiation cross-linking
The first commercial cross-linked products were produced by radiation in

the mid-1950s [3,8]. When PE is SUbjected to p or y rays (accelerated
electrons and electromagnetic waves from the C0 60 isotope, respectively) the
resulting macroalkyl radicals (R) combine to form a three-dimensional
network by C-C cross-linkages:
RH
f3 or r
a
.. RH
--b--i"~ R + 1/2H2
R + R ._-...... R - R
Scheme 5.1
Whereas y radiation is commonly used for laboratory experiments and

only some limited commercial applications such as sterilisation of films and
thin bottles the y rays, i.e. electron beams produced in big accelerators, are
commercially used for the cross-linking of PE. The high energy required to
199
penetrate deeply enough into the PE (e.g. 0.55 MeV and 1 MeV for 1 mm
and 3 mm thick cross-sections, respectively) represents the main limit of this
technique. Thus, high voltages are needed for cross-linking thick sections,
and circular objects have to be rotated, or several beams have to be used,
in order to achieve even irradiation. Irradiation cross-linking is a 'one-step'
process leading directly to the cross-linked structure, i.e. the irradiation is
done on the shaped polymer and not in the processing equipment.
The main application of irradiation cross-linking is, therefore, in the wire
and cable area where the insulating layer is not too thick and high output
extrusion can be used as there is no risk of pre-curing in the extruder.
Although advances in high-energy accelerators have reduced the price of
electron beams, the investment costs of irradiation cross-linking processes
are still considerable [6,7].
5.2.2 Peroxide cross-linking
The macroalkyl radicals (R) which combine to generate a three-dimensional network via C---C bonds may be formed into the PO matrix by other
means too. However, thermal decomposition of peroxides (POOP) is the
pOOP P()O+RH
..
2P()O
POH+R'
Scheme 5.2
only reaction of commercial importance:

Only those peroxides whose radicals are capable of abstracting hydrogen
atoms from the polymer can be used for cross-linking. The radicals may be
derived directly from the peroxide or produced during subsequent reactions.
Ultrahigh-frequency initiated decomposition of some special peroxides and
the generation of macroalkyl radicals by the thermal decomposition of azo
compounds gained very limited commercial use. As in the irradiation of PEs
all these methods are based on the formation of the macro alkyl radicals by
hydrogen abstraction from the polymer chain.
From a practical point of view, peroxide cross-linking is usually a
'two-step' process involving:
obtaining a cross-linkable polymer in the processing equipment by melt
incorporation of suitable peroxides into the polymer matrix;
obtaining the cross-linked polymer by heat treatment applied on the
finished article, normally made on-line directly after the extrusion step.
The peroxide is the key factor in this technology. Both the incorporation
200
Table 5.1 Dependence of the halflife
(till)
of some peroxides on temperature

till
Dcpa
5.7
24.0
DTBPHy b
CH 3
I
1.8
8.2
CH 3
I
DCP: C6HS - C - 0 - 0 - C - C6HS

I
CH 3
CH 3
0.6
2.8
12
54
(min)
4.5
20.0
CH 3
I
2
9
1.0
3.1
1.1
CH 3
I
DTBPHY: CH 3 - C - C :: C - C - CH 3
I
C(CH3b
C( CH 3b
of the peroxide in the PO melt and the processing of the resulting

cross-linkable polymer into finished items such as cable insulations, pipes
and profiles have to be performed at low temperatures, where the decomposition of the peroxide is slow, in order to avoid unwanted premature
cross-linking during processing, usually named 'pre-curing'or 'scorching'.
The risk of pre-curing is consequently related to the melting point of the
PO. Thus, HDPE with its higher melting point (about 13SC) presents more
risks than LDPE (melting point about 1lOC).
Peroxides suitable for cross-linking should slowly decompose at the
processing temperature used for their incorporation into the PO melt, i.e.
they should have long halflives (t 1/2) in comparison with the retention times
in the extruder, which are normally a few minutes (Table S.1).
For cable applications dicumyl peroxide (DCP), which is very suitable
for LDPE, has been used for more than 20 years giving safe processing up
to 12SC. The scorch temperature, i.e. the upper temperature limit for safe
processing, is normally mentioned in the technical data of the peroxide
suppliers. A slower decomposition peroxide, 2,S-dimethyl-2,S-bis(t-butylperoxy)hexyne-3 (DTBPHY), gives safe processing up to a temperature of
1S0C and is consequently more suitable than DCP for the cross-linking of
higher melting point POs such as HDPE (Table S.1).
During the cross-linking of the PO by the heat treatment applied on the
extruded product a reverse behaviour of the peroxides would be favourable
because faster decomposing peroxides will result in higher cross-linking
rates. Indeed, after about ten halflives (lOt 1 / 2 ) the peroxide has decomposed
almost completely (99.9%) and the maximum possible efficiency has been
achieved. Thus, the slow decomposing peroxide DMTBH needs 23 min at
180C to reach 90% of its final cure level instead of only 7 min for DCP.
The production speed is strongly dependent on the cross-linking rate, so
optimisation between safe processing and fast cross-linking should be
achieved. Approaches to realise the optimal compromise of safe processing
201
and fast cross-linking resulted in the development of different cross-linking

techniques within the area of cables and pipes, i.e. in the main applications
of peroxide cross-linking.
In the cable area, after the extrusion step the insulated conductor is
immediately subjected to vu1canisation by heat treatment. Both steam and
dry curing (pressurised nitrogen, silicon oil, eutectic salts) are used in
catenary, vertical and horizontal continuous vu1canisation lines, mainly
depending on the thickness of insulations. Direct contact heating vu1canisation is another technique used for heating a lubricated die around 25 m long
[6,7].
In hot water pipe applications stiffer POs such as HDPE have been of
main interest. The improvements in creep, impact and chemical resistance
achieved by cross-linking resulted in pipes with longer lives not only for hot
water but also for the transport of chemically aggressive media. Owing to
the higher melting point of HDPE a much higher temperature has
to be used than is the case for LDPE in cable insulation. Consequently, this
has complicated the utilisation of peroxide cross-linking in the pipe area
[6,7].
The Pont a'Mousson process is similar to the techniques used in the cable
field and involves the melt incorporation of the peroxide into HDPE grades
of molecular weight 200000-500000 followed by the cross-linking of the
extruded pipe in a salt solution at temperatures above 200C. Two other
different manufacturing processes have been developed to avoid the risk of
peroxide decomposition in the extruder.
The Engel process, the first process developed for HDPE, uses a reciprocating plunger extruder instead of a screw extruder. The pellets of high
molecular weight HDPE (Mw around 500000) are mixed with peroxide and
sintered together under high pressure (200-500 MPa). The mixture is not
subjected to high temperatures as in a screw extruder but is passed through
a long heated die where the cross-linking takes place.
The Daoplas technique completely avoids the presence of the peroxide in
the extruder. The peroxide is diffused into extruded HDPE pipes or profiles
immersed into a surrounding medium containing the peroxide. Crosslinking takes place by peroxide decomposition when extrudates are heated
above 160C under pressure.
Peroxide cross-linkable PEs are used for other processing techniques as
well, e.g. injection and rotational moulding. By optimisation of the rheological and cross-linking properties of the products as well as the processing and
curing conditions the polymer is melted and cured in the same mould.
5.2.3 Silane cross-linking

Both irradiation and peroxide cross-linking processes suffered some disadvantages such as high investment costs for irradiation equipment, the risk
202
Table 5.2 Organofunctional silanes, Y-(CHZ)n-SiX3 (n
0, ... ,3)
Silane type
Molecular weight
Boiling point at
760mm Hg (0C)
Specific gravity
VMSI"
VESI b
MMSI'
SMSI d
NMSI'
GMSI f
148
190
248
196
179
236
123
158
85
85
194
90
0.968
0.900
1.047
1.060
1.020
1.070
'VMS!: vinyltrimethoxysilane,
H2C = CH - Si(OCH3h
bVESI: vinyltriethoxysilane,
H2C = CH - Si(OC 2HJ3
'MMSI: 3-methacryloyloxypropyl-trimethoxysilane,
H2C
dSMSI: 3-mercaptopropyl-trimethoxysilane,
HS - (CH2hSi(OCH 3h
=f - coo - (CH2)3Si (OCHJ3

CH 3
'NMSI: 3-aminopropyl-trimethoxysilane,
H2N - (CH2)3Si(OCH3)3
fGMSI: 3-glycidyloxypropyl-trimethoxysilane,
H2C - CH - CH 20 - (CH2)3Si(OCH3)
\ I
of pre-curing in peroxide cross-linking processes, the inability to cross-link

POs with tertiary-bonded carbon atoms such as PP by the action of free
radicals and the formation of voids in cable insulations. Research efforts to
improve cross-linking technology resulted in the development of silane
cross-linking techniques which not only overcame some disadvantages of
the classical cross-linking processes but also gained new applications for the
cross-linked POs.
The new cross-linking technology is based on the chemistry of organic
silicon compounds [9,10] and uses organofunctional silanes (SI), i.e. compounds already employed in practice as surface modifiers of inorganic and
organic materials and as adhesion promoters or coupling agents between
inorganic materials (glass, minerals, metals) and organic polymers (thermosets, thermoplastics, elastomers).
Organofunctional silanes are bifunctional compounds of general formula
Y-(CH2)n-SiX3 (n = 0, ... , 3) (Table 5.2). The silicon as the central unit
of a silane is combined with two different functional groups. The organofunctional group Y:
c~
=CH -,
CH2 =C(CH 3)COO - ,
CH 2 - CH - CH 20 - ,
\01
H2N -,
HS -,
and
CI-
is strongly bound to the silicon via a stable unreactive carbon chain and is
responsible for the adhesion-bonding to the polymer by different pathways
203
such as chemical bonding, hydrogen bonding, wetting and surface energy

effects and acid-base interactions.
The silicofunctional groups X: -OR (R: CH 3 , C 2 H s), -Cl, -oCOCH 3 ,
mostly alkoxy groups which are directly attached to the silicon, are
relatively easy hydrolysable groups. After their hydrolysis to silanol groups
these can react with the active centres of an inorganic substrate (usually OH
groups) or by condensation and thus form stable bonds.
When used as surface modifiers and adhesion promoters or coupling
agents the organofunctional silanes establish linkages between polymers and
inorganic materials. Attached to the polymer chains by different means such
as random and graft copolymerisation, polymer analogous reactions (reactions between silane and a functionalised polymer containing suitable
reactive groups) the silanes function as cross-linking agents.
In 1968 Midland Silicones (Dow Corning) patented a two-step silane
cross-linking process for PEs [11,12]. The SIOPLAS technology [13,14]
involves, as in the irradiation and peroxide processes, the post-reactor
modification of POs, but the cross-linkages are siloxane (Si-O-Si) bonds
instead of C-C bonds. Unsaturated alkoxysilanes such as vinyltrimethoxysilane (VMSI) and vinyltriethoxysilane (VESI) (Table 5.2) have
been melt grafted in processing equipment, usually extruders, under normal
processing conditions in the presence of small amounts of peroxides as
grafting initiators. The silane-grafted POs are cross-linkable products, still
thermoplastic materials which are processed in the usual way in finished
articles subsequently subjected to cross-linking in the presence of water. The
alkoxy groups hydrolyse to form silanol groups which condense to generate
the siloxane bonds responsible for the formation of the three-dimensional
network. Before the moisture cross-linking step a master batch containing a
suitable catalyst, usually an organotin derivative such as dibutyltin dilaurate, is melt mixed with the silane-grafted PO in order to achieve crosslinking rates of practical importance.
In 1974 Maillefer and BICC patented [15,16] the MONOSIL process
which is a one-step version of the SIOPLAS technology. All the components, i.e. polyethylene + silane + grafting initiator + cross-linking catalyst,
are added in a high-shear mixing extruder provided with a longer screw
(length:diameter 30:1-35:1). This extruder, specially designed for optimal
mixing and grafting, also produces the finished articles, usually cables or
pipes, which are subsequently moisture cross-linked as in the SIOPLAS
process [14,17].
In the late 1980s a new range of silane cross-linkable PEs was introduced,
this time by the in-reactor modification approach. Union Carbide and
Mitsubishi Petrochemical [18] pioneered the addition of the vinyl silanes to
the high-pressure reactors used for the production of LOPE.
204
Although the moisture cross-linking of the resultant ethylene-vinyl silane

random copolymers takes place in the same way as for the silane-grafted
PEs differences in the properties of the products have been noticed mainly
arising from the structural difference of the silane-modified polymer, i.e.
random compared with graft copolymerisation of the silane.
5.3 The chemistry of silane cross-linking
Among the organofunctional silanes with polymerisable C=C bonds (Table

5.2) only the vinyltrialkoxysilanes and, most particularly, VMS!, gained
industrial acceptance for the commercial processes. From the chemical point
of view all the silane cross-linking processes have two distinctly separated
steps:
the synthesis of the silane-modified PO by silane grafting onto PO chains
or ethylene copolymerisation with silane;
the moisture cross-linking of the silane-modified polyolefin.
The mechanisms of silane random and graft copolymerisation are basically the same as for other vinyl monomers. Therefore, much attention is
paid in this chapter to the second stage, i.e. the moisture cross-linking of the
silane-modified polymers.
5.3.1
Synthesis of silane-modified polyolefins
The C-C double bond of the organofunctional silanes can be polymerised

in the presence of free-radical initiators. Whereas by the grafting approach
the silane moieties are attached to the PO chain the copolymerisation
approach yields random copolymers with the silane moieties distributed
within the chain.
(a) Graft copolymerisation of silanes onto polyolefins. The grafting of

silanes onto POs proceeds via a free-radical mechanism. Different freeradical-induced grafting methods such as high-energy and ultraviolet-(UV)induced grafting and solution grafting have been used [5]. However, only
the melt grafting of silanes in the presence of peroxides by 'reactive
processing' in processing equipment has gained industrial application.
The reaction mixture in the processing equipment, usually an extruder,
consists of polyolefin + silane (usually 2% VMS!) and a peroxide as
initiator (usually 0.1 % DCP). At the elevated processing temperatures
(140C-240C), peroxides thermally decompose to yield free radicals (RO')
which abstract H atoms from the PO chain. The resulting alkyl macroradicals (PE') will break the unsaturation in the silane (VMS!) and are
205
thus the active sites for the grafting of silane to the PO chain (PE-g-VMSI).
Termination occurs through chain transfer to the polymer (PE-gVMSI + PE)
ROOR
----aheat
-CH 2 -CH2 (PE)
2RO,
+ROo ~ -C~-C:H(PE)
-CH2-C:H- +H2C=CH
I
(PE)
(VMSI)
- CH 2- CH I
SI(OCH3)3
----a--
+ ROH,
-CH2 -CH- ,
I
CH 2
I
CH - SI(OCH 3)3
(PE - 9 - VMSI)
-CH2 -CHI
+-C;H-CH2 -
CH2
CH2
(CH - SI(OCH3h
CH2 - SI(OCH~3
(PE - 9 - VMSI)
-CH 2 -CH2 -
Scheme 5.3
The silane grafting reaction is very fast, and this is extremely important,
because it allows the choice of reactive processing to be the industrial
synthesis method. In spite of the short reaction times of only a few minutes
determined by the residence time in the extruder, very high grafting yields
are obtained, i.e. at least 80% of the added silane is grafted in an optimised
industrial process.
Under the conditions of reactive processing the possibility of silane
homopolymerisation may be almost excluded because of:
the low concentration of silanes in the system (usually about 2%),
the short reaction time (a few minutes in extrusion), and
the low reactivity of silanes for propagation owing to their steric hindrance.
Because the grafting reaction is a non-terminating one, combination and
other reactions will take place before the radicals present in the reaction
mixture become inactive. Some of these side reactions may have important
practical consequences. Thus, although the amount of peroxide used for
grafting is about 20 times smaller (0.1 %) than that used for peroxide
cross-linking (about 2%) the alkyl macroradicals (PE) formed by the
peroxide can combine to generate C-C bonds. Consequently, a pre-cure
process may take place in the extruder before the aimed at cross-linking via
206
Si~O~Si bonds is performed in the presence of water. Indeed, a drop-in

melt flow rate of the parent PO is always observed during the grafting
processes.
Alternatively, the alkyl macro radicals can consume the antioxidants that
have to be present in the PO for its processing and long-term thermal
stabilisation. The grafting process is therefore limited by the choice of
antioxidants as many of them are effective radical scavengers and can inhibit
the grafting reaction.
(b) Random copolymerisation of ethylene with silanes. LDPE is produced

by ethylene polymerisation at high pressure (150-350MPa) and temperature (lSOC-290C) in autoclave and tubular reactors in the presence of
free-radical initiators, usually peroxyl compounds. The high-pressure processes are also suitable for the copolymerisation of ethylene with polar
co-monomers such as vinyl acetate and acrylic esters [2]. The ethylene
copolymerisation approach seems to be the most obvious route to functionalise the non-polar chains.
Although the first patents for reactor-obtained ethylene-vinyltrialkoxysilane copolymers were published in the 1960s [19,20] and claimed the
production of cross-linkable materials, none of them alluded to the role of
water in the cross-linking mechanism. The cross-linking was attributed to
be 'solely by the application of heat' [19] or to be the result of 'mechanically working the product' [20]. This mistake may be explained today by
the fact that ethylene was copolymerised with VESI, which is less effective
in water cross-linking than is VMSI, and the lack of any catalyst to increase
the rate of the water cross-linking speed. The first commercial products did
not appear until the 19S0s, when Union Carbide and Mitsubishi Petrochemical [IS] pioneered the addition of the organofunctional silanes to the
high-pressure reactors used for the production of ethylene polymers [21,22].
Copolymerisation of ethylene with vinyltrialkoxysilanes proceeds in the
same way as in the case of other co-monomers commercially used in the
production of high-pressure ethylene copolymers. The resulting copolymers
with a silane fraction of less than 5 wt%, usually 1.6-2.3 wt%, have the
silane units more or less randomly distributed in the polymer chain (Scheme
5.4).
The basic properties of the products, e.g. molecular weight distribution,
CH2 =CH 2 +CH 2 =CH
I
Si(OCH
(Ethylene)
(VMSI)
- CH 2 - CH 2 - CH2 - CHI
Si(OCH
3)3
3)3
(PE-co-VMSI, or E-VMSI copolymer)
Scheme 5.4
207
can be optimised in the same way as for LDPE homopolymer. Crosslinkable terpolymers, by addition of another co-monomer, usually butyl
acrylate, together with the silane, are also possible to produce.
In comparison with the grafting route the silane copolymerisation is a true
one-step process with some important advantages. The silane is more
homogeneously distributed in the polymer chain so that it is possible to
achieve a certain degree of cross-linking with less silane incorporated in the
polymer. There is no limitation in the choice and consumption of antioxidants as in the case of peroxide and silane grafting cross-linking processes.
5.3.2
Cross-linking of silane-modified polyolefins
Both silane-grafted POs and ethylene-silane random copolymers are crosslinkable polymers. In the absence of water they are still thermoplastic and
can be processed in the same way as the unmodified polymer. Therefore,
cross-linking takes place separately from the grafting or copolymerisation
step and it is accomplished on the shaped finished article in the presence of
water.
(a) Moisture cross-linking. There are basically no differences between graft
and random copolymers concerning the cross-linking mechanism. Crosslinking proceeds through hydrolysis of alkoxyl groups and subsequent
condensation of the resulting silanol groups. Hydrolysis and condensation
reactions occur almost instantaneously. Siloxane cross-linkages between
adjacent polymer chains are thus generated. The water resulting from the
condensation of silanol groups can participate in the hydrolysis of alkoxyl
groups (Scheme 5.5).
The cross-linking reaction continues slowly without any addition of
catalyst. Consequently, a characteristic of these polymers is their sensitivity
to water on storage, i.e. the risk of premature curing leading to the
formation of discoloured unmeltable particles, so-called scorch, that drastically reduces the breakdown and mechanical strength of the products and
reduces the time of the continuous operation of the shaping extruder.
The moisture sensitivity of the grafted copolymers is higher than that of
the random copolymers and results from the mobility of the longer pendent
trialkoxyl moiety, i.e. the presence of the ---CH 2-CH 2 - group, that is
obtained from the grafting process. In the random copolymers the
-Si(OR)3 functionality is directly attached to the polymer chain (see
PE-g-SI and PE-co-SI, Scheme 5.5). Concerning the silane type, VESI is less
effective in water cross-linking than is VMSI.
Having a rather limited shelf-life the commercial products are normally
stored in moisture-proof, aluminium-foil-lined packages and must be converted immediately after opening. Scorch-retardant additives have been
208

or random copolymer: - CH 2 - CH 2 - CH2 - CH -
Grafted copolymer: - CH 2 - CH -
Si(ORh
CH 2 - CH 2 - Si(ORh
(PE-g-SI)
(pE-co-SI)
(R: CH3" for VMSI, and C2 Hs" for VESI.)

Reaction steps:
-------r------RO-Si-OR
I
+ H20
OR
-------r------RO-Si-OR
I
OH
OH
I
-------r------RO - Si - OR
I
+ ROH
(Hydrolysis),
+ H2 0
(Condensation).
OH
------,-------RO-Si-OR
I
o
I
RO-Si-OR
______ L ______ _
RO-Si-OR
_______ L- _____ _
Scheme 5.5
developed to inhibit both water and thermal cross-linking during processing

[6, 7, 22].
To achieve a cross-linking rate of practical importance the addition of a
suitable catalyst and the use of elevated temperatures are necessary. The
active catalyst is usually organo-tin-derived, normally dibutyltindilaurate
(DBTDL), which is dry blended as masterbatch with the silane-modified
polymer before processing into finished articles. Cross-linking takes place
beside the production line in hot water tanks or steam chambers, normally
at 60C-90C. Under these conditions the curing time may be in the order
of a few hours or days. However, recent developments in catalyst masterbatches are enabling curing times of a few days at ambient conditions, i.e.
room temperature and 50%-55% relative humidity [6, 7,22].
As for the peroxide cross-linked POs the cross-linking performances of
the silane-modified POs may be evaluated by establishing the cross-linking
speed, the final cure level and the pre-curing behaviour. All of these involve
the measuring of the cross-linking degree or cross-linking density, i.e. the
fraction of polymer chain units, normally the repeat units, that are crosslinked [1].
For measuring the cross-linked degree of cross-linked PE three methods
are mainly used:
extraction in aromatic solvents such as toluene, xylenes and decaline
(ASTM D 2765) to measure the gel content, widely used because of its
simplicity;
hot set test (lEC 811) to measure the heat elongation of dumb-bells at a
209
specific load and temperature;

rheometers for more detailed studies [6,7].
The chemistry of the silane cross-linking is much more complicated than
the chemistry of peroxide and irradiation cross-linking. Unwanted thermal
cross-linking during the processing of silane-modified POs leads to the
formation of C---C bonds instead of the intended Si-o-Si linkages by
water cross-linking. In the early studies on silane-grafted POs the water
cross-linking was followed mostly by measuring the changes in gel content
and mechanical properties [13, 14, 23-26].
Owing to its simplicity the measurement of the gel content and mechanical properties is still used, especially for practical purposes, to follow the
cross-linking process. However, a better understanding of the cross-linking
chemistry was achieved by analysing the structural changes by different
analytical techniques such as infra red (IR) and Fourier transform IR
(FTIR) spectroscopy, X-ray diffraction, differential scanning calorimetry
(DSC), size exclusion and gel permeation chromatography (SEC and GPC,
respectively) and transmission and scanning electron microscopy (TEM and
SEM, respectively). These techniques have been used to investigate the
silane-grafted POs [27-38] and the ethylene-silane random copolymers
[39-42], not only concerning the cross-linking step but also concerning
different aspects of synthesis and structure.
Gazel et ai. [27] followed the hydrolysis of LDPE-g-VMSI films (2%
grafted silane) by IR spectroscopy. Ungrafted VMSI shows three absorption
bands, at 1190cm-1, 1095cm- 1 and 795cm- 1 , and all of them completely
disappear following the silane hydrolysis. Although grafted VMSI exhibits
the same three absorption bands, only the 1190cm- 1 and 795em- 1 bands
completely disappear following the polymer hydrolysis. The intensity of the
1095 cm -1 band decreased and a shoulder developed around 1060 cm - 1
when no catalyst was introduced. An additional shoulder appeared around
1120cm- 1 only when hydrolysis was performed in the presence ofDBTDL.
The 1060 cm -1 band was attributed to the Si-O-Si bond vibration in
single linkages, and the 1120 em - 1 band to the same vibration of the
siloxane bonds implied in double or triple linkages (Scheme 5.6).
However, it was generally assumed that it is not possible that all three
alkoxyl groups present at each silicon atom can react. Based on kinetic and
thermodynamic considerations the most probable hypothesis was accepted,
i.e. that on average only two of the three alkoxy groups react. Thus, a chain
of PO-g-SI is capable of reacting with two or more similar chains to form
networks with Si-O-Si cross-links [5-7, 13, 14, 23, 29].
The cross-linking chemistry of the reactor-made materials has been
investigated too [6, 7, 22, 39-42]. Hjertberg, Palmlof and Sultan [40]
studied the cross-linking of PE-co-VMSI (1.6% VMSI) in water at 90C in
the presence of 0.05% DBTDL. The kinetics of the cross-linking were
210
I
/OCH3
CH-Si-OCH 3
I
'OCH 3
I
/OH
CH-SI-OCH3
I
'OCH
OCH 3
I
I
I
OCH 3
I
I
CH-Si-O-Si-CH I
OCH 3
I
/OH
CH-SI-OH
I
'OCH
CH-SI-O-SI-CH -
/ 0........
OCH 3
OCH 3
I
/OH
CH-SI-OH
I
'OH
........
CH - Si I
OCH3
(1060cm- 1)
1
~
-
SI - CH
........0 ..........
I
(1120 crrrl)
Scheme 5.6
followed by measuring the gel content and by the determination of the

content of different structures (-Si-OCH 3 , free -Si-OH and hydrogen
bonded -Si-OH ... HO-Si-, -Si-O-Si-) using FTIR spectroscopy.
The maximum gel content of 70%-75% was obtained in a much shorter
time (25 h) than the period required for the levelling of the absorption index
for the Si-O-Si band at 1030 cm -1 (100 h) (Figure 5.1). This indicates
that the formation of Si-O-Si linkages a long time after maximum gel
content was obtained should be mainly within the existing gel. Measurements of mechanical properties provided additional evidence for the appearance of the new linkages to the following possible reactions:
molecules already part of the network form even more cross-links, i.e. an
increased cross-linking density within the gel (reaction a in Scheme 5.7);
formation of cyclic siloxanes is, however, less likely as it involves a
2
~
'0
..!:
100
r
0
-Si-O-Si-
....-
!!-
Gel
50
C
.l!!
c:
0
0
(jj
(!)
100
200
Time (h)
Figure 5.1 Gel content and absorption index for the Si-O-Si band at l030cm -1 of E-VMSI
copolymers as a function of time of treatment in water at 90C. Reproduced from Hjertberg,
T., PalmI of, M. and Sultan, B.A., Journal of Applied Polymer Science, 42, 1185, 1991.
;;d{oH
-Si-
OH
OH
211
HO-SI-OH
-SI-
~
HO-SI-OH
I
o
I
HO-SI-OH
~
I
OH
OH
~
HO-Si-OH
I
o
I
:::h
HO-Si-OH
~
Scheme 5.7
four-membered ring with considerable strain which should therefore be

thermodynamically unstable (reaction b);
reactions between molecules with only one silane group each (reaction c).
(b) Thermal cross-linking. Silane-modified POs subjected to thermal treatment during processing could undergo premature cross-linking. The practice
showed the disadvantages of the grafted-type materials [6,7]. The use offree
radicals for grafting leads to side reactions, in particular molecular enlargements, in the same way as observed in connection with compounding and
processing prior t~ peroxide cross-linking.
Studies on the cross-linking reactions of ethylene-silane random
copolymers at processing temperatures showed that an external supply of
water as well as heat and catalyst are the most important factors for
212
100.----------------------.
(d)
~
~
Qi
Ol
15 50
C
Q)
C
0
200
300
400
Temperature (ee)
Figure 5.2 Gel content of ethylene-silane copolymers (O.2mm films) after heat treatment for
10min under different conditions: (a) E-VMSI copolymer under dry nitrogen, (b) nitrogen
presaturated with water, (c) nitrogen presaturated with water, catalyst added, and (d)
E-VMSI-BA terpolymer under dry nitrogen. Reproduced from Palmlof, M., Hjertberg, T. and
Sultan, B.A. Journal of Applied Polymer Science, 42, 1193, 1991.
premature curing during processing [39,41]. The evolution of gel content

with temperature in the PE-co-VMSI (1.6% copolymerised silane) under dry
conditions showed behaviour very similar to that of ordinary LDPE, i.e.
very low gel contents independent of temperature. This could be expected
as water is the actual cross-linking agent. Indeed, in the presence of water,
formation of gel can be observed, and the amount of gel increases with
temperature. Addition of a cross-linking catalyst (DBTDL) considerably
decreases the onset temperature and increases the gel content [41] (Figure
5.2).
The measurement of the gel content by solvent extraction is less well

suited for a definitive differentiation between samples of low levels of
cross-linking as expected during processing. Bullen, Capaccio and Frye [39]
used a dynamic mechanical spectrometer to follow continuously the changes
in storage modulus during heat treatment of PE-co-VMSI above 140C.
This technique is very sensitive towards molecular enlargements before
major cross-linking occurs and proved that no molecular enlargement
ocurred at the processing temperatures under dry conditions and in the
absence of the catalyst.
SEC analysis with an on-line low-angle laser light scattering (LALLS)
detector which has a high sensitivity to high molecular weight species
emphasises also the necessity to avoid cross-linking reactions during processing in order to maintain proper processing properties [40,41]. Indeed,
at very low levels of gel the molecular weight increases rapidly in the soluble
213
part of PE-co-VMSI. At somewhat higher contents of gel the molecular

weight values drops drastically because larger molecules should be more
easily attached to the gel compared with smaller ones.
E-VMSI - BA terpolymers are much more susceptible to gel formation
during processing than E-VMSI copolymers. Palmlof, Hjertberg and Sultan
[41] investigated the thermal cross-linking of a E-VMSI - BA terpolymer
(2.3% VMSI and 20% BA). Neither water nor catalyst was needed for the
formation of gel in comparison with E-VMSI copolymers where safe
processing occurred under the same conditions. Up to 240C only small
amounts of gel were formed, but at about 250C the rate of cross-linking
started to increase rapidly for the terpolymer (Figure 5.2). Although the
moisture content of the terpolymer (342 ppm) was higher than that of a
E-VMSI copolymer (135 ppm), owing to the lower crystallinity and the
hydrophilic nature of the ester group, the included amount of water is three
to four times lower than the quantity required to match the observed gel
contents. Through use of FTIR spectroscopy and blends of model polymers
(E-VMSI plus E-AA and E-MA copolymers) it was proved that the water
responsible for cross-linking was supplied from an internal source. Butylacrylate groups from the terpolymer were thermally degraded under formation
of butene-l and carboxylic acid groups along the chain. The carboxylic acid
groups may react with each other and thus form anhydride under simultaneous formation of water [41].
The FTIR spectra show that formation of both non-cyclic and cyclic
anhydride may occur (reactions in Scheme 5.8). Saturated non-cyclic anhydrides could be formed by intermolecular reactions (reaction b) or an
intramolecular reaction between two well-separated acrylic acid units (reaction c, where n> 1). Cyclic anhydrides may result from intramolecular
reactions between two acrylic acid units that are adjacent or separated by
one or two ethylene units (reaction c, where n = 0, 1). For both non-cyclic
and cyclic anhydrides the in situ generation of water leads to the hydrolysis
of -Si-OCH 3 to -Si-OH groups, which subsequently condense to form
the -Si-O-Si- cross-linkages [41].
Additional factors may explain the higher sensitivity of E-VMSI - BA
terpolymers to cross-linking during processing:
the carboxylic acid group being a Bmnstedt acid might have a catalytic
effect;
the formation of other kinds of cross-links besides the water-induced
generation of -Si-O-Si- bonds:
reactions of carboxylic groups leading both to non-cyclic and to cyclic
anhydrides (-CO-O-CO- cross-links) as shown in Scheme 5.8;
reactions between carboxylic acid and silanol groups (-Si-O-Cocross-links), as shown in Scheme 5.9;
thermal-induced condensation of alkoxysilane groups (-Si-O-Si-
214

heat
- CH 2 - CH - CH2 - CH 2 -
COOC4 H,
COOH
-CH2 -CH - CH2 - CH 2 -
- CH 2 - CH - CH2 - CH 2 -
COOH
CO
I
non-cyclic anhydride
COOH
CO
- CH 2 - CH - CH2 - CH2 -
+ CH2 =CH-CH 2 -CH 3
-CH2 -CH-CH2 -CH 2 -
- CH2 - CH - CH2 - CH2 -
(CH2 - CHJ n - CH2 - CH

I
COOH
-H 0
/(CH2 - CH2)n - CH2 - CH

I
CO
I
----L.
R\
c
0
I
CooH
n =0, 1, cyclic anhydride,

n > 1, non-cyclic anhydride
CO
(CH2 -CH)
2 n -CH 2 -CH-
(CH2-CH2)n-CH2-CH-
Scheme 5.8
R-CHI
-Si-OH
R-CH-
-CH-R'
I
-CH-R'
-SI-O-CO-
HooC
Scheme 5.9
OMe
OMe
OMe
OMe
R-SI-OMe
MeO-Si-R'
I
OMe
OMe
I
R - Si - 0 - SI - R' +
I
OMe
Me - 0 - Me
OMe
Scheme 5.10
cross-links) that may occur in E- VMSI copolymers too as shown in

Scheme 5.10 [22].
( c) Cross-linking catalysts. Although the cross-linking process takes place
spontaneously in the presence of water, unaided cross-linking is relatively
slow so that a small addition of a suitable catalyst is necessary to make the
cross-linking rate more attractive in practical terms. The cross-linking
process is strongly accelerated in the presence of some organo-tin compounds. These cross-linking catalysts should be compatible with the silanemodified PO. They are incorporated into the polymer at concentrations of
215
(C4H9hSn(OCOCllH23)2+ H2 0
(DBTDL)
(DBTL-OH)
(LA)
Scheme 5.11
0.05%-0.15%, usually 0.10%, and usually as masterbatches.

It seems that the catalysts accelerate both the hydrolysis of alkoxysilane
groups to silanols and their subsequent condensation to siloxane bonds by
decreasing the activation energy of these reactions. Indeed, both steps are
catalysed by Bmnstedt acids [43,44]. However, no quantitative data were
reported about the kinetics of these two reactions.
Although DBTDL is widely used in practice as a cross-linking catalyst
both for silane-grafted and for copolymerised materials, its true role in
the moisture cross-linking process remains unclear. It is suggested that
DBTDL undergoes partial hydrolysis to give dibutyltin laurate hydroxide
(DBTL-OH) and lauric acid (LA) (Scheme 5.11), and that it is this
hydrolysis product that is the 'true' catalyst. The mechanism seems to
involve an intermediate containing a weak Sn-O-Si linkage, but there is
no solid evidence for this.
Toynbee [45] showed that there is a dynamic equilibrium in DBTDL
which is greatly affected by the polarity of the surrounding medium. IR
spectra of DBTDL clearly show two carbonyl resonances centred at
1740 cm -1 and 1720 cm - 1. The absorption at 1740 cm - 1 typically for ester
compounds is assigned to the carbonyl absorption in DBTDL, and it was
the major component in the IR spectra of the catalyst solutions in polar
solvents such as diethyl ether. However, in non-polar media such as heptane
or PE the 1740 cm - 1 band almost disappeared and the major component
was the 1720 cm - 1 band, attributed to the hydrolysis product, i.e. arising
from lauric acid, the organo-tin hydroxide DBTL-OH, or both. Thus, in
non-polar polymers such as PE the formation of the so-called 'true' catalyst
(DBTL-OH + LA) is favoured, i.e. the active catalyst is already present
and does not need subsequent hydrolysis which may result in a faster cure
than in polar polymers such as E-VA random copolymers.
5.4 Silane-grafting processes
As stated before, moisture cross-linkable silane-grafted POs are obtained by
'reactive processing', i.e. the melt grafting of POs with silanes in the
processing equipment in the presence of peroxide as grafting initiators. The
'two-step' SIOPLAS process and then the 'one-step' MONOSIL process
(Figure 5.3) were initially developed for cable insulations based on LDPE.
216
SIOPLAS PROCESS
MONOSIL
PROCESS
DIRECT INJECTION
:=::;~;:=':::::lOI____~
Figure 5.3 Silane grafting processes for cross-linked polyolefins.
Then, other POs have been grafted and the applications of the resulting
materials have progressed outside the cable industry.
The state of the art of silane grafting including patents, processes,
development work required, etc. has already been covered [5]. In this
chapter, more emphasis is to be put on the main process variables and on
data contributing to a better understanding of the grafting process.
5.4.1
Reactive processing equipment
The reactive processing uses processing equipment such as a chemical

reactor. The equipment should provide a highly efficient mixing action for
the reaction mixture: poly olefin + silane + grafting initiator. Antioxidants
may also be incorporated into the reaction mixture, especially for the cable
grades. Silane-grafted POs are usually produced in extruders, but internal
mixers can also be employed. Cross-linking is normally done in a separate
step so that differences appear only in the grafting and shaping steps.
(a) 'Two-step' processes. The 'two-step' SIOPLAS process separates the
grafting step from the shaping step (Figure 5.3). High-shear compounding
extruders or co-kneaders are used as grafting extruders. The feeding of the
217
extruder with the reaction mixture may be done by several means, such as:
tumble mixing, which is not very efficient and requires high-shear extruders,
discontinuous or continuous metering and mixing of ingredients into the
extruder hopper provided with a stirrer,
direct injection of the silane and peroxide solution either in the base of
the feeding hopper or in the extruder barrel into the melted polymer
(Figure 5.3) [5].
In the second step the silane-grafted PO and the catalyst master batch are
blended and formed into product by extrusion or moulding. Processing
conditions for extrusion, injection moulding and rotomoulding are the same
as for the base polymer. Thus, standard PO extruders provided with screws
with a length-to-diameter ratio (L:D) of at least 20:1, but preferably 25:1,
and a compression ratio of about 3:1, are used as shaping extruders for cable
insulation and pipes.
(b) 'One-step' processes. The MONOSIL process performs both the
grafting step and the shaping step in the same extruder. All components,
i.e. polyolefin + silane + peroxide + cross-linking catalyst are added in a
specially designed extruder for optimal grafting and mixing. The extruder is
provided with a long screw (L:D = 30:1-35:1) capable of developing
high-shear (Figure 5.3). Very good temperature control and distributive
mixing are required. If good mixing does not occur then gel is likely to form
in discrete areas as 'nibs' in the product.
In comparison with the 'two-step' process, the MONOSIL process has a
lower investment cost, smaller space requirements for the production unit,
and avoids moisture pre-curing because the grafted PO is not stored at all
before it is shaped into the finished item. As a 'one-step' process it can be
used only for extruded products such as cable insulations and pipes. Other
processing techniques such as injection moulding and rotomoulding have to
use silane-grafted POs made by the SIOPLAS process or ethylene-silane
copolymers made by high-pressure processes.
Other 'one-step' processes have been developed with the aim of replacing
the expensive extruder specially designed for the MONOSIL process with
more or less 'standard' PO extruders. Thus, in a process developed by
Kabel-Metal Co. [5] both grafting and shaping are performed as one
operation within the same extruder provided with a normal PO screw
(L:D = 25:1). The extruder is fed with dry PO granules or powder containing all the ingredients (silane + peroxide + antioxidant + catalyst). The ingredients are incorporated into the PO particles stirred in a high-speed
mixer (500-3000 rpm) at 80C-100C. This temperature is below the
softening point of the polymer which retains its geometrical shape but it is
high enough to favour the homogeneous dispersion of the ingredients in the
218
Table 5.3 DYNASYLAN SILFIN grades.

DYNASYLAN
SILFIN
VMSI (wt%)
01
02
03
04
05
06
11
12
92.4
90.9
87.0
85.7
90.5
88.7
85.0
92.5
Peroxide
type (wt%)
TBCpa
DCP
DCP
DCP
DCP
DCP
DCP
DCP
5.3
6.8
9.7
10.7
7.2
7.8
15.0
7.5
DBTDL (wt%)
2.3
2.3
3.3
3.6
2.3
3.5
Grafting
process
One step
One-step
One-step
One-step
One-step
One-step
Two-step
Two-step
Source: Hiils, A.G., 1990, Application of Organofunctional Silanes D YNASYLAN.

aTert-butylcumene peroxide; mixture specially stabilised against homopolymerisation.
polymer matrix, thus avoiding the need of highly efficient mixing extruders.
Although direct injection of all ingredients into the polymer melt may
appear to be a simple alternative the slow laminar mixing of the standard
low-shear PE screw will produce zones of high additive concentration for
periods long enough for gel formation. The highly efficient blending device
called a cavity transfer mixer (CTM) was developed by Rapra Technology
Ltd for fitting as an add-on unit to the barrel and screw of existing
extruders. This made possible the production of silane-grafted POs by
injection of the silane + peroxide + catalyst solution directly to the PO melt
just prior to the CTM device (Figure 5.3). The process may be an alternative
to other methods and a suitable way of using currently idle extrusion lines
and expanding the market for silane-cross-linked PO [46, 46a].
Silane producers also supply ready-to-use mixtures of silane + peroxide,
and of silane + peroxide + catalyst for the 'one-step' and 'two-step' processes,
respectively (Table 5.3). Particular mixtures are specially recommended for
selected applications, e.g. for cable sheatings for the low-voltage sector
(SILFIN 01 and 06) and for the medium-voltage sector (SILFIN 03) [47].
For customers' special requirements 'tailor-made' silane mixtures may be
also delivered. The silane mixtures are sensitive to moisture, heat and
impurities. At temperatures above their self-accelerating decomposition
temperature (e.g. > noc for SILFIN mixtures 01 and 06) they react
exothermally with homopolymerisation. Thus, storage temperatures above
30C have to be avoided. After five weeks storage at 30C the relative
decrease in silane content is less than 2% [47].
( c) Internal mixer processes. Internal mixers are less used for the production of silane-grafted POs than extruders. PO pellets are usually tumble
blended with a silane solution of peroxide before mixer loading, but other
alternatives are possible. After grafting the polymer melt is discharged in an
219
extruder to be converted into pellets or directly into finished articles. The

antioxidant and the cross-linking catalyst may be added pure or in the form
of masterbatch, usually at the end of the mixing cycle [5]. Lower temperatures (140C-180C) and longer reaction times (5-30min) may be used
than for extruder grafting. The employed silane should have a boiling point
(Table 5.2) above the processing temperature in order to avoid its evaporation.
In comparison with extrusion processes internal mixer grafting is especially suitable for:
direct grafting of bale elastomers such as EP and EPDM rubbers [25,48];
grafting of higher silane levels, e.g. 5%-30%;
compounding of the silane-grafted POs with other ingredients in the same
mixing cycle.
More details on various technical modifications of the grafting processes
are provided elsewhere [5].
5.4.2
The effects of various parameters on the grafting reaction
The literature concerning PO cross-linking by silane grafting consists

mainly of patents. This situation is most likely a consequence of the
technological character of the method. The result of the grafting is generally
evaluated only as the gel content of the cross-linked PO, with no data on
the grafting yield, i.e. the ratio of reacted to unreacted silane. In 1985 the
author emphasised the need for detailed data on the dependence of the
grafting process on the grafting formulations and reaction conditions [5].
Since that time very few studies on this topic have been published [28-34].
Silane grafting on POs depends on the following main variables:
the type of the PO and silane as well as their ratio,
the type and concentration of the grafting initiator,
the stabilisation package.
The silane grafting reaction is very fast. This is certainly an important
advantage because very high grafting yields are obtained during the short
reaction times of only a few minutes in extruders. Such a behaviour allowed
the reactive processing to become an efficient method for silane grafting in
practice, but from the scientific point of view it may be regarded as a
disadvantage as well. Indeed, it is difficult to follow the kinetics of the
grafting reaction directly during the reactive processing. To date there is still
a need for broad-based knowledge and expertise in this field. For a better
understanding of the processes and also for more useful commercialisation
it is important to know quantitatively the variables and kinetic parameters
that affect the grafting as well as the cross-linking processes.
220
(a) Polyolefins and silanes. The reactive processing techniques are capable
of silane grafting onto any kind of olefin homopolymer or copolymers:
ethylene polymers (LDPE, HDPE, medium-density PE (MDPE), linear
LDPE (LLDPE), very-low-density PE (VLDPE), PE waxes), high-pressure
ethylene copolymers (EVA, ionomers), propylene polymers (homopolymers,
random and impact copolymers, atactic PP), EP and EPDM rubbers,
polyisobutene [5].
Concerning the silane type, the most widely used is VMSI, whereas VESI
and especially 3-methacryloyloxypropyl-trimethoxysilane (MMSI) have
limited applications. Grafting of silanes onto PO blends and grafting of POs
with mixtures of silanes and different co-monomers such as glycidyl methacrylate and stearyl acrylate are also reported, with the aim of improving
certain properties for selected applications [5].
However, the materials available on the market seem to be produced only
by the grafting of VMSI onto the most important commodity POs such as
LDPE, HDPE, LLDPE, PP, EVA copolymers, EP and EPDM elastomers.
In most instances the grafting receptacles contain about 2% silane. At this
level a high gel content may be achieved following the moisture crosslinking of the grafted PO.
The free radicals generated by the peroxide decomposition under the
conditions of the reactive processing abstract hydrogen atoms from the PO
chain. The resulting PO macro radicals are the active sites for silane grafting
but can also be involved in subsequent side reactions, such as:
disproportionation to form unsaturated species,

fJ-scission in the polymer chain, and
recombination leading to chain extension.
Both hydrogen abstraction and the side reactions depend on PO type. The
free radicals abstract hydrogen easier from tertiary carbon (CIIl) atoms than
from secondary carbon atoms, but the reactivity of the resulting macroradicals is in the reverse order. Therefore, higher grafting yields are expected for
PE types with higher amounts of CIII atoms along their chains.
Wong and Varral [34] performed grafting of VMSI (1.2%) onto LDPE,
LLDPE and HDPE in the presence of DCP (0.1 %) and evaluated the
amounts of grafted silane by measuring the 1090 cm - 1 absorption band
attributed to the Si-O-C stretching vibration of silane. Although this
method does not give the exact content of the grafted silane, because no
calibration curve was used, it is useful to compare the grafting efficiency of
different PE types subjected to identical grafting conditions. Whereas LDPE
and LLDPE showed comparable amounts of grafted silane the grafting
efficiency for HDPE was about two times lower owing to its lower content
ofCIIl atoms (usually HDPE has only 1-3 methyl groups per 1000C atoms
in the chain).
221
10 6 . - - - - - - - - - - - - - - - - - - - - - - - - - ,
(a)
(b)
( c ) - - -_ __
Shear rate (rad/s)
Figure 5.4 Shear viscosity curves at 180C of: (a) LLDPE-g-VMSI, (b) DCP-treated LLDPE,
and (c) unmodified LLDPE. Reproduced from Wong, W.K. and Varrall, D.C., Polymer, 44,
1153, 1992.
The dependence of shear viscosity on shear rate for unmodified, peroxidetreated and silane-grafted PEs emphasised how side reactions depend on the
polymer structure too. LLDPE, with its fair number of randomly distributed
short chain branches, resulted in the highest degree of chain extension
reaction, mainly because of the formation of stable Cm free radicals which
could then recombine to form chain extensions (Figure 5.4). The LDPE,
owing to its more clustered short chain branches, suffers a certain amount
of p-scission and therefore a lower degree of chain extension. The HDPE is
not very highly chain extended by free radicals owing to the very low
amount of em atoms along its chain [34].
For ethylene-propylene (EP) and ethylene-propylene-diene (EPDM)
elastomers, where em atoms are part of the repeat unit and not 'structural
defects' of the chain, the grafting yield strongly depends on their composition. The cross-linking potential of the EP copolymers with narrow molecular weight distribution decreases with increasing propylene segment content
(in the range of 20%-70%) because in propylene segments the tendency of
polymer chains to undergo degradation is higher and the tendency of the
relatively stable macro radicals to be stabilised through a graft or crosslinking reaction is lower than in ethylene segments of the chain [25]. Sen et
al. [33] found that the values of the activation energy (Ea) of silane grafting
are about the same for both LDPE and an EP copolymer with high
percentage of ethylene units (about 75%). The grafting reaction seems to
proceed through the same reaction sites, i.e. the -CH 2-CH 2 - units, for
both polymers.
No data are reported on the influence of the PO molecular weight
distribution on the grafting yield. It would be necessary to know the
222
'chemical heterogeneity' of the silane-grafted PO, i.e. the content of the

grafted silane in chains of different molecular weights and not only the
average content. The distribution of grafted silane units is certainly of
practical importance because low molecular chains make very little contribution to the formation of cross-linked networks. This behaviour was
observed for EP copolymers of very broad molecular weight distribution
which contain a large proportion of oligomers and showed, following silane
grafting, a much lower cross-linking potential (gel content) than the medium
and narrow molecular weight distributed copolymers [25].
To overcome the difficulty of following the kinetics of the very fast
grafting reaction directly during reactive processing, Sen et al. [33] used
differential scanning calorimetry (DSC) for this purpose because this
method potentially allows determination of the rate of polymerisation as a
function of temperature. This approach made possible the study of the
effects of some parameters on the grafting reaction. The DSC traces of
reaction mixtures (PO + silane + DCP) showed that the heat evolved
during the grafting reaction increased with increasing silane content (5%25%) for both VMSI and VESI grafted onto LDPE and EP copolymers.
Under identical reaction conditions no such sharp exotherms have been
obtained for MMSI, probably because of the steric hindrance imparted by
the acryloyloxyl group. However, there are patents claiming the grafting of
MMSI at the usual concentration of about 2% employed in practice [5], i.e.
much lower than the concentration used to compare the reactivity of VMSI,
VESI and MMSI (112.5 mmol silane per 100 g PE, i.e. 22% MMSI in the
reaction mixture) [33].
30r-----------------------------~
(c)
------(b)
E 20
iii
.s:::
~
I::
1
a:
75
150
VTMO (mmol)
225
300
Figure 5.5 Dependence of DSC reaction exotherm of VMSI grafting onto LDPE on silane
concentration (mmol per 100gPE) and peroxide content: (a) 0.8, (b) 1.2, and (c) 1.4mmol DCP
per 100 g PE. Reproduced from Sen, A.K., Mukherjee, B., Bhattacharya, A.S. et al. Journal of
Applied Polymer Science, 44, 1153, 1992.
223
The degree of grafting increased with both increasing silane and peroxide
concentrations in the reaction mixture and reached a steady value, also
dependent on silane and peroxide concentrations (Figure 5.5). The grafting
reaction follows first-order kinetics for both LDPE and EP copolymers
regardless of the concentration and type of silanes (VMSI and VESI). The
Ea values are independent of the concentration of silane and DCP and are
similar for LDPE and EPR (170kJ/mol for VMSI and 185kJ/mol for VESI
[33].
(b) Grafting initiators. Grafting initiators thermally decompose into free

radicals which abstract hydrogen atoms from the PO chains to create the
active sites for the grafting of silanes. Only organic peroxides which may
easily abstract H atoms can be used as efficient grafting initiators. The
peroxide should be completely decomposed in a time interval shorter than
the residence time of the reaction mixture in the processing equipment.
Therefore, peroxide has to be selected as a function of grafting temperature
too, depending on its halflife at this temperature (Table 5.1), i.e. 6-10 t1/2 at
the processing temperature should be about equal to the residence time in
the processing equipment (see ch. 2 for detailed discussion).
The grafting initiator is usually DCP, as in peroxide cross-linking.
However, the use of an excess of silane relative to DCP normally ensures
that silane grafting prevails over cross-linking by C--C bonds formed by
direct coupling of PO macroradicals. Indeed, the peroxide is added at a level
of 0.05%-0.50%, but usually 0.1 %-0.2% for a typical grafting reaction
containing 2 % silane in the reaction mixture.
For a certain silane concentration the grafting yield increases with
increasing peroxide concentration (Figure 5.5). The competition between
peroxide-induced cross-linking and silane grafting reaction depends on the
peroxide concentration. Sen et al. [33J noticed a small difference in values
of Ea for silane grafting onto LDPE and EPR (170kJ/mol and 185kJ/mol
for VMSI and VESI, respectively) and DCP-induced cross-linking of these
polymers (140kJ/mol and 130kJ/mol for LDPE and EPR, respectively).
Because of this small differences at low concentrations of DCP the crosslinking reaction is suppressed by silane, and the grafting reaction predominates. However, at DCP concentrations higher than 1.6mmol per 100g
polymer, i.e. about 0.4%, the cross-linking reaction predominates over the
grafting reaction and it is no longer possible to increase the grafting yield
by increasing the peroxide concentration.
Other peroxides such as t-butylcumene peroxide are also used in commercial grafting processes (Table 5.3). Patents claim the use of many other
types of grafting initiators [5]. Peroxides which are not characteristic for the
cross-linking of PEs have been used too. Peroxides such as dibenzoyl
peroxide and dilauroyl peroxide are less capable than DCP of abstracting
H atoms from the PO chain and consequently will reduce the possibility of
224
the appearance of C-C cross-linkages during silane grafting. An interesting

case is the use of an organic peroxide containing an unsaturated group
bondable to the PO. Thus, during the extrusion at 200 C of LLDPE with
2% VMSI in the presence of 0.06% 1-(2-tert-butylperoxy-isopropyl)-3-isopropenylbenzene this compound decomposes to create the free radicals to
initiate the grafting, and the rest of the molecule containing the C=C
double bond became attached to the PO chain, also by grafting, giving an
odourless material for use as pipes giving no odour to potable water [49].
However, DCP still remains the most widely used grafting initiator in
practice.
D
( c) Reaction temperature and time. Both reaction temperature and time

are determined mainly by the type of reactive processing equipment. The
grafting rate of silane increases with temperature as established by Sen et al.
[33J by means of isothermal DSC measurements (Figure 5.6).
At the elevated temperatures used in reactive extrusion (180 DC-240DC)
almost complete grafting (80% grafting yield) may be achieved during the
short residence time of the reaction mixture in the extruder barrel (a few
minutes). Unreacted silane has to be removed by different means, e.g.
extruder venting. Production lines should be provided with good ventilation
1.0,-------:::;;;;::0----::::=::==-------,
r:::
o
.~
o
o
<5
~
a,
o
Q)
0.4
10
Time (min)
Figure 5.6 Dependence of silane conversion on reaction time at different temperatures

measured by isothermal DSC (reaction mixture: 100gLDPE, 112.5mmol VMSI, 1.6mmol
DCP). Reproduced from Sen, A.K., Mukherjee, B., Bhattacharya, A.S. et al. Journal of Applied
Polymer Science, 44, 1153, 1992.
225
to maintain low atmospheric concentrations of silane 10 ppm) [5]. The

correlation between reaction temperature, halftife of the peroxide and the
residence time in the extruder has already been mentioned.
Internal mixer processes may require lower temperatures (140C-180C)
than extruder processes, but the reaction time is no longer limited by the
equipment so that complete grafting may be achieved, in spite of lower
reaction rates owing to the lower temperatures, by selecting longer mixing
cycles (5-30min) [5, 25, 48].
(d) The stabilisation package. For processing as well as long-term heat
stabilisation antioxidants have to be incorporated into the polymer before
or after the grafting step. The level of antioxidants depends on the end use
of the cross-linked PO and may vary across a wide range. For many
commercial applications requiring very good long-term heat resistance,
cable insulation being the typical example, the antioxidant level has to be
high, up to 0.5 wt%. Therefore it is necessary to incorporate a suitable
stabilisation package into the silane-grafted PO because most commercial
PO grades used as grafting backbone are usually provided only with a 'base
stabilisation', i.e. a stabilisation package unable to protect the polymer in
more demanding applications.
When present in the reaction mixture during grafting, as in the case of
'one-step' processes, antioxidants clearly may inhibit the grafting reaction as
many of them are effective radical scavengers. Such behaviour is typical for
the sterically hindered phenols, the most widely used antioxidants for POs.
Consequently, the grafting processes are limited by the choice of antioxidants. If antioxidants are added during the grafting step they will
decrease the grafting yield of silane and thus the cross-linking degree of the
resulting polymer. Indeed, moisture cross-linked EP-g-VMSI showed a
gradual decrease of the gel content when grafting was performed in the
presence of increasing amounts of octadecyl-3-[3',5' -di(tert-butyl)-4' -hydroxyphenylJpropionate (up to 0.3%). The decrease of the gel content (88%
gel in the absence of antioxidant) appears to level off at higher amounts
(65% gel above 0.2% antioxidant) [25]. In practice, therefore, adjustments
made to the grafting initiator level to compensate for these inhibitive effects
can ensure a high cross-linking degree of the materials stabilised during
grafting.
As aromatic amine antioxidants have a much lower tendency to scavenge
and 'kill' the free radicals they have been used in silane cross-linking,
especially for cable grades. The cross-linkable POs in which these antioxidants have been incorporated during grafting showed a yellowish coloration [5].
'Polymer-bound' antioxidants represent, at least from a theoretical point
of view, the best approach to avoid the physical losses that can occur during
processing and long-term use of the polymers stabilised with the usual
226
antioxidants, e.g. by volatilisation, 'blooming', 'leaching'. For POs, grafting

of monomeric stabilisers seems to be the most obvious route to obtain such
permanent stabilisers [50]. This approach involves the use of bifunctional
compounds having a stabilising moiety, which acts as antioxidant or
photostabiliser, and a polymerisable C=C double bond, or alternatively
other functionalities such as SH groups, able to be substantially grafted on
the PO chains in the presence of free radicals generated by different means
(mechanochemically, by peroxides, by irradiation). This route has been
investigated intensively by AI-Malaika [51] (see ch. 6 for more detailed
discussion).
Silane grafting of POs could certainly be a field where monomeric
stabilisers might be used much easier than in other applications. Indeed, free
radicals are already present in the system to initiate the silane grafting so
that a monomeric stabiliser might be regarded as a 'drop-in' stabiliser that
will also be grafted under the conditions of the reactive processing used to
produce the silane-grafted POs. Some patents claim the use of 2,2,4trimethyl-1,2-dihydroquinoline as amine antioxidant added during silane
grafting of POs but report no data concerning its bonding onto the PO
chain [5]. However, it has been shown [52] that in similar conditions, i.e.
the reactive processing of HDPE in the presence of DCP, the reactivity of
the C C double bond of the heterocycle ensures antioxidant grafting onto
HDPE.
5.4.3
The effects of various parameters on the cross-linking process
Moisture cross-linking of silane-grafted POs takes place on shaped articles,

i.e. in the solid state. Because the saturation concentration of water in POs
is very low (30-60ppm in PE at 20C) the quantity of water consumed for
hydrolysis of alkoxysilane groups has to be compensated by water diffusion
into the solid polymer matrix. Thus, the cross-linking rate will depend on
the rate of water diffusion into the polymer. The rate and final degree of
cross-linking are determined by various parameters concerning both polymer structure and cross-linking conditions.
(a) Parameters concerning polyolefin structure. It is obvious that the
cross-linking behaviour of silane-grafted POs basically depends on the
content of the grafted silane and on the possibility of water to have access
to the reactive alkoxysilane groups for their hydrolysis and subsequent
condensation. The cross-linking potential increases with the content of
grafted silane so that values of the gel content of samples cross-linked under
the same conditions have often been used to estimate the grafting yield. The
materials used in practice contain about 2% grafted silane, i.e. a level high
enough to achieve a high degree of cross-linking (over 70%-80% gel
content) and thus the useful properties of the network structure. Therefore,
227
100r----------------------------,
;g
80
"E
(l)
"E
(c)
60
t.l
Qj
CJ
(b)
40
96
144
192
240
288
Time (h)
Figure 5.7 Dependence of gel fraction on time of cross-linking at 30C for LDPE-g-VMSI (6%
grafted SI, 0.02% DBTDL) with different moisture contents: (a) 60ppm, (b) 120ppm, and (c)
210ppm water. Reproduced from Sen, A.K., Mukherjee, B., Bhattacharya, A.S. et al. Journal
of Applied Polymer Science, 44, 1153, 1992.
studies on the cross-linking behaviour of silane-grafted POs generally

investigate samples with 1%- 3% grafted silane [27-38].
For a certain grafted PO and under constant cross-linking conditions
(temperature, catalyst type and concentration) the rate and degree of
cross-linking increase with the water content in the polymer matrix (Figure
5.7). It was found that the cross-linking rate follows first-order kinetics with
respect to moisture concentration [33]. The saturation concentration of
water in POs depends on their structure. High-pressure ethylene copolymers
with polar co-monomers (vinyl acetate, butyl acrylate) have a certain degree
of polarity and consequently will incorporate more water than the nonpolar PE. However, although the saturation concentration of water in these
copolymers may reach levels of up to 300-400 ppm, depending on the type
and content of the copolymerised co-monomer, this quantity is still insufficient for complete cross-linking and therefore the process is controlled by
moisture diffusion into the polymer.
Crystallisation of silane-grafted POs takes place prior to moisture crosslinking. In the solid state the grafted silane units are located only within the
amorphous regions of the polymer matrix. The supramolecular structure of
the crystallised polymer can affect silane cross-linking in two ways: it
controls the moisture diffusion into the resin, which is the rate-determining
step for the formation of Si-O-Si cross-linkages; and it determines the
distribution of the grafted silane groups in the resin which affects the
cross-link distribution.
Water penetration into the semi-crystalline POs increases with decreasing
degree of crystallinity. Under identical grafting and cross-linking conditions
228
Table 5.4 Calculated number of silane cross-links formed per

20000 Mn of the network chain during different curing periods.
Curing period (min)
60-120
60-1000
HDPE
LDPE
LLDPE
0.006
0.26
0.56
1.41
3.72
1.59
Source: Wong, W.K. and Varrall, D.C., Polymer, 35, 5447, 1994
LDPE- and LLDPE-based materials will be much more permeable to

moisture than will HDPE-based materials which will require a longer time
for moisture to penetrate and facilitate the cross-linking reaction. Early
studies [13, 14, 23, 24] simply noticed that grafted LDPE shows higher gel
contents and cross-linking rates than does grafted HDPE.
Recent studies showed that cross-linking is a much more complicated
phenomenon where not only water diffusion but also the PO structure
determines the process. Thus, Wong and Varrall [34] determined the
cross-link density of VMSI-grafted PEs, cross-linked for different periods of
time (Table 5.4). Following the short curing period (60-120min), where
differences may largely be caused by the different moisture diffusion rate for
various PEs, upon the prolonged curing period (1000min), where all the
grafted silane molecules should be cross-linked, there are still differences.
This suggests that a large amount of alkoxysilane groups grafted onto
LDPE is not cross-linkable owing to their physical separation upon
crystallisation. The mobility of these groups in grafted HDPE is even lower.
In contrast, the structure of LLDPE contributes to the increased mobility
of the grafted silane groups in the amorphous phase and enhances their
chance of reacting with neighbouring silane groups when moisture crosslinked. Additional evidence was supplied by transmission electron microscopy (TEM) of the cross-linked polymers.
The variation in cross-link density with very short curing periods (up to
60min) was attributed to the differences in peroxide-induced C---C chain
extension during silane grafting which follows the order LLDPE >
LDPE> HDPE. For the initial period only a small fraction of the grafted
silane was moisture-condensed to form cross-links. The highest cross-link
density was, therefore, achieved for LLDPE which, because of its structure,
suffered the highest degree of chain extension. After the initial period the
extra silane cross-links effectively turn the chain-extended PE into a threedimensional network structure, the cross-link density of which reflects the
degree of chain extension generated prior to the silane cross-linking. Thus,
a PO such as LLDPE will require less silane cross-linking and hence a
shorter time period to generate a network of high cross-link density than
will POs with a lower degree of peroxide-induced chain extension or POs
degraded or scissioned during silane grafting [34].
229
100r---------------------------------------~
80
10
12
14
16
18
20
Time (h)
Figure 5.8 Gel content of LDPE-g-VMSI versus cross-linking time at different temperatures.
Reproduced from Sen, A.K., Mukherjee, B., Bhattacharya, A.S. et al. Journal of Applied
Polymer Science, 44, 1153, 1992.
(b) Parameters concerning cross-linking conditions. The degree of moisture

cross-linking of silane-grafted POs, usually measured as gel content, increases
with the cross-linking time and, for a certain amount of water in the polymer
matrix, basically depends on catalyst type and concentration as well.
The rate and degree of cross-linking increases with temperature (Figure
5.S). From the observed linear temperature dependence of the cross-linking
reaction an activation energy of 65 kJ/mol has been calculated for this
example [33].
100
80
~ 60
'E
o
Qi
C}
40
20
o~~~--~~~~~~--~
0.01
0.02
0.03
0.04
0.05
Catalyst concentration (%)
Figure 5.9 Gel content of LDPE-g-VMSI (cross-linked at 90C) versus concentration of

different cross-lmking catalysts: (a) stannous octanoate, (b) DBTDL, and (c) dialkyl tin
mercaptide. Reproduced from Sen, A.K., Mukherjee, B., Bhattacharya, A.S. et al. Journal of
Applied Polymer Science, 44, 1153, 1992.
230
At constant temperature the degree of cross-linking increased with

catalyst concentration (Figure 5.9). The differences noticed for the efficiency
of various tin compounds disappeared at higher concentrations (above
0.03%). At lower concentrations (0.02%) plots of gel content versus crosslinking time confirmed that catalyst efficiency follows the order dialkyl-tin
mercaptide> DBTDL > stannous octanoate, and this was attributed to the
Lewis acid strength of the tin compounds which follows approximately the
same order. For all investigated catalysts the rate and also the final degree
of cross-linking increased with catalyst concentration. The rate of crosslinking follows first-order kinetics with respect to the catalyst as well as
moisture concentration [33].
5.5 Silane copolymerisation processes
Moisture cross-linkable silane-modified POs can also be produced by olefin
copolymerisation with silanes. This 'in-reactor' route is, however, restricted,
at least for the moment, to the ethylene polymers produced by radical
initiated polymerisation of ethylene in high-pressure reactors.
5.5.1
High-pressure ethylene polymerisation plants
The free-radical-initiated polymerisation of ethylene at elevated temperature

and high pressure in autoclave or tubular reactors produces branched
LDPE (Figure 5.10). The autoclave functions as an adiabatic continuous
stirred-tank reactor, with the heat of reactions being removed by the fresh
ethylene entering the reactor. The ethylene conversion is typically 20% and
Molecular weight
regulator
02 or
peroxide recycle purification
Tubular reactor
L.P.
H.P.
compressors
autoclave
1.-'
l,:t, 1...r
H.P.
flash
L.P.
flash
,e.':~ ~
Figure S.10 High-pressure ethylene polymerisation plant. L.P.

pressure.
= low pressure; H.P. = high
231
the reaction pressure, 150-250 MPa. The tubular reactors work in the plug
flow regime with heat transfer to the jacket. Higher ethylene conversions (up
to 35%) and reaction pressures (200-350 MPa) than for autoclave reactors
are used [2].
The high-pressure processes are also suitable for the copolymerisation of
ethylene with one or more co-monomers such as vinyl acetate (V A) and/or
acrylic esters. Technically, any LDPE plant can produce copolymers provided some principal modifications are performed:
liquid pumps need to be added to pump the co-monomer into the suction
of the secondary compressor,
additional equipment is needed for separation and purification of the
co-monomer,
an improved system is required for removing final traces of monomer
because the co-monomers are generally more soluble than ethylene and
they have more offensive odours.
However, the autoclave process is generally preferred for its well-defined
operating conditions and its ability to produce a useful conversion at a low
maximum temperature. With the exception of EV A and to a lesser extent
ethylene-acrylic esters, copolymers (10%-12% and 0.7%-0.8% share of
total LDPE and LLDPE markets, respectively) may be regarded as commodity polymers the other high-pressure copolymers are speciality or even
exotic polymers of much lower tonnage consumption [53]. The nameplate
capacity of LDPE plants increased from 2500-5000 metric tonnes per
annum per line during 1950-60 to about 100000 metric tonnes per annum
or even more during the 1990s. However, owing to the competition with
LLDPE which strongly entered the market in the 1980s, many of the LDPE
plants today, especially those utilising autoclave technology, were built more
than 20-25 years ago [54,55]. Production lines of lower capacity seem to
be used preferentially for the production of speciality copolymers.
The relationship between the composition of the reactor feed, copolymer
and recycling gas depends on the reactivity ratios r l and r2 from the
well-known copolymerisation equation and has implications for the type of
reactor and low-pressure recycling system as well [1]. When the reactivities
of ethylene and a co-monomer are virtually identical (rl = 1, r 2 = 1), and
this is the case for vinyl acetate (V A), both monomers are consumed at the
same rate. The reacting monomer mixture and the produced copolymer
maintain a constant composition even in multi-zoned reactors, but the
recycling system must handle high concentrations of co-monomer because
the mixture of unreacted monomers in the recycling gas also has the same
composition as the reactor bed. Additional equipment is thus necessary to
collect the co-monomer which condenses in the low-pressure recycling
system and to purify it before returning it to the liquid pump.
232
The converse is the case for the acrylate esters where r 1 is much lower
than 1, which means that the copolymer is much richer in acrylate than is
the reactant mixture. If a multi-zoned autoclave or a tubular reactor are
used the composition varies in the different zones, but the recycled product
is nearly pure ethylene. Thus, in a continuous stirred tank reactor which
operates with the co-monomer concentrations in a dynamic equilibrium to
make a copolymer containing 20 wt% ethyl acrylate (EA) the feed composition would contain typically 4 wt% EA, but the reactor and the stream
leaving the reactor would contain only 1.6 wt% EA. In the case of a
continuous plug flow reactor corresponding to a tubular reactor or a
laboratory batch autoclave the corresponding figures would be 3.1 wt% EA
in the reactor feed and 0.7wt% EA in the recycling system. The resulting
E-EA copolymer would have a broad distribution in terms of the content
of EA, ranging from 38 wt% to 9 wt% as the co-monomer is used progressively along the reactor.
The first commercial products obtained by direct copolymerisation of a
vinyl silane in a high-pressure reactor appeared in the 1980s and have been
developed by Union Carbide [17a] and Mitsubishi Petrochemical [18]. The
process, developed by Mitsubishi for their LINKLON-X polymers [18], has
been licensed to A. T. Plastics, Canada, for their AQUALINK process
[21,22]. Ethylene-silane copolymers are available on the market only from
a few other suppliers, e.g. Quantum Chemical Company USI Division
(AQUATHENE resins) and Union Carbide (SI-LINK resins) in the USA
and Borealis (VISICO resins) in Europe. BP Chemical, a former producer
of such copolymers [53] sold its interests in wire and cable compounds to
Borealis.
As for grafted POs, in the random copolymers the silane is normally
VMSI at a content of less than 5 wt%. Commercially, grades usually contain
1.6-2.3wt% VMSI and are available in the range of melt flow index
0.6-4.0g per 10min and density 0.920-0.929gjcm. By addition of another
co-monomer, together with silane, cross-linkable terpolymers are also possible to produce. Poly(ethylene-co-vinyltrimethoxysilane-co-n-butyl acrylate)
(E-VMSI-BA copolymers) are already available on the market [6, 7, 42].
Owing to the relatively high content of BA, e.g. 20wt% in some commercial
grades, in comparison with only about 2 wt% VMSI, these terpolymers can
be soft and rubber-like.
Concerning the synthesis step in producing silane-modified POs, reactor
copolymerisation has some important advantages in comparison with
extruder grafting. The silane is more homogeneously distributed in the
polymer chain and there is no limitation in the choice and consumption of
antioxidants. Unreacted silane is recovered in the gas purification systems
of the plant more efficiently than in extruder grafting. In grafted compounds
the decomposition products of the peroxide as well as unreacted silane
(about 20% in an optimised grafting process) give the compound a strong
233
odour. Silane copolymerisation is more easily controlled than is silane

grafting, where a significant drop in viscosity and a broadening of molecular
weight distribution occur as a consequence of the grafting mechanism.
Difficulties in controlling the grafting step may result in variable final melt
flow rates, silane yields and silane distributions.
As for other high-pressure copolymers the main process parameters are
reactor type, polymerisation temperature profile, polymerisation pressure,
type and concentration of the initiator and chain transfer agent and
conversion of monomers. However, no data are available in the literature to
report the influence of these parameters on the most important structural
features of the copolymers, e.g. molecular weight distribution, chemical
heterogeneity of silane distribution and crystallinity. This is quite understandable because of the secrecy of producers. For a research team not
belonging to such producers studies on the influence of process variables are
much more difficult to perform for silane copolymerisation compared with
silane grafting, mainly because of the more specialised and sophisticated
equipment and synthesis conditions, i.e. high-pressure reactors and pumps,
instead of a conventional extruder. The data reported in the literature are
concerned especially with the performance and applications of the
copolymers where product differentiation is very much emphasised, i.e. the
advantages for silane copolymers relative to grafted materials. Developments in moisture cross-linking procedures are also reported.
5.5.2 Product differentiation

Ethylene-silane high-pressure copolymers are an alternative only to the
LDPE-based grafted copolymers so that their main use is within the wire
and cable area. Offering storage stability and processing advantages over the
graft copolymers they can use existing PE and PVC extrusion lines without
any modification except for a feeder for addition of the catalyst masterbatch
and preferably a dryer for colour and catalyst masterbatches. The rubberlike E-VMSI-BA terpolymers can be filled to a great extent without losing
their physical properties, which is of importance for such applications as
semiconductor and non-halogenic flame-retardant compounds.
(a) Storage stability. Storage stability is an important advantage for

reactor silane copolymers relative to graft copolymers. This behaviour is the
result of the much lower moisture sensitivity of the random copolymers
PE-Si(ORh in comparison with the graft copolymers PE-CH 2-CH 2 Si(ORh with their higher mobility in the longer pendent trialkoxy chain
(Figure 5.11).
For copolymers aged at 50% relative humidity and 20 C the melt index
retention after 150 days was about 90%. Thus, products in moisture-proof
packaging have a very long shelf life and have been found to be within
D
234

~
0.8
.~ 0.7
r'-----------------.
PE-co-SI
...............................................................
~ 0.6
lii
Co 0.5
S 0.4
e 0.3
<D
0.2
~ 0.1
:2
0
10
20
30
40
Storage time (weeks)
50
60
Figure 5.11 Storage stability test of random and graft copolymers by measuring melt flow rate
as a function of storage time. Reproduced from Sultan, B.A. and PalmlOf, M., Plastics, Rubber
and Composites Processing and Applications, 21, 65, 1994.
specification even after a storage time of three years [22]. Owing to the
higher storage stability of reactor copolymers the elaborate and expensive
packaging used for graft copolymers may be not necessary at least for
moderate storage times. Developments in North America resulted in the
delivery of silane copolymers in bulk railcars with a capacity of up to
80 tonnes. The cars are sealed against rainwater ingress and normally
breathe through vents on a diurnal temperature cycle. In spite of their
higher hydrophilicity catalyst masterbatches containing about 20% carbon
black may be shipped in bulk too [22]. As a general rule, silane copolymers
delivered and stored in bulk without special packaging should be used
within two to three months of receipt to ensure best processing.
(b) Processing stability. Silane-containing polymers are rather sensitive to
pre-curing. PE contains around 50 ppm water when stored during ambient
conditions, and water is formed also during extrusion as the main decomposition product when PE is oxidised. Water quickly reacts with the silane
groups at the high temperatures used in extrusion and Si-O-Si cross-links
are formed. Thermal cross-linking may occur too, resulting both in
Si-O-Si and in C-C cross-links. All these reactions can lead to formation of scorch that drastically reduces the breakdown and mechanical
strength of the products. The premature cross-linked products are collected
on the filtering screens of the processing extruder, slowly building up over
time and thus gradually decreasing the extruder outputs. The extruder has
eventually to be stopped for the cleaning of its screw and die.
Another advantage of the reactor copolymers over graft copolymers is
that they have a longer continuous processing stability (Figure 5.12) and are
less sensitive to the processing temperature (Figure 5.13). In the presence of
cross-linking catalysts the higher the extrusion temperature the bigger the
235

12~--------------------------~
~10
"5
a.
88
60~--~10~--~20~---3~0~---4~0~--~50
Extruding time (h)
Figure 5.12 Continuous processing stability test of random and graft copolymers by measuring
extruder output as a function of extruding time (extruder diameter = 4Omm, 160 C). Reproduced from Eagles, D.C., Proceedings of SP'92 Polyethylene World Congress, Zurich, December
7-9, 1992, paper IV-3.1-15; published by Maack Business Services, Zurich, 1992.
D
M121
70.----------------------------,
60
(c)
50~r__::-.--.:.;~--
......
40
.......
30 i\
...~).......
20
"
"' ...~
10
160
(a)
"
' ............
....... ------------~,-.::::-::::.
180
200
220
240
260
280
300
Exit temperature (DC)
Figure 5.13 Processability test of random and graft copolymers (5% catalyst masterbatch
added) by measuring melt flow rate as a function of extruder exit temperature (extruder
diameter = 60mm): (a) PE-g-SI (Sioplas process), (b) PE-co-SI (Visico) without SRA, and (c)
PE-co-SI (Visico) with scorch retardant additive. Reproduced from Sultan, B.A. and Palmlof,
M., Plastics, Rubber and Composites Processing and Applications, 21, 65, 1994.
drop in melt flow rate (Figure 5.13). The longer more pendent silane groups
may again be a factor in the lower stability of graft copolymers to thermal
cross-linking. Moreover, a small amount of peroxide used to initiate the
silane grafting may also induce chain extension and cross-linking reactions.
Intensive research work has been performed to make the silane-modified
polymers less sensitive to pre-curing at processing temperatures and thus to
increase their processing window to a similar level of that of unmodified
thermoplastic polymers. Scorch-retardant additives (SRA) aiming to stop
molecular enlargements have thus been developed. The role of the scorch
retardant is either to react faster than the polymer itself with any water
236
present in the material during extrusion conditions, or to desensitise the

Si(OR)3 alkoxyl groups to condensing in the absence of water. In an SRA
such as n-octyltriethoxy-silane, CH 3(CH 2 hSi(OC 2 H sh, the long alkyl tail
makes it compatible with the ethylene-silane copolymer whereas the
alkoxyl groups are responsible for the scavenging of the water [56]. The
SRA is incorporated into the polymer melt at addition levels of 0.1-1.0%,
either following polymerisation or with the cross-linking catalyst, as masterbatch in the shaping step.
The addition of a compatible and non-volatile SRA brings the following
important advantages:
improved storage stability, if SRA is incorporated before shaping;
improvements in processability, giving compounds not sensitive to high
temperatures (Figure 5.13);
makes the polymer more insensitive to residence time, which is of major
importance during tool changes and interruptions on the production line
when the screw speed is reduced to a minimum (without any SRA the
surface finish quickly deteriorates and very often it is impossible to get rid
of formed gels without taking the extruder apart and cleaning it);
the formation of die drool, which is a problem for silane cross-linkable
PE, is also significantly reduced [6, 7, 42].
As a water scavenger during extrusion it would be expected that SRA will
affect the moisture cross-linking speed too, which is one of the most
important properties of these materials. Data comparing the cross-linking
of silane copolymer with and without an SRA showed that in practice,
where cross-linking levels over 50% have to be reached for all applications,
the observed differences are of minor importance [7]. The SRA initially
slows down the cross-linking reaction, but when it is consumed the crosslinking reaction goes faster than without the additive (Figure 5.14).
9or------------------------------,
80
~ 70
g> 60
:.i2
50
~e
30
90C
---
.!: 40
() 20
10
%~----5~----1~0-----1~5~---2~0~----725
Time (h)
Figure 5.14 Gel content of silane copolymer (Visico, 1.8 mm thick tape) (a) with and (b)
without a scorch retardant additive as a function of the cross-linking time in water at 60C and
90C, respectively. Reproduced from Sultan, B.A. and Palmi of, M., Plastics, Rubber and
Composites Processing and Applications, 21, 65, 1994.
237
(c) Ambient cure. The long time required for the moisture cross-linking of
the silane-modified POs has always been regarded as a disadvantage of this
cross-linking method. The wish to reduce 'in-process' inventories, especially
by wire coaters, has resulted in a continuous search for faster curing
processes. For thin-wall constructions such as wire insulation it is often
possible to achieve high cross-linking rates, i.e. cure for several hours in hot
water tanks. However, the achievement of the same realistic cross-linking
times but at ambient conditions (normally 22C and 50%-55% relative
humidity) would be more advantageous.
The approach of faster cure copolymers by changing cure rates through
selection of the silane co-monomer is theoretically possible but it would
sacrifice the storage stability. The catalyst masterbatch approach has
therefore been pursued for practical purposes. However, the use of masterbatches containing more potent catalysts was possible only after the
introduction of the compatible SRA concept, which is today dominating the
silane copolymer market [7, 22, 42].
The use of SRA increased the processing window of the copolymers to
such an extent that the producers have been able to introduce more and
more active catalyst masterbatches.These masterbatches drastically increased the cross-linking speed, especially at lower cross-linking temperatures (Table 5.5). Both hot creep elongation (Table 5.5) and gel-content
measurements (Figure 5.15) proved that with 'fast-cure' masterbatches
effective cross-linking has been achieved in eight to ten days under ambient
conditions. Wire and cable makers are now able to obtain satisfactory
curing on thin coatings within a week to ten days on the shop floor, under
normal indoor conditions of temperature and humidity [7, 22, 42].
The more active masterbatches affect, however, the processability or'the
copolymers even in the presence of an SRA. Thus, the drop in melt flow
ratio as a function of proce~sing temperature increases with the activity of
the masterbatches (Figure 5.16). However, safer processing is achieved with
the most active catalyst in the presence of an SRA than with the classical
Table 5.5 Time to reach 60% hot set (lEC 811, 200 C, 0.2 MPa, 1.8mm thick extruded tapes)
with catalyst masterbatches (CMB, 5% added) of different activities.
D
Cross-linking conditions
CMB
Year of
introduction
(Borealis)
90 C, water
(min)
60 C, water
(min)
Ambient"
(days)
A
B
C
1986
1993
1993
240
110
80
20
9
2.5
>40
15
10
Source: Sultan, B.A., Proceedings of the 43rd International Wire and Cable Symposium.
pp. 460-7; 1994
"Relative humidity, 55%, 22 D C.
238
70
(a)
60
50
l40
(jj
C!l
30
20
10
7
21
14
28
Time (days)
Figure 5.15 Gel content of silane copolymers as a function of cross-linking time under ambient
conditions (RT, 55% relative humidity) in the presence of (a) fast cure and (b) standard catalyst
masterbatches. Reproduced from Eagles, D.C., Proceedings of SP'92 Polyethylene World
Congress, Ziirich, December 7-9,1992, paper IV-3-1-15; published by Maack Business Services,
Zurich, 1992.
system, i.e. a low-activity catalyst masterbatch without any SRA addition

[42].
The composition of these active masterbatches is not disclosed by their
producers. Polyhydroxyl compounds, compatible with the copolymer, are
used at addition levels of about 0.5%. These very hydrophilic compounds,
such as dibenzylidene sorbitol, certainly enhance water absorption in the
polymer matrix thus resulting in faster curing [57].
The copolymerisation of olefins with vinyl trialkoxysilanes in the presence of coordination catalysts is not yet possible because silanes act as
catalyst 'killers' as a result of their strong polarity. Therefore, applications
where other properties than LDPE-re1ated properties are required will
continue to be supplied by silane-grafted POs.
60~--------------------------'
~ 50
~ 40
~ 30
~-
~
:2
20
~(al
~(b)
(c)
10
0140 160
180
200
220
240
260
280
Exit temperature (OC)
Figure 5.16 Processability of silane copolymers containing a scorch retardant additive and 5%
catalyst masterbatches (CMB) with different activity (CMB A-C in Table 5.5). Reproduced
from Sultan, B.A., Proceedings of the 43rd International Wire and Cable Symposium, pp. 460-7,
1994.
239
5.6 Structure and general properties of silane cross-linked polyolefins

The structure of the silane cross-linked POs is very different from that of the
POs cross-linked by free-radical methods. Peroxide and radiation crosslinking involves the formation of a network in which each cross-link point
results from the coupling of two PO chains by C-C bonds (Figure 5.17).
A chain of silane-modified PO is capable of reacting with two or more
similar chains to form siloxane cross-links. It is assumed that, on average,
only two of the three alkoxyl groups for each silicon atom can react.
Consequently, four polymer chains are bound in each cross-link point of the
network by Si-o-Si bonds. The siloxane cross-links may form threedimensional tetrahedral 'bunch-like' networks (Figure 5.17). This structure
was postulated by Voigt [23] at the appearance of silane-grafted PE.
As stated before, in comparison with conventional cross-linking methods,
silane cross-linking has many advantages with regard to cross-linking
technology. Moreover, many properties of the resulting products are better
than those of irradiation or peroxide cross-linked products. Most of these
advantages are the consequence of separating the cross-linking step from the
shaping step and of the specific structure of the network as well.
Silane cross-linked polymers usually give lower values for the degree of
cross-linking than do peroxide cross-linked products: around 70% gel
content by solvent extraction compared with 80%, and less than 50% heat
elongation compared with about 80%, respectively [6,7]. However, the
specific structure of the silane cross-linked networks gives better thermomechanical properties than does that of peroxide cross-linked networks.
Early studies on moisture cross-linkable silane-grafted POs emphasised the
better behaviour concerning the dependence of the hot elongation, deformation under mechanised load under isothermal conditions and the swelling
value on the gel content [5, 13, 14]. In comparison with peroxide cross-
:r
Si
OR
-E3-
-0-
~j
rff-r
(c)
> :>
Figure 5.17 Structures of cross-linked polyethylene. Possible sterical configuration for polyfunctional bridge heads of (a) uncross-linked and (b) cross-linked silane-grafted PE;
(c) structure of radiation or peroxide cross-linked PE network.
240
120
100
80
;g- 60
!!,...
80
C
c:
0
60 ~
Qi
CJ 40
20
100
40
00
20
2
Cure time (h)
.e
Q)
100
Figure 5.18 Dependence of gel content and deformation on the cross-linking time of PE-coVMSI at 90C in water. Reproduced from Eagles, D.C., Proceedings of SP'92 Polyethylene
World Congress, Zurich, December 7-9, 1992, paper IV-3.1-15; published by Maack Business
Services, Ziirich, 1992.
linked PE, for samples with the same gel value, all these properties have
lower values, thus indicating better resistance to deformation and solvents.
Consequently, the same value of a certain property, for example hot
elongation, is obtained with a lower gel content.
Reactor-made copolymers showed the same advantage over peroxide
cross-linked PE, achieving equivalent thermal deformation resistance at a
lower gel content. Thus, although the curing of these copolymers continues
to yield an ultimate gel concentration of 78% the deformation very quickly
drops to less than 5% at a corresponding gel level of only 60%-70% (Figure
5.18). For peroxide cross-linked PE a gel content of about 85% is required
to achieve deformations lower than 5% [22].
The low after-cure deformation is the consequence of the fact that the
moisture cross-linking takes place on shaped articles in the solid state. Thus,
polymer crystallisation precedes cross-linking and the polymer is allowed to
anneal at least in the early stages of the cross-linking process. The annealing
maximises the polymer crystallinity and associated physical properties. In
contrast, in peroxide cross-linking the cross-links are formed in the melt and
permeate through the amorphous regions of the polymer.
Studies by DSC, X-ray diffraction and dynamic mechanical thermal
analysis (DMT A) of the thermal properties of cross-linked PE and EPR
rubber showed that networks produced by peroxide cross-linking create
more disturbances to the crystallisation of the chains and imperfections in
the crystals compared with the networks of cross-linked silane-grafted
polymers. Owing to their dense tetrahedral network structure silane crosslinked systems have better high-temperature properties, e.g. a higher dynamic modulus at high temperature [58].
From the practical point of view the resistance of silane cross-linked POs
to thermal, thermo- and photo-oxidative degradation may be regarded as
good as, if not better than, that of the peroxide cross-linked systems.
241
Although the technical properties and service performances are very much
dependent on the nature and degree of cross-linking this dependence has not
received much scientific attention and very few studies on the stability of the
silane cross-linked POs are available [27,59].
Silane cross-linked systems should have superior stability in comparison
with peroxide cross-linked systems. The 'bunch-like' network structure
(Figure 5.17) is expected to result in higher thermal stability than is a planar
network structure (Figure 5.l7). Moreover, the bond energy of an
Si-O-Si linkage (779kJjmol) is higher than that of a C-C single bond
(628 kJjmol). Peroxide cross-linking leads to chain scission of the polymer
molecules, at least to some extent. Whereas in silane grafting the possibility
of chain scission is much reduced owing to the lower peroxide content
required as grafting initiator, in silane copolymerisation no chain scission
occurs. The amount of secondary and especially tertiary carbon atoms
which are more vulnerable to radical and oxidative attack may be higher in
peroxide cross-linked POs than in silane cross-linked polymers. However,
the differences were not sufficient to be of practical importance.
A comparative study of the degradation of silane and peroxide crosslinked PE and EPR rubber [59] showed superior properties to the silane
cross-linked systems: higher activation energy of both thermal and thermooxidative degradation (investigated by non-isothermal thermogravimetry
(TG) and derivative thermogravimetry (DTG) in nitrogen and air, respectively), higher onset temperature of oxidative degradation (measured by
DSC) and better retention of mechanical properties during oven ageing.
However, in the VMSI-grafted PE and EPR samples the grafting degree was
three times higher than the usual value in the commercial materials, i.e. 6%
VMSI compared with about 2% VMSI, respectively. More detailed studies
are necessary for a better understanding of the mechanisms of degradation
in order to develop efficient stabilisation packages for different applications.
Other specific properties such as electric properties, environmental stress
cracking resistance (ESCR), adhesion and shape memory will be discussed
in connection with the applications of the cross-linked products.
5.7
Applications of silane cross-linked polyolefins
Silane cross-linking technology is applied in those areas where peroxide and

radiation cross-linked POs are already used, but it may also be applied in
areas where these conventional cross-linking procedures either have gained
no entry or have made only a minor inroad. Besides the very good
properties of the silane cross-linked POs, the technological advantages are
decisive in expanding application fields. Silane cross-linking offers several
clear advantages over the traditional cross-linking processes, being competitive in price, requiring significantly less capital investment and offering easy
242
processability. However, for applications involving thick and very thick wall
constructions, e.g. medium- and high-voltage cables, peroxide cross-linking
still remains the preferred technology. For applications where LDPE-related
properties are required reactor-made copolymers compete with the silanegrafted POs. Research efforts are continuously being made to enhance the
application potential of silane-modified POs.
5.7.1
Specific requirements for the use of silane cross-linkable polyolefins in

practice
The practical approach of making cross-linked products from both extruder

grafted and reactor copolymerised silane-modified POs consists of several
stages with special requirements imposed on each of them.
(a) Storage and catalyst addition. Following storage, the silane-modified
POs are mixed with the catalyst masterbatch, e.g. by tumble mixing or
metering into the hopper of the shaping extruder (except in 'one-step'
extrusion processes for grafted materials). During storage and especially
when extruding silane cross-linkable POs it is essential to keep the moisture
content as low as possible. Owing to its non-polar structure and low silane
content (about 2%) PE-based materials absorb low amounts of water,
usually below 150ppm, when stored at ambient conditions. Silane crosslinkable POs based on more polar structures such as EV A-g-VMSI graft
copolymer and E-BA-VMSI reactor-made copolymer absorb higher
amounts of water, up to 350 ppm. The catalyst masterbatches, which usually
include stabilisers, can also carry flame retardants and carbon black and
other required additives or colourants. These masterbatches which contain
a large amount of more polar chemicals will, however, quickly absorb high
levels of water, normally far more than 100 ppm. They should be stored
separately from the silane-modified resin. Masterbatches are usually packaged in boxes with sealed foil liners and are recommended for immediate use
after package opening. If the product is exposed to moisture during storage
it should be dried to a water level below 200 ppm, e.g. eight hours at 60C,
before use.
(b) Polymer conversion into finished articles. The conversion of silanemodified PO/catalyst masterbatch mixture into finished articles is similar to
the processing of the unmodified PO. Extrusion is the main processing
technique (wire and cable insulation, pipes, films) but other techniques are
also used for different applications (injection, roto- and blow moulding). In
the absence of water the silane cross-linkable POs are still thermoplastic
polymers so that extruder process temperatures and line speeds should be
similar to those used to produce the same constructions with the unmodified
polymer. However, as seen before, the essential problem in processing silane
243
cross-linkable POs is that molecular weight increases already during processing as a result of water and thermally-induced cross-linking reactions. It
is therefore essential to optimise the extrusion process in order to avoid, or
at least to reduce, premature curing. This is achieved mainly by minimising
residence time and processing temperature. The residence time increases
with screw cooling, with mesh number of the screen pack and reduction of
the screw speed. The designs of the extruder, screw and die are very
important for the residence-time distribution and for avoiding hot spots.
Thus, advantageously narrower distributions of residence time are obtained
with streamlined flow paths and the use of a conical screw top.
Reactor-made copolymers are less sensitive to pre-curing during processing than are graft copolymers. The addition of an SRA has significantly
widened the processing window of the cross-linkable POs. It thus became
possible, e.g. for low-voltage wire insulations, to use existing PE and PVC
lines, without any modification, to produce very thin insulation at high
speeds. It has been also possible to use the more thermally sensitive
E-VMSI-BA terpolymers for production of cables and pipes with stable
production conditions and excellent surface finish [6, 7,42].
(c) Moisture cross-linking. Moisture cross-linking of silane-modified POs
is done separately from their shaping into finished articles according to three
basic techniques that are used in practice:
the 'sauna' technique, in which articles such as reels of insulated conductor or cable are cured in just a few hours by exposure to steam in steam
rooms;
the 'swimming pool' technique, where immersion in hot water eliminates
any potential problems that might occur in generating and handling
steam, but the cure time increases to about 16-24h at 90C;
the 'ambient cure' technique, in which the action of humidity during
storage can take a few weeks, but the advent of the more active catalyst
masterbatches has reduced the required cross-linking time to only 7-10
days.
As stated before, for grafted materials the cross-linking process depends
on parameters concerning both polymer structure and cross-linking conditions.
The structure of the polymer strongly influences its cross-linking rate
and, consequently, the time to achieve a satisfactory degree of cross-linking.
Polymers with higher molecular weights require fewer cross-links to attain
the desired properties than do lower molecular weight polymers. Silanemodified POs, with a higher degree of crystallinity, need more time to
achieve the same level of cross-linking than less crystalline material, owing
to the reduced penetration of the water into the more ordered supermolecular structure of the solid material, e.g. HDPE-g-VMSI compared with
244
LDPE-g-VMSI, or E-co-VMSI copolymer compared with E-BA-VMSI

terpolymer. The molecular configuration of the polymer, including the type
of silane functionality and its steric hindrance (from branching and the
position of the functional groups relative to the Si atom and the backbone),
is important too. Although various functional groups hydrolyse at different
rates, thus affecting the cross-linking rate, VMSI is mainly used in practice
to produce both random and graft copolymers. Steric hindrance around
the silicon atom can slow the cross-linking reactions, making reactor
copolymers more difficult to cross-link than graft copolymers but also more
resistant to premature cross-linking during both storage and processing.
Cross-linking is always accelerated in practice by adding suitable catalysts. Various polymer additives may be used to enhance different useful
properties in the cross-linked products. The influence of these compounds
on the cross-linking behaviour has already been discussed.
Concerning article construction and cross-linking conditions the main
parameters are article thickness and shape and cross-linking temperature,
respectively. For example, a large reel of a thick insulated conductor needs
a longer time to cross-link than does a small bobbin of a thin insulated wire.
The higher the cross-linking temperature the lower the time for the required
degree of cross-linking to be achieved.
(d) Recycling. Being still thermoplastic polymers in the absence of water
silane-modified POs could basically be recycled. However, owing to their
moisture sensitivity 'in-plant' scraps formed during synthesis and processing
are not usually recycled in practice. However, research efforts have been
made to recycle waste silane-modified POs. Thus, when 1% dicyclohexylcarbodiimide or its polymer was added to EVA-g-SI waste, after three
months of storage and subsequent milling no gel developed, in comparison
with 44% gel content for the same polymer milled following storage in the
absence of the additive [60].
Cross-linked products made both from silane-grafted POs and from
ethylene-silane copolymers are present on the market for certain applications, the most important ones being wire and cable insulation. Other
applications, such as tubes, mouldings and foams, consume much lower
quantities. Research efforts have been made to extend the application
possibilities of these polymers. A number of patents claim improved properties for different applications, as shown in a review of silane-grafted POs
[5]. The vast majority of the patents appearing in the mean time are
concerned with silane-grafted materials. This is most probably owing to the
fact that the grafting process has more variation possibilities than does the
high-pressure copolymerisation of ethylene with silanes, e.g. all PO types
may be used as grafting backbone. Owing to the large number of patents, it
is possible to cover only a limited selection of examples of the most recent
applications.
5.7.2
245
Wire and cable insulation
The outstanding electrical and dielectric properties of PE resulting from its

non-polar structure are combined with good mechanical properties, easy
processability and a low price-to-performance ratio. These properties made
PE a key material in wire and cable insulations by around 1940, when the
first industrial quantities of LDPE were produced [2]. Today, about 2.5%
of the total world consumption of PE is in the wire and cable sector. The
shares of the different PE types are as follows: LDPE, 65%; LLDPE, 21 %;
and HDPE, 14% [61]. In Western Europe, for example, about 4% of LDPE,
2% of LLDPE and 1.4% of HDPE consumption in 1995 was for wire and
cable insulations [62].
For power cable insulation, heat-deformation properties as well as the
dielectric properties are of great importance. With thermoplastic LDPE or
PVC the maximum operating temperature of cables is limited to 70C. The
cross-linking of LDPE drastically improves the heat deformation properties,
thus allowing a maximum operation temperature of 90C and increasing the
short-circuit rating from 130C to 250C. Several additional properties are
also improved: increased chemical, creep and stress cracking resistance,
impact and tensile strength, better low-temperature properties and decreased shrinkage.
Despite these advantages the share of XLPEs in the materials for
insulating low-voltage 10 kV), medium-voltage (10-30 kV) and highvoltage (30-50kV) cables is not uniform. Today peroxide cross-linking has
become the dominant technique for the production of medium- and highvoltage cables, which usually consist of three peroxide cross-linkable layers
applied in a triple extrusion process. Latest developments indicate the
feasibility of using XLPE for cable insulation at extra high voltages, i.e. up
to 300kV [63,64].
The use of peroxide cross-linking for low-voltage applications is rather
limited owing to the high investment costs of the long vulcanisation lines
(80-200m), restriction in production speed limited by the cure rate and the
need of a certain residence time in the vulcanisation tube. For this application thermoplastic materials, especially PVC or electron-beam cross-linked
PE, seem to be more economical [6, 7, 42].
The silane cross-linking technology drastically changed this picture.
Low-voltage wire and cable insulation has become the main area of
commercial application of silane-grafted POs (SIOPLAS and MONOSIL
processes) and, later, of reactor-made copolymers (high-pressure processes)
[5-7, 13, 14,21-24,42,65-68]. The share of silane systems in this market
as well as the competition between graft and random copolymers depends
on the country. Thus, whereas in Canada 72% of the market has been
gained by the silane systems, with about an equal proportion of grafted and
copolymerised materials, in the USA peroxide cross-linked PE dominates,
246
Table 5.6 Materials share (%) in the low-voltage wire and cable market
Polymer
Peroxide-XLPEa
Electron-beam XLPE"
PVC/nylon
Silane copolymer
SIOPLAS graft copolymer
MONOSIL graft copolymer
Total:
percentage
tonnes in 1992
USA
62
5
12
18
Canada
11
16
41
26
5
100
39000
100
6400
Source: Eagles, D.C., Proceedings of SP'92 Polyethylene World Congress,

Ziirich, December 7-9, 1992, paper IV-3.1-15; published by Maack
Business Services, Zurich, 1992
aCross-linked polyethylene
silane systems consisting mainly of copolymers accounting for only 21 % of

the market (Table 5.6).
The use of silane cross-linked materials for wire and cable insulation
results from advantages both in material properties and in cross-linking
technology. In peroxide cross-linked PE the volatile products resulting from
peroxide decomposition, e.g. acetophenone, cumyl alcohol, methane, 0(methylstyrene and water from DCP decomposition, generates microvoids in
the dielectric (about 100/mm). This negatively affects the long ageing
performance of the cable as the risk of the electrical ageing phenomenon,
water treeing, will increase. The presence of acetophenone, for example,
causes increased development in water trees [64]. In order to avoid
microvoid formation the vulcanisation zone is pressurised (12-20bars). In
the early steam curing process water diffuses into the insulation and
condenses leading to additional formation of microvoids (to a level of
104-106/mm 3). The dry curing processes do not add any other microvoids
than the one generated by the decomposition of the peroxide, enhancing the
electrical strength by 20% [6,7].
The silane cross-linking technology reduces the contamination level of
the insulation. For silane grafting systems the amount of peroxide is about
20 times lower than in peroxide cross-linking. In silane copolymers, as no
peroxide is added to the polymer, no void formation due to volatile
decomposition products will occur. Therefore, in comparison with peroxide
cross-linked PE, silane-modified polymers cure into products with superior
electrical properties. Thus, dielectric loss is lower in si!ane copolymers
(4 x 10- 4) than for peroxide cross-linked PE (16 x 10- 4). Because the
silane copolymers are processed and cross-linked at lower temperature the
size and density of microvoids is smaller. Although both materials are
equally susceptible to water treeing the retention of AC breakdown strength
of the copolymers after accelerated ageing proved to be better than in
247
peroxide cross-linked PE [22]. This was attributed to a preferential reaction

of the ingressed moisture with the residual alkoxysilane groups contributing
to an increased cross-link density within the already existing gel in the treed
region [69].
Insulation thickness increases with power cable power reaching up to
30-50mm for medium-voltage and high-voltage cables. The thinner insulation of low-voltage cables has been made possible to exploit the advantages
of the silane cross-linked materials, the values of the moisture curing times
being acceptable for the production requirements. For higher voltage cable
insulations (> 10 kV) little or no development appears to have taken place.
Such thicker insulations certainly need higher cure rates than are currently
obtained to make the moisture cross-linking system of practical interest.
Companion water cross-linkable semiconductive compounds for multilayered medium-voltage and high-voltage cables are also required.
Concerning the silane-grafted POs, higher insulation speed without melt
fracture, insulations with better gloss and smoothness, increased stress
cracking resistance, fire-resistance and self-extinguishing insulations with
non-drip properties are claimed to be obtained by different means, such as
suitable additives (lubricants, antioxidants, flame retardants), silane grafting
onto PO blends, PO grafting with silane/co-monomer mixtures, selection of
the PO type and properties and compounding of the grafted POs with other
polymers [5]. Applications such as semiconductive and non-halogenic
flame-retardant insulations for communication and power cables are under
development with rubber-like E-BA-VMSI terpolymers which can be filled
to a great extent without losing their physical properties [6, 7,42].
5.7.3 Pipes
The market for pipes and conduits accounts for about 3.6% of total PE
world consumption with the following shares for the different PE types: 72%
HDPE, 22% LDPE and 6% LLDPE [61]. In Western Europe, for example,
about 14% of HDPE, 2.5% of LLDPE and 2.5% of LDPE consumption in
1995 was in this sector [62]. Propylene polymers have a limited application
for pipe and cable insulation as well, about 0.3 % of total world consumption
for each application [62].
The improvement of thermo-mechanical properties and ESCR achieved
by PE cross-linking makes cross-linked PEs very attractive for pipes where
applications involve elevated temperatures and the transport of chemically
aggressive media. The stiffer HDPE is the natural choice in this field where
a 50-year lifetime at the service temperature has usually to be guaranteed.
The lifetime is estimated from a pressure test curve showing the circumferential stress in the pipe wall, i.e. the hoop stress as a function of failure time
at a certain temperature (Figure 5.19). In these curves failures at stage I are
caused by ductile creep, stage II failures have low stress cracking as the
248
25
20
15
;f1O
III
40C
60C
en
Cl
I
I
10 -1
100
101 10 2 10 3 10 4
Time to failure (h)
I
105 II 106
50 years
Figure 5.19 Pressure test water/water at 40C and 60C for VISICO ethylene-silane copolymer
pipes (32 x 3mm) cross-linked at 90C for 16h (73% gel content by decaline extraction).
Reproduced from Sultan, B.A. and Palmi of, M., Plastics, Rubber, and Composites Processing
and Applications, 21, 65, 1994.
predominant failure mechanism and stage III is caused by chemical deg~

radation of the polymer. Cross~linking eliminates stage II on the pressure
test curve and this permits making a linear extrapolation to the standard
50~year time value used for design calculation [4-7].
The market of cross~linked pipes is dominated by the Engel process for
cross~linked HDPE and there is a growth for applications such as under~
floor heating. Silane cross~linking technology may be applied in this field
too, eliminating the difficulties of the peroxide cross~linking within the pipe
area. To fulfil some existing standard for hot water pipes in higher pressure
applications, e.g. DIN 16892 which calls for HDPE, the silane~grafted
HDPE has to be used. Frantz [65] presented the processing conditions for
extrusion of such a HDPE~g~ VMSI pipe in an 'one-step' grafting process on
a twin screw extruder (Werner Pfleiderer Type ZSK 58 W96E). For
applications where these standards are of no importance and where relatively moderate pressures are used silane~grafted LDPE and ethylene-silane
copolymers may be used.
The network structure of the silane cross-linked POs ensures excellent
long time properties of the pipes. The chemical life (failure time to stage III)
has been established by pressure tests of the pipes (inside water/outside air)
which showed for ethylene-silane copolymers a lifetime over 50 years at
60C [6,7].
Cross~linked pipes made from silane~modified POs, e.g. LLDPE~g-VMSI
[49] and HDPE-g-VMSI [70,71], have less odour than peroxide cross~
linked PE, which is important for potable water. The good resistance to hot
chlorinated water makes cross~linked LLDPE~g~VMSI suitable for hot
water pipes for baths [72]. Cross-linkable pipes have shape memory which
is used for the production of heat shrinkable sleeves and tubes [73].
249
The main actual and potential applications for silane systems in the pipe
market seem to be:
hot water pipes for ground heating such as melt away pipes, lowtemperature district heating, underftoor heating and central heating;
pipes for transport of aggressive media, especially at elevated temperatures;
shrink sleeves for cable and pipe connections.
5.7.4
Mouldings
Cross-linkable silane-modified POs may be processed by injection moulding, blow moulding and roto-moulding. A variety of injection moulded
goods where performance requirements are very severe can be produced.
Blow moulded and roto-moulded articles generally consist of bottles and
containers for industrial chemicals. Silane-grafted HDPE is used in most of
these applications. Thermoforming is another possible processing technique
for silane-modified POs, as an example for E-co-VMSI copolymers shows
[74].
5.7.5 Adhesion-related applications
Silane-modified POs give a very high adhesion to different substrates such

as aluminium, steel, glass, paper and different polymers. Studies on the
adhesion between aluminium and E-co-VMSI copolymers have been reported [75,76]. The improvement in the adhesion of non-polar POs may be
explained by the increase of their polarity owing to the presence of the
alkoxysilane groups. Moreover, silanol groups not involved in cross-linking
reactions to yield siloxane bonds are available to reactions with the
substrate. This mechanism of action is in fact similar to that which makes
silanes valuable 'adhesion promoters' and 'coupling agents'. Silane-modified
POs are therefore interesting products in applications requiring adhesion
properties, e.g. coatings, laminates and other multilayered structures.
The multilayered articles are obtained by the usual processing techniques,
e.g. extrusion on supports, co-extrusion. After cooling, the articles are
subjected to water for the cross-linking of the silane-modified PO layer. The
high bonding strength in these laminates ensures their successful use even at
elevated temperatures or in the presence of organic solvents. In all these
applications mainly silane-grafted POs are used.
Different types of laminated paper are mainly used for electrical applications such as insulating paper [5]. Reclaimable waterproof paper is obtained
by paper coating with VMSI-grafted atactic PP [77] which showed good
adhesion to aluminium foils too [78]. Silane-grafted POs are used as
intermediate layers in metal/metal, metal/unmodified PO and polymer/
250
polymer laminates [5]. Thus, metallic pipes are protected against the
environment by extrusion of the polymer as the outside layer of the
laminate. Internal coating of the steel pipes is performed for better resistance
to the media transported, e.g. hot water. Before coating, aluminium pipes
and steel pipes are usually primed with silanes or titanates in order to
increase the adhesion between the metal surface and the LLDPE-g-VMSI
polymer [79-82]. Thermo-formable composites for automotive roofs are
obtained by sandwiching glass fibre mats between films of silane-grafted
HDPE [83].
Multi-layered containers of polyester/silane-modified poly(ethylene-coethyl acrylate)/HDPE have improved layer bonding strength as a result of
the polymer of the middle layer which 'ties' the extreme layers owing to its
compatability with both polyester and HDPE [84].
Polymer films and sheets with good surface hardness and gloss are
obtained by their coating with silane-grafted POs [5]. Anti-fogging agricultural films for greenhouses are made by coating an LDPE-g-VMSI film with
poly(2-hydroxyethyl methacrylate-co-methacrylic acid) [85].
There are many other examples of adhesion-related applications where,
in most of the cases, a certain kind of bonding between the silane-modified
PO and the other components of the multilayered structure seems to be
exploited.
5.7.6 Foams
Silane-modified POs can be expanded with conventional chemical and

physical blowing agents, such as azodicarbonamide and CF 3CH2F, respectively. Following exposure to water, cross-linked foams with 75% gel content
and 50kg/m 3 have been obtained from a variety of silane-grafted POs
[5, 86-88]. Cross-linked foams are forming an emerging market for
ethylene-silane copolymers too [22]. Owing to the difficulties in the PP
cross-linking by peroxides and multifunctional monomers the silane-grafting
approach is very attractive for PP foams.
5.7. 7 Other applications
Cross-linkable films, tapes, plates, sheets and non-woven fabrics are useful
especially for electrical applications. They have very good electrical properties, e.g. high treeing resistance and breakdown voltage (35-40kV/mm),
dimensional stability and heat- and oil-resistance. Some examples include
winding of tapes onto cables to give a heat-resistant insulation, electrical
insulating paper substitutes and electrical insulator sheets [5].
Silane cross-linked POs may have applications in the medical sector.
Studies on HDPE-g-VMSI suggest that the cross-linked material could be
251
an alternative to the ultrahigh molecular weight PE for prosthetic applications [89,90]. Cross-linked VLDPE-g-VMSI is a flexible and transparent
material for use in catheters, tubing and other medical instruments [91].
Silane-grafted POs have been added as modifiers into polymers such as
POs and PVC to improve some of their properties, especially the thermomechanical properties [5].
To enhance the material properties of the PP blends with EP rubbers
(EPR: EPM copolymers and EPDM terpolymers) Anderlik and Fritz
[35-38] prepared blends in which the elastomeric phase was moisture
cross-linked via silane grafting. The process takes place in a twin screw
extruder with an adequate design for reactive compounding and excellent
dispersing effect and mixing behaviour. Indeed, the material properties of
thermoplastic elastomers based on thermoplastic/rubber blends are strongly
related to the degree of dispersion of the rubber particles in the thermoplastic matrix material. The extruder was fed with EPR which is grafted by
injection of VMSI/DCP solution into the reaction zone. Then, PP was
metered into the next compounding zone where PP melting and its intensive
mixing with the grafted EPR occurred. To avoid PP degradation all the
peroxide added to initiate the grafting should have been completely decomposed at the beginning of the compounding zone. In contrast to standard
cross-linking systems (epoxy, sulphur, peroxide) the silane-grafted EPR can
be mixed with PP above its melting point without starting any cross-linking
reaction. When the well-dispersed EPR-g-VMSI component in such blends
was cross-linked in the usual way, i.e. by immersing the polymer blend in
hot water, the desired rubber-like properties were not obtained. Therefore,
with use of another twin screw extruder, the EPR-g-VMSI particles within
the blend with PP were cross-linked under the action of high shear by
injecting a mixture of water, ethandiol and catalyst into the polymer melt.
These 'dynamically cross-linked' PP/EPR blends showed outstanding material properties in comparison with those of only 'physically' mixed
PP/EPR blends [35-38]. Water injection into the barrel of the shaping
extruder processing the PE-g-VMSI/DBTDL masterbatch mixture was
earlier reported as an alternative to the usual moisture cross-linking
techniques [5].
5.8 Other silane cross-linking approaches
The two pathways to obtain moisture cross-linkable POs, i.e. random and
graft co-polymerisation of vinyl alkoxysilanes, have been used for other
polymer systems too. Alkoxysilane groups are incorporated into the polymer structure to make it moisture cross-linkable via Si-O-Si bonds. For
example, one component moisture curing varnishes are obtained during the
252
synthesis of acrylic resins by adding an alkoxysilane with a suitable

polymerisable group, such as MMSI, and another organofunctional silane
such as SMSI, as chain transfer agents to a mixture of monomers, e.g. I, II
and III, and subjecting the formulation to radical polymerisation:
CH 2 = CH - COO(CH2)3Si(OCH3h ; HS - (CH 2h - SI(OCH 3h ; CH 2 = CH - COOR;
I
CH3
CH 3
(MMSI)
(SMSI)
(I, where R = CH 3 , C4H9)
CH 2 = CH - COOX
A different approach of incorporating alkoxysilane groups into the PO

structure employs alkoxysilanes with no polymerisable bonds in the organofunctional group. The PO containing reactive groups directly from the
polymerisation step or a subsequent functionalisation (PO-X) reacts with
a silane having a suitable reaction group (Scheme 5.12):
PO-X+Y-Si(ORh
PO-Z-Si(OR)3
Scheme 5.12
Moisture cross-linkable materials with pendent alkoxysilane groups have

been obtained by 'attachment reactions' that occur during the melt mixing
of ethylene-butyl acrylate-methacrylic acid copolymer with the epoxy silane
GMSI (Table 5.2) [92J and of chlorosulphonated PE with epoxy- or
mercaptosilanes (GMSI and SMSI in Table 5.2) [93].
Alternatively, the function ali sed PO and the silane may bond via an
intermediate compound acting as a kind of coupling agent because it is
capable of reacting with both polymer and silane (Scheme 5.13):
PO - X + Y - R - Y + Z - Si(ORh
PO - R - Si(OR)3
Scheme 5.l3
Thus, chlorinated ethylene-butene-1 copolymer and C1(CH2)3Si(OCH3)3

have been roll kneaded in the presence of compounds having two identical
groups capable of reacting with the chlorine atoms from both copolymer
and silane [94].
The attachment of the alkoxysilane groups to the polymer chain via such
reactions is often called grafting although it does not involve the breaking
253
of a C=C bond in the silane. As in the 'true grafting' of unsaturated silanes

not all the added silane reacts and the 'attachment or modification yield'
(similar to the grafting yield) depends on the silane reactivity for the
functional group of the modified po. However, such approaches are more
complicated than the random and graft copolymerisation of silanes and are
restricted to only some functional or functionalised PO types and the silanes
bearing suitable reactive groups. Therefore, for POs, the attachment of
alkoxysilane groups by such polymer analogous reactions seems to lead to
no industrial exploitation. For other polymers, however, this route may be
much more attractive or even the only possibility of modification with
silanes. For example, when an epoxysilane such as GMSI (Table 5.2) is
thoroughly mixed during the shaping (extrusion or injection molding) of the
polyamide Nylon-12 the epoxide group of silane reacts spontaneously with
the reactive sites at the chain ends. The structure of the resulting polymer
will depend on the amount of added silane: chain lengthening by Si-O-Si
bridges in the case of too few silane molecules (IV), and a network with
multifunctional condensed silicon centres for excess silane molecules (V)
[95]:
OR
OR
- R - XXX - SI- 0 - SI- XXX - RI
OR
OR
- R- XXX-SI-O-SI- XXX - RI
OR
OR
(IV)
-R -XXX-SI- 0- SI- XXX-RI
OR
-R-XXX-SI-OR
I
OR
(V)
The silane cross-linking technique is an excellent alternative for polymers

where radical cross-linking is not very efficient, thus requiring additional
cross-linking agents, or where it is even impossible. The next major tonnage
of thermoplastics after PEs are PVC and PP, and they are much more
difficult to be cross-linked by peroxides or irradiation than is PE.
PVC shows many valuable properties that are suitable for a broad range
of applications but it has a relative low toughness and heat-deflection
temperature. For applications requiring such properties toughness can be
improved by addition of plasticisers or polymeric modifiers. Blending with
suitable polymers increases the heat-deflection temperature of PVC but the
best method would be its cross-linking. Although many ways of PVC
cross-linking are known they always bring technological limitations and
affect polymer properties, especially the thermal stability. The only process
that seems to have reached some commercial importance for flexible PVC
254
is cross-linking via irradiation together with reactive plasticisers. The silane

modification of PVC to make moisture cross-linkable products proved to
be a viable alternative to eliminate the disadvantages of the known crosslinking methods.
Whereas for POs the silane-grafting approach was initially followed the
first known attempt to obtain moisture cross-linkable products was the
copolymerisation of VC monomer with unsaturated silanes, described in a
patent awarded to Dow Corning Co. [96]. Reactor-made copolymers of VC
with silanes, e.g. containing 2% MMSI [97J are claimed even in these days
for the manufacture of moisture cross-linkable PVC products. Grafting of
silanes with C=C bonds (VMSI, VESI, MMSI) onto PVC chains seems to
have no chance of resulting in products with valuable properties for the
same reasons that make peroxide cross-linking poorly efficient.
The most investigated route to introduce alkoxysilane groups into the
PVC structure was their attachment to the PVC chain by reactions
involving the chlorine atoms and a suitable organofunctional group of the
silane, i.e. SH or NH z (Scheme 5.14). Aiming at industrial development the
PVC was modified by a suitable method, i.e. reactive processing. A patent
awarded also to Dow Corning CO. [98J describes the reaction of
amino silane with PVC during its processing. However, in these compounds
the basicity of the amino groups leads to elimination of HC!. A decrease in
the thermal stability is accompanied by premature cross-linking during the
modification process.
The system PVCjSMSI therefore gained much more attention [99-106].
Suitable additives have to be added to the system in order to scavenge the
HCI molecules resulting from the modification reaction. Early attempts used
various amino compounds [99-101J or, for example, the complex of
mercaptosilane with the organic compounds of cadmium [102J, but these
additives increased the sensitivity of PVC to degradation. By performing the
processing of PVC in the presence of suitable thermal stabilisers the
mercaptosilane can be bonded onto the PVC chain through nucleophilic
substitution of the CI atom, without great participation of competitive
elimination of HCI, thus retaining sufficiently high thermal stability of the
modified and moisture cross-linked products [103-106].
An approach to make moisture cross-linkable PVC compounds but
avoiding the difficulties involved in PVC modification with silanes is PVC
- CH 2- CH -CH 2- CHI
CI
CI
+ HX - (CH2)3Si(OCH3la _
- CH2 - CH - CH2 - CH I
I
CI
X - (CH2laSi(OCH3la + HCI
For SMSI (Table 5.2), X = S; for NMSI (Table 5.2), X = HN
Scheme 5.14
255
blending with different polymers already having alkoxysilane groups in the

structures, e.g. silane-grafted EVA copolymers and chlorinated PE, random
copolymers of different acrylates with MMSI [107-112]. Usually, a VC
copolymer containing hydroxyl or ether groups capable of reacting with the
silane-modified polymers is employed [109]. Thus, an improvement of
immiscible blend properties by chemical bonding between components may
be achieved. For the same purpose, co-cross-linking of PVC/chlorinated PE
was studied. Both polymers have been modified with SMSI, under similar
conditions, at best during their mixing [113].
Owing to different reasons all these approaches to obtain moisture
cross-linkable PVC compounds have not shown the same success as for
POs. PVC is generally inactive towards nucleophilic substitution except by
strong nucleophiles. Whereas amino silane is too aggressive and reduces the
thermostability of the PVC resin, the mercaptosilanes showed a rather poor
grafting efficiency.
A new approach to moisture cross-linkable plasticised PVC compounds
was introduced by Norsk Hydro for the NORVINYL DX 550 grade
launched in late 1992 [114]. In the mean time other grades of silanemodified PVC have been developed [115]. The main difference from earlier
methods is that the PVC resin is modified during VC polymerisation into a
reactive one, making it possible to use non-aggressive silanes. The silane
modification of PVC takes place during compounding where the gelation
degree must be kept low for achieving good processing properties when
extruding. The process offers a combination of high grafting efficiency with
good thermostability. The nature of the reactive sites in PVC and the silane
type are not disclosed. The compounds are extrudable on conventional
cable extruders. Following moisture cross-linking the mechanical properties
at high temperatures, heat ageing performance, abrasion and chemical
resistance are better than those of conventional plasticised PVC compounds.
This technology may be a viable alternative to irradiation cross-linked PVC,
cross-linked PE and different kinds of elastomers [116].
When subjected to free radicals the molecular weight of PP decreases
owing to p-scission reactions. Cross-linking of PP by peroxide and irradiation may be performed with much difficulty only in the presence of
cross-linking co-agents, i.e. multifunctional cross-linking monomers such as
triallylcianurate and divinylbenzene. The outstanding properties of PP as
well as the enhancement of some properties that could potentially be
achieved by cross-linking (low temperature brittleness, poor impact resistance, high chemical de grad ability) justify the research effort in this field
(ch. 2).
Moisture cross-linkable products have been obtained by PP grafting with
unsaturated trialkoxysilanes. Reactor-made products by copolymerisation
of propylene with these silanes cannot be obtained because owing to their
polarity the silanes are 'killers' for the actual polymerisation catalysts.
256
A number of patents awarded to Mitsui Toatsu Chemicals [117-138]

claim a different 'in-reactor' approach to obtain silane-modified crosslinkable PP. Propylene is copolymerised with an alkenylsilane, e.g. vinylmethyl silane, by using a normal catalytic system, i.e. MgCl 2 -supported
Ti-based catalyst plus alkylaluminium co-catalyst. This polymerisation was
possible because of the lack of polar groups in the silane structure. As the
ethylene-vinyltrialkoxysilane copolymers the propylene copolymers contain
a small amount of copolymerised silane, normally 1.3%.
The hydrogen atoms of the silicon are more reactive than in C-H bonds
and are thus reactive sites for the subsequent polymer modification by
grafting or cross-linking reactions. For example, graft copolymers resulted
from the treatment of the PP-co-SI with propylene oxide in the presence of
rhodium catalysts [118-120]. Cross-linking occurs when the copolymers are
treated with catalysts such as butyltitanate [124-126] and metallocenes, e.g.
dicyclopentadienyl zirconium dichloride [129] or with compounds such as
maleic anhydride [121, 128] able to react with the Si-H groups and thus
to generate linkages between the chains. These compounds, having two
reactive groups in the molecule, usually react in the presence of catalysts.
Several cross-linking systems are claimed: divinylbenzene plus metallocene
[117] or Zr(OEt)4 [130], polyethylene glycol plus Ti(OBu)4 [123] and
polysiloxane from SiPh 2 Cl 2 hydrolysis (degree of polymerisation, 1800) plus
metallocene [122]. For all these modifications the reaction takes place at
elevated temperatures (over lOOC), usually during the melt mixing of the
components. This interesting chemistry seems to generate different types of
cross-linkages between the chains, depending on the cross-linking system.
Sindiotactic copolymers, by propylene copolymerisation with dimethylallylsilane CH 2 =CH-CH 2-SiH(CH 3 h in the presence of metallocene catalysts, have been also synthesized [138]. However, to evaluate the potential
of this new method for its use in practice additional data are required.
5.9 Concluding remarks and future trends

Moisture cross-linkable silane-modified POs are of interest for both academics and technologists. The silane cross-linking technique involves a
different cross-linking chemistry in comparison with the traditional crosslinking processes. This results in technological advantages and improvements of many useful properties of silane cross-linked POs in comparison
with irradiation and peroxide cross-linked POs.
The modification of POs with unsaturated alkoxysilanes has been
achieved by both graft and random copolymerisation. This is one of the very
few cases where materials aimed at certain applications or markets can be
produced in practice by both graft and random copolymerisation. Both
routes incorporate the alkoxysilane groups in the PO structure and have
their balance of advantages and limitations.
257
The grafting approach resulted in the first moisture cross-linkable POs

launched on the market. Owing to its high potential to perform very
different functional modifications of POs [53, 139-141], the silane grafting
can be applied to all PO types, i.e. homopolymers, copolymers and multipolymers, PO blends of POs or POs' other polymers. Even today the vast
majority of the publications, especially patents, is concerned with the
silane-grafted POs.
The copolymerisation approach is restricted as yet to the moisture
cross-linkable products obtained by ethylene copolymerisation with silanes
in the high-pressure processes. For applications where LDPE-re1ated properties are required these copolymers have some established advantages
in comparison with silane-grafted LDPE, e.g. better storage and processing
stability. The addition of another suitable co-monomer such as butyl
acrylate can result in the tailoring of properties for specific applications.
The balance between grafted and copolymerised materials might be
subjected to important changes in the future. The outstanding potential of
metallocene catalysts in the copolymerisation of olefins and the tailoring of
the PO structure has resulted in the development of polymer types impossible to obtain with the classical Ti- or Cr-based catalysts. Copolymerisation
of ethylene with increasing amounts of higher ct-olefins such as n-octene
continuously decreases the polymer density: VLDPE (0.900-0.915 g/cm 3 )
and ULDPE (0.880-0.900 g/cm 3 ). The incorporation of unusually high
amounts of ct-olefins into the PE chain produced new polymer types:
plastomers or fiexomers (10%-20% co-monomer content) which bridges
the gap between thermoplastics and elastomers, and PO elastomers (20%35% co-monomer content). Cyclic olefin copolymers have been produced
by ethylene copolymerisation with norbornene. Precise tailoring of
stereo regularity in propylene polymers has also been achieved on an
industrial scale. It seems the copolymerisation of ethylene with polar
co-monomers in the presence of metallocenes will not be impossible in the
future. If such olefin-vinylalkoxysilane copolymers will become available
they will bring on the market products competing with the corresponding
grafted POs, e.g. HDPE-g-VMSI. Copolymerisation of olefins with unsaturated silanes (vinyl- and allyl-silanes) without hydrolisable groups
(alkoxy) have already been reported but this involves another cross-linking
mechanism without siloxane cross-linkages generated by water.
The literature on moisture cross-linkable silane-modified POs consists
mainly of patents. This situation is most likely a consequence of the
technological character of the method and the secrecy kept by producers.
Very little data have been published on the dependence of the silane-grafting
and random copolymerisation processes on the reaction conditions, as well
as on the dependence of polymer properties on its structure. Such data would
certainly contribute to a better understanding of the silane modification
and cross-linking steps and also for more useful commercialisation. To date
there is still a need for broad-based knowledge and expertise in this field.
258
Despite such unclarified theoretical aspects the moisture cross-linking of

silane-modified POs has become an industrial method employed in practice.
In comparison with peroxide and radiation cross-linking the silane crosslinking processes have their own balance of advantages and limitations.
Silane cross-linking has not to be regarded as a total replacement for the
classical cross-linking processes. However, for certain applications, especially those involving thin-walled articles, silane cross-linking is a serious
competitor. This is the case in low-voltage wire and cable insulation where
it offers several clear advantages, such as significantly less capital investment, competitiveness in product price, easy processing on conventional
extrusion lines and improvements in important properties of the crosslinked products.
Research efforts have already succeeded in enhancing the competitiveness
of the silane cross-linking method, e.g. improvements in storage and
processing stability with scorch-retardant additives and systems which cure
at ambient temperatures and humidity. Further work, aimed at increasing
the cross-linking speed, following the same routes or new approaches, will
make possible the more advantageous use of silane cross-linking for thicker
walled articles, e.g. insulation of medium-voltage and high-voltage cables.
Actual production units are based more on extrusion, for longitudinally
extended articles such as cable insulation, pipes, profiles, films, sheets and
the like. It is expected from other processing techniques, e.g. injection
moulding, blow moulding and roto-moulding to be employed also on a
larger scale.
The potential of the silane cross-linking technique has been far from fully
exploited. New modification approaches for the functionalisation of polymers with silanes are under investigation. Some of these developments have
already succeeded in commercialisation as in the case of moisture crosslinkable flexible PVC compounds.
Developments in silane synthesis have resulted in new silane types which
might bring unexpected properties when applied to silane cross-linking.
Thus, 'new silane' structures have been developed in which one or two of
the silicofunctional groups of the 'standard silane' structures, e.g. alkoxyl
groups, are replaced by the inert methyl group, thus imparting special effects
[47]:
('standard silane')
('new silane')
These structures could be of great interest, at least from a theoretical point

of view, e.g. for the study of the moisture cross-linking reactions and the
resulting structures. With these silanes only one or two OH groups will
259
result for each silicon atom, thus making possible the tailoring of the
cross-linkages in the network.
Other unusual alkoxysilanes such as H 2 C CH-(CH 2 )sSi(ORh
(R=CH 3 , C 2 H s) have been employed to prepare moisture cross-linkable
ethylene copolymers in the high-pressure process. Owing to the very long
pendent alkoxysilane groups, i.e. increased mobility, the copolymers cure
very quickly, e.g. 65% gel content after two days at 25C and 50% relative
humidity or 80% gel content after three hours in water at 80C [142-44].
The economic factor will, however, be decisive in the practical use of any
new silane type, which has to yield the lowest cost to performance ratio
possible.
One area where silane cross-linking might have important applications is
that of polymer blends. An improvement of blend properties may be
achieved here as a result of the chemical bonding between the immiscible
components of the blends. Developments in adhesion-related applications
are also expected.
Actually, moisture cross-linkable silane-modified POs cover a small
market but they have expanding possibilities. Although for different reasons
the silane cross-linking method has not shown for other thermoplastic
polymers the same success as for POs new applications should be found.
Some of such developments are in progress and others are expected in the
future.
Appendix S.A
S.A.l
5.A.l.l
Polymers
EPDM
EPM
EPR
HDPE
LDPE
LLDPE
MDPE
PE
PO
PP
PVC
ULDPE
VLDPE
XLPE
5.A.l.2
E th Ylene-propylene-diene terpol ymers

Ethylene-propylene copolymers
Ethylene-propylene rubbers
Medium-density polyethylene
Polyethylene
Polyolefin
Polypropylene
Poly( vinyl chloride)
Ultralow-density polyethylene
Very-low-density polyethylene
Crosslinked polyethylene
Monomers and chemicals
AA
BA
DBTDL
DCP
DTBPHY
E
EA
GMSI
MA
MMSI
NMSI
P
SI
SMSI
SRA
VA
VESI
VMSI
Acrylic acid
Butyl acrylate
Dibutyl tin dilaurate
Dicumylperoxide
2,5-Dimethyl-2,5-bis(t-butylperoxy)hexyne-3
Ethylene
Ethyl acrylate
3-Glycidyloxypropyl-trimethoxysilane
Methacrylic acid
3-Methacryloy loxypropy1-trimeth oxysilane
3-Aminopropyl-trimethoxysilane
Propylene
Organofunctional silanes
3-M ercaptopropy1- trimethox ysilane
Scorch-retardant additive
Vinyl acetate
Vinyltriethoxysilane
Vinyltrimetoxysilane
5.A.l.3
261
Miscellaneous
DMTA
DMTBH
DSC
DTG
ESCR
FTIR
GPC
IR
LALLS
SEC
SEM
t1/2
TEM
TG
Dynamic mechanical thermal analysis

2,5-Dimethyl-2,5-bis(t-butylperoxy)hexyne-3
Derivative thermogravimetry
Environmental stress cracking resistance
Fourier transformed infra red
Gel permeation chromatography
Infra red
Low-angle laser-light scattering
Size exclusion chromatography
Halflife
Thermogravimetry
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Reactive antioxidants for polymers

S. AL-MALAIKA
6.1
Introduction
The term 'antioxidants' is used here to refer to all chemical agents which act
to protect organic polymer substrates primarily against the deleterious
effects of molecular oxygen during manufacture and service and includes
melt, thermal and photo-stabilisers which are used to inhibit polymer
oxidation.
Hydrocarbon polymers vary in their inherent resistance to oxidation
depending on their chemical structures and their physical and morphological characteristics, and would, therefore, require varying degrees of protection by antioxidants [1 ~ 3]. Polyolefins dominate the world thermoplastics
market in terms of consumption of thermal and photo antioxidants [4].
Antioxidants are normally incorporated in polymers at low levels (generally
200~5000 ppm) during the processing or fabrication stage: the more demanding the application the greater the need for more efficient stabilisers to
achieve optimum properties and performance of the final polymer product.
The effectiveness of antioxidants depends not only on their intrinsic
chemical activity but also on their physical retention in the polymer. Loss
of antioxidants, for example, through migration into the surrounding
environment, by leaching out into contact food constituents (e.g. oils, fats)
or by extractive action of aggressive solvents (e.g. dry cleaning cycles, under
the bonnet environment), leads not only to premature failure of the polymer
article but also to problems associated with health hazards and toxicological
effects. The effects of the various physical factors (e.g. solubility, diffusion,
volatility, leachability) on polymer oxidation, stabilisation and antioxidant
behaviour both during high-temperature processing and in service have
been described [5~8].
In recent years, much research has been targeted at the different aspects
of antioxidant permanence in an attempt to address the problem of their
physical loss from polymers. A number of approaches have been developed
based on the concept of polymer-reactive antioxidants to restrict the 'free'
mobility of antioxidants in polymer substrates [9~23]. This would, in
principle, go a long way to satisfying the requirement of physical retention
of antioxidants during polymer conversion and in service and can be
expected to meet the more stringent legislations on the safety of additives,
especially in applications involving contact with the human environment
(e.g. food, pharmaceuticals, medical applications, cosmetics).
Chapman & Hall 1997
REACTIVE ANTIOXIDANTS FOR POLYMERS
267
This chapter will outline briefly some fundamental concepts in polymer oxidation and antioxidant mechanisms and will discuss the different
approaches available for utilising reactive antioxidants as efficient and safe
stabilising systems for polymers. The performance of selected reactive
antioxidant systems will be compared with that of traditional stabilisers
bearing the same antioxidant function.
6.2 Antioxidants and polymer oxidation: a mechanistic overview
6.2.1
Polymer oxidation
The chemistry of polymer oxidation is based on the classical free-radical

chain reaction theory involving molecular oxygen (Scheme 6.1) [24-29].
The central feature of this autoxidation mechanism is the initial peroxidation of the polymer substrate through the reaction of the alkyl peroxyl
radical (ROO), a key free-radical intermediate, with the substrate generating the hydroperoxide (ROOR) (Scheme 6.1, reactions b and c) which is a
crucial free-radical generator in the autoxidation cycle (reaction d).
The effect of oxidative degradation on polymers is most pronounced
during the high-temperature high-shear conversion processes (e.g. extrusion, injection moulding, internal mixing, milling, calendering) of the polymer to finished products, including reprocessing and recycling. The prior
thermal-oxidative history of polymers determines, to a large extent, their
photo oxidative behaviour in service [30]. The initiating species, e.g. hydroperoxides, and their decomposition products are responsible for the changes
in molecular structure and overall molar mass of the polymer, resulting in
a'
RH
o
R' +
g~
f
02
~~
RO'+'OH
C~n~u~n
R.
Chain
'Breaking
ROO
Antioxidant Mechenieme end cla_
~'"
'Prevendve
Chain-Breaking Acceptor
Chain-Braking Donor
Preventive Antioxidant.
MD
IUVAt
Q
Chain-Breaking Antloxldente
CB-A
CB-D
:d
rru
Heat
Light
Metal Ion.
ROOH
PO
UVA
MD
Q
RH
Peroxide Decomposer
U~raviolet Absorber
Metal Deactivator
Excited State Quenchers
Trmr/",Uoo'
2R'
......L.. }
2ROO'
......l.....-.
R' + ROO.......!L..
Non-radical products
Scheme 6.1
268
the loss of mechanical properties, e.g. impact, flexural and tensile strengths,
elongation, and changes in the physical characteristics of the polymer
surface, e.g. gloss, colour, crazing.
The extent of oxidative degradation of the macromolecular chain during
melt processing and in service depends ultimately on the nature and
structure of the base polymer. Polyolefins exhibit widely different oxidative
stabilities owing both to chemical and to physical effects. The greater
susceptibility of polypropylene (PP) and high-density polyethylene (HDPE)
towards photodegradation than LDPE has been attributed to morphological differences [31]. PP undergoes mainly oxidative chain scission during
processing whereas cross-linking reactions (associated with increases in both
molar mass and melt viscosity) predominate in low-density polyethylene
(LDPE) [32].
6.2.2
Antioxidant classes and mechanisms of action
Antioxidants cover different classes of compounds which can interfere with

the oxidative cycles to inhibit or retard the oxidative degradation of
polymers. The two major antioxidant mechanisms-chain breaking and
preventive mechanisms-are outlined in Scheme 6.1 [33,34]. Examples of
commercial antioxidants are shown in Table 6.1 under their primary mode
of action, albeit most antioxidants operate by more than one mechanism.
Chain-breaking (CB) antioxidants (sometimes referred to as primary
antioxidants) interrupt the primary oxidation cycle by removing the
propagating radicals, ROO and R- [33, 35, 36]. Chain-breaking donor
antioxidants (CB-D) operate by reducing ROO to ROOH (hydrogen atom
donors) (stabilisation reaction) (Scheme 6.2a).
AH
+ ROO
C8-0
..
ROOH
+ A
Non-radical
+
products
-/r----..,... AH + R
A
~ ~RH .. AOOH + R.
Stabilization
Reaction
+ RH
Propagation
reactions
''----'+'-''0;.00.2---.;.... ROO.
C8-A
Oydeficient
..
Non-radical products
Where: A is a CBD antioxidant and A is the antioxidant radical

Q is a CBA antioxidant
Scheme 6.2
Stabilization
Reaction
269
To perform their function, CB-D antioxidants (e.g. hindered phenols, AH)

must compete effectively with the chain propagating step (Scheme 6.2,
reaction c), and that the antioxidant radical (A-) produced in reaction a,
Scheme 6.2, must lead to stable molecular products; i.e. A does not continue
Table 6.1
Selected commercial antioxidants classified according to their function

Commercial or common
name
Antioxidant
Chain-breaking antioxidants
Hindered phenols
Cl-I
tButBu
I -.;::
(AH)
CHz-R
= -H
R = -CH 2C02C'BH 17
R = -(-CH2C02CH2)4C
R
----
CD
BHT
Irganox 1076
Q)
Irganox 1010
Ethanox 330
Irganox 1330
G>
Goodrite 3114
Irganox 3114
Me
Oy~O
/N1;'N ....
Me
tBu
tBu
(~-Q---tH-CH2-dH- ~Cl-I
Me
tB~CH2_AtBu
CH3
Topanol C
\J)
Cyanox 2246
CH 3
Aromatic amines
H
Rl-@-N--@- R2
Rl = R2 = tOct
Rl = H; R2 = HN-CH(CH3h
Nonox OD
Nonox IPPD
270
Table 6.1
(Continued)
Preventive antioxidants
Peroxide decomposers
Phosphite esters
(C'2H2S0->a- P
Phosc1ere P312;
Ultranox TLP
Irgafos 168
Ultranox 626
Sulphur compounds
II
[ RO-C-CH 2CH 2-12-S

R = C ls H 37
@
@
C 12 H25
Irganox PS802
Irganox PS800
.M~S~
'}:C-NR2] 2
M = Zn; R
M=Fe:
@
@
= C4 H 9
RobecZ bud
Iron dithiocarbamate
Metal deactivators
[ ~~-CH2CH2~~R_l
~
IBu
R=H
R=H-(CH 2h
2
R=H:
R = H-(CH2h:
@
@
Irganox MD-1024
Irganox 1098
Photo-antioxidants (hindered amine light stabilisers)
tt-POCO(CH2l8OCOq- H
Tinuvin 770
CH3-POCO(CH2l8OCOq- CH3
Tinuvin 292
Table 6.1
271
(Continued)
Ultraviolet absorbers
@
@
Tinuvin 326
Tinuvin P
Cyasorb UV 531;
Chimassorb 81
Nickel complexes
_ Ni<:..;: - -H2N-C 4 Hg
0
~s~
eEl
Cyasorb UV 1084;
Chimassorb N-705
ICaH 17 ICaH 17
Nickel dialkyl
dithiophosphate
(NiDRP)
the kinetic chain either by hydrogen abstraction or by reaction with oxygen,

propagation reactions (Scheme 6.2, b and c). Hindered phenols and
aromatic amines (see Table 6.1, antioxidants (AOs) 1-9) are important
examples of commercial CB-D antioxidants. Chain-breaking acceptor antioxidants (CB-A) act by oxidising alkyl radicals in a stoichiometric reaction (R are removed from the autoxidising system in competition
with the chain propagating reaction; Scheme 6.1, reaction b) and hence are
only effective under oxygen-deficient conditions, stabilisation reaction
(Scheme 6.2d). Quinones and stable free radicals which can act as alkyl
radical trapping agents are good examples of CB-A antioxidants.
Hindered amine derivatives (often referred to as hindered amine light
stabilisers, HALS, e.g. AOs 19 and 20 in Table 6.1) also function by a
chain-breaking mechanism and, through their transformation products, are
able to trap both R and ROO in a cyclical regenerative mechanism
(Scheme 6.3 shows a simplified reaction mechanism) [37-43].
Preventive antioxidants (sometimes referred to as secondary antioxidants), on the other hand, interrupt the second oxidative cycle by
preventing or inhibiting the generation of free radicals [34]. The most
important preventive mechanism is the non-radical hydroperoxide decomposition, PD. Phosphite esters and sulphur-containing compounds, e.g. AOs
10-16 in Table 6.1, are the most important classes of peroxide decomposers.
272
ROO~ROO'
(
>N-H
ROOH
ROO'
.. >NO.
(~)
..
~>N~R
:
~ ~
~t
\"'
---"':""""..,>NOH(+>C=C<)
;>au<
HALS
ROOH
ROO'
Scheme 6.3
Phosphites reduce hydroperoxides to alcohols and are themselves

oxidised to the corresponding phosphates with a 1: 1 stoichiometry and
hence are referred to as stoichiometric peroxide decomposers (PD-S):
P(OR)3 + ROOH
PO - S
= P(OR)3 + ROH
Scheme 6.4
In addition to their stoichiometric peroxidolytic activity, some phosphite

esters also behave as catalytic peroxidolytic agents (PD-C) and others (e.g.
hindered aryl phosphites, e.g. AOs 11 and 12 in Table 6.1) are also capable
of functioning by a chain-breaking mechanism; the contribution of each of
these modes to the overall mechanism depends on the structure of the
phosphite, the oxidisability of the substrate and the reaction conditions
[44,45].
Sulphur compounds, e.g. thioethers and esters of thiodipropionic acid
and metal dithiolates (Table 6.1, AOs 13-16), decompose hydroperoxides
catalytically (PD-C) whereby one antioxidant molecule destroys several
hydroperoxides through the intermediacy of sulphur acids [46-49]:
R-S-R' +ROOH
pO-C
o=s
"R
'R'
+ROH
[011
Sulphu r acids
(ionic catalysts for hydroperoxide decomposition)
Scheme 6.5
Metal deactivators (MD) act primarily by retarding metal-catalysed oxidation of polymers; they are important under conditions where polymers are
in contact with metals, e.g. wires and power cables. Metal deactivators are
usually polyfunctional metal chelating compounds (e.g. Table 6.1, AOs 17
273
and 18) that can chelate with metals and decrease their catalytic activity
[50-52].
Ultraviolet absorbers (UV A) act by absorbing UV light hence retarding
the photolysis of hydroperoxides. Typical examples are based on 2-hydroxybenzophenones (AO 23) and 2-hydroxybenzotriazoles (e.g. AOs 21 and 22);
both are photo-stable with high molar absorptions over the region 300360 nm. Their activity is based essentially on absorption of the harmful UV
radiation and its harmless dissipation as heat; for example, UV light induces
intramolecular hydrogen transfer in 2-hydroxybenzophenones to give an
enol which is converted in a radiationless process back to the original
ketone [53]:
Scheme 6.6
6.3 Effect of chemical structure and physical factors on antioxidant

permanence
The commercial success of antioxidants depends not only on their inherent
chemical effectiveness but also on their physical characteristics, as well as
their toxicological behaviour and cost considerations. Under aggressive
service conditions antioxidant performance can be dominated by their
physical characteristics. Significant amounts of antioxidants are often lost
from polymers through volatilisation during processing and fabrication or
as a result of exudation and solvent extraction during end use. This problem
is particularly severe in the case of semicrystalline polymers and with
polymers artifacts having high surface-to-volume ratios, e.g. coatings, fibres,
films [5,7]. In practice, therefore, the efficiency of antioxidants is a product
of a complex relationship between all the chemical and physical factors: the
chemical structure of the antioxidant, the thermal and photochemical
stability both of the parent antioxidant and of its transformation products,
and their physical behaviour (e.g. solubility, diffusivity, volatility, leachability) and their interactions with the polymer substrate with due account to
chemical and morphological features.
Stringent regulations exist, in most countries, on the use of antioxidants
in applications involving the human environment, e.g. food packaging and
medical applications. Physical loss of antioxidants into the contact media
can have severe toxicological consequences in addition to risks associated
with premature failure of the polymer product. Although all antioxidants
274
which are licensed for use in polymers for food contact and medical
applications have to undergo strict toxicity testing regimes, their approval
does not necessarily mean that their oxidation products (derived from the
parent antioxidant during processing or as a result of its antioxidant action
in the substrate) are also non-toxic, and these are generally not tested for
their toxicity.
In view of the above problems which are generally associated with
the use of traditional low molar mass antioxidants, research in recent years
has focused on alternative types of antioxidants. Reactive antioxidants,
which can be chemically anchored on the polymer backbones to prevent
their physical migration from the polymer during processing or while in
service, have been synthesised and exploited as non-migratory antioxidants
[54-60].
6.3.1
Chemical effects
The intrinsic chemical activity of antioxidants is a function of their molecular structure. This can be determined accurately in a model substrate where
the antioxidant is fully soluble and in a test where no physical loss is
possible. However, use of the chemical activity alone as an indicator can
lead to unreliable predictions of the efficiency of antioxidants in polymers
under practical conditions owing to the dominating influence of physical
factors under certain environments. For example, the hindered phenol BHT
(Table 6.1, AO 1) is amongst the most efficient antioxidants known for
liquid hydrocarbon (based on its intrinsic chemical activity determined by
oxygen absorption) but is ineffective in protecting thermoplastic polymers
(during accelerated air oven ageing) because of its rapid depletion through
volatilisation from the polymer [32]. Commercial developments, however,
have led to the synthesis of higher molar mass antioxidants based on the
same hindered phenol function, e.g. Irganox 1010, Ethanox 330 (Table 6.1,
AOs 4 and 5), which have successfully outperformed BHT under these
conditions [2,61].
6.3.2 Physical effects

The physical behaviour of antioxidants is a major factor affecting their
permanency, efficiency and acceptability, especially when the polymer artifacts (e.g. fibres, films) are in contact with aggressive environments, e.g.
organic solvents including dry cleaning solvents, hot water and detergents,
hot oils, acids, fatty food, hot air and intense solar radiation. Physical
factors which control the effectiveness and permanence of antioxidants
include distribution, solubility, diffusivity, volatility and leachability.
(a) Distribution of antioxidants and polymer morphology. In order to

inhibit the oxidation of polymers, the antioxidants have to be present in
275
sufficient concentration at the various oxidation sites. In this respect, both

the distribution of antioxidants and the morphology of the host polymer
assume important roles. Examination of the distribution of photoantioxidants in typical commercial semicrystalline polymers, such as polyolefins,
has shown that they are rejected into the amorphous region on the
boundaries of spherulites [5,62]. Such non-uniform distribution of antioxidants leads to an increase in their concentration in the amorphous region
which is most susceptible to oxidation (the crystalline phase is normally
impermeable to oxygen) [5]. However, in the case of polymer blends, a
non-uniform distribution of antioxidants can undermine the overall stability
of the blend, especially if it does not occur in favour of the more oxidisable
component of the polymer blend.
(b) Compatibility of antioxidants with polymers. Antioxidants are generally less soluble in polymers than in lower molar mass liquid models.
Although antioxidants are usually highly soluble at the elevated processing
temperatures (present in the polymer as homogenous solution), they come
out of solution on cooling to room temperature and the solid polymer
becomes supersaturated with the antioxidant. In turn, the antioxidant may
precipitate as a separate phase, and exudes to the polymer surface (this is
called 'blooming') [5] leading to a build up of a concentration gradient near
the surface forcing further migration of antioxidant from the bulk. Consequently, an antioxidant with low solubility and high diffusion rate is prone
to blooming and to loss to the surrounding medium by evaporation (air
stream as contact media) or through leaching (extraction by a liquid contact
media), leaving behind an unprotected polymer surface.
Generally, the compatibility of antioxidants in polymers is improved
when the antioxidant and the host polymer have similar characteristics.
Compatibility of antioxidants in non-polar hydrocarbon polymers, therefore, decreases with increasing antioxidant polarity and increases with the
number, length and branching of the inert alkyl substituents attached to the
antioxidant function [63,64]. Many commercial antioxidants with higher
molar masses (e.g. Table 6.1, AO 4 compared with AO 1) have been
developed and many have inert long (8-18 C atoms) alkyl chains (e.g. Table
6.1, AOs 3, 13, 14,23 and 24).
(c) Antioxidant diffusion, volatility and leachability by contact media. The
permanency of antioxidants is affected by diffusion characteristics of the
antioxidant, the nature (gas, liquid, solid) of the surrounding medium, and
the temperature [5,8,63]. Generally, the diffusion coefficient of antioxidants
decreases with increasing polar interactions with the polymer, increasing
molar mass of antioxidants and branching in their alkyl side chain.
In the presence of a stream of hot air or high temperature and low
pressure (e.g. during polymer melt processing) volatility becomes very
important: it is governed by the rate of diffusion of antioxidants which in
276
turn determines the rate at which the surface is replenished [5]. The
influence of polymer sample shape and the structure and molar mass of
antioxidants on volatility has received much attention. The rate of evaporation of antioxidants from rubber and polyethylene, for example, was found
to be inversely proportional to the thickness of the sample and directly
proportional to its surface area [63]. Furthermore, an increase in molar
mass results in an increase in intermolecular dispersion forces which brings
about a decrease in volatility of the antioxidants from the polymers.
In liquid contact media (e.g. foodstuffs, oils, solvents) the rate of loss of
antioxidants from the polymer surface depends both on their diffusion
coefficient and their partition coefficient between the liquid and the polymer.
This is complicated by the varying ability of different solvents (liquid media)
to swell polymers giving rise to an increase in the diffusion coefficient of the
antioxidant, which leads to higher loss rates [8]. As in the case of volatilisation, the rate of leachability of antioxidants from the surface of polymers
into liquid contact media increases with temperature and the ratio of surface
area to volume, e.g. in thin polymer samples.
6.4
Reactive antioxidants and routes to antioxidant permanency in polymers
The majority of commercial antioxidants are low molar mass organic

compounds. Although these have been shown to be quite effective, their
performance is drastically curtailed under extractive environments, especially when used in thin polymer samples. Under these conditions, low molar
mass antioxidants are rapidly consumed owing to unfavourable physical
characteristics, e.g. high diffusivity, rapid volatility and/or leachability in
presence of solvents, leading to the loss of polymer properties and ultimately
to the premature failure of the polymer artifact.
Higher molar mass commercial antioxidants, which are well characterised and often bulky (e.g. Table 6.1, AOs 3, 4, 5 and 6) perform more
effectively than their lower molar mass counterparts (e.g. AO 1) owing to
better physical characteristics, e.g. lower diffusion and volatility. Such
antioxidants, however, are physically lost, e.g. by leaching, from the polymer
under extremely aggressive service conditions.
Further attempts to overcome the problem of physical loss of antioxidants has led to the development of oligomeric and macromolecular
antioxidants. A broad range of such antioxidants (both thermal- and photoantioxidants) has been synthesised by a variety of methods, e.g. free-radical
polymerisation, ring-opening polymerisation and polycondensation processes [57] (Table 6.2 provides selected examples). The superior performance of these antioxidants (as a result of their retention) when used in
polymers (both plastics and rubbers) for demanding applications, e.g. at
elevated temperatures in the presence of oils and other solvents, has been
277
Table 6.2 Selected examples of oligomeric and macromolecular antioxidants (AO 30-32)
Commercial or common
name
Antioxidant
.R =
- N"o
+rt
'--'
Cyasorb UV3346
ffl
O-'--t-(CHzl:z-O-C-(CHz)a-C [
Chimassorb 944
Cyasorb UV-3346
Tinuvin 622
CH.
Flectol H,
Goodrite 3140
Poly TDP-2000
Poly AO-79
Poly phosphite
Source: Pospisil, J., ch. 6 in Oxidation Inhibition of Organic Materials, vol. 1 (eds P. Klemchuk
and J. Pospisil); published by CRC Press, Boca Raton, 1990.
demonstrated (Tables 6.3 and 6.4) [65,66J. However, the synthetic routes
for macromolecular antioxidants are generally more expensive than those
used for their low molar mass analogues, and their characteristics are not
always fully defined. Furthermore, their high molar masses could lead to a
lowering of compatibility with the host polymer, with serious consequences,
especially in crystalline polymers; this would further undermine their apparent advantages. Indeed, only a relatively few cost-effective macromolecular
antioxidants are in commercial use [57].
A more attractive route to producing antioxidant systems, which suffer
minimal or no physical loss during fabrication and exposure to severe
278
Table 6.3 Effect of thermal treatment and latex application on polypropylene multifilaments
(fibre 130/37): exposure time (in hours) in Xenotest 1200 to 50% loss of tenacity
Treated
Antioxidants
Control
Tinuvin 770 (AO 19):
0.15
0.30
0.60
Tinuvin 622 (AO 28):
0.15
0.30
0.60
Untreated
20 min at
120 C
Acrylic latex
and 20 min at
120 C
490
550
460
3600
4600
7400
1800
2300
5200
570
650
750
2950
4250
5500
2200
4200
5500
2450
3711
5600
Source: Sedlar, J., ch. 1 in Oxidation Inhibition of Organic Materials, vol. 2 (eds P. Klemchuk
and J. Pospisil), ch. 1; published by CRC Press, Boca Raton, 1990 with permission.
service conditions, would be to utilise reactive antioxidants which can form

an integral part of the macromolecular chain of the polymer.
Reactive antioxidants (Rv-AOs) can be defined as compounds containing
one or more antioxidant functions (the antioxidant component) and one or
more chemical functions capable of reacting either with monomers (same
or different) or with polymers (the reactive component). The antioxidant
moiety can be based on any of the conventional antioxidant functions discussed in section 6.2.2, and the reactive group can be chosen from a variety
of polymerisable or non-polymerisable functions, e.g. vinyl, allyl, r:t.-fJ un-
Table 6.4 Effect of HAF carbon black and antioxidant on heat stability
in peroxide-cured ethylene-propylene rubber in air at 80 C: percentage
retention of properties after 203 days ageing. UTS = ultimate tensile
strength; MlOO = Mooney viscosity; EB = elongation at break
D
Vu1canisate
UTS
MlOO
EB
No antioxidant
1% Flectol H, AO 29
2% Poly (BQ/PPD)"
2% Poly (NonoxjDME)b
69
86
108
92
86
103
123
117
81
86
99
92
Source: Thomas, D.K., ch. 4 in Developments in Polymer Stabilisation, vol.

1 (ed. G. Scott); published by Applied Science Publishers, London, 1979
with permission.
"Polymeric aromatic amine antioxidant produced by room temperature
reaction between p-phenylenediamine and benzoquinone.
bPolymeric aromatic amine antioxidant produced by diphenyl-pphenylenediamine and xylenen glycol dimethyl ether in the presence of
stearic chloride as catalyst.
279

(01 E..m...... of _ I " . function.
R
~=CH2
~
; CH,= C-@;
R0
,II
CH~-
~~
; CHo=C~@);c~
."...".
..0
R=HjR=CHa ; n=0-4
Rv-I
Rv-2
Rv-3
Rv-4
.,..,.,
RO
I II
CH~NH'CHoffi
space,
Rv-5
(bl Schematic repreoenI81Ion of oumpIH 01 """'lcal attachment 01 ont'OIlIdo"'o on poly.,.,.
-r
VI
,
Copolymerisation during
potymer manufacture
[!J
I
@)
Grafting on saturated or functional polymers
II
Grafting on functionalised polymers

II
~
Scheme 6.7
saturated acyl or amide groups (e.g. acryloyl, acrylamide, methacryloyl or

methacrylamide), styrene, isopropenyl, epoxy and mercaptan (Scheme 6.3).
The reactive function, which is the point of attachment to the polymer
chain, can either be directly connected to the antioxidant moiety or can be
separated by an inert flexible and short chemical link (aliphatic or aromatic)
which acts as a spacer (Scheme 6.7). It has been suggested that the presence
of a spacer minimises the influence of the main polymer chain and its
characteristics on the activity of the antioxidant function [67] and that the
chemical nature of the spacer affects the overall antioxidant activity and
.-au
OR
~ OH-Ot(CH2l1x.g-h=CHR"
'-Bu
.-au
=NH; 0
n=O-4
R = H; CH 3
R" = H; CH 3 ; Phenyl
R
I
CH20C
.-au
Where X
Spacer
Vary length
Where
R"
Spacer
Vary bulkiness
Scheme 6.S
R = CH 3; ROO =H
R C2 Hs ; R" H
R =CH 3 ; . R" =CH3
280
performance of the reactive antioxidant [68]. For example, examination of

the effect of the chemical structure of spacers on the antioxidant activity
(measured by oxygen absorption test) of two reactive antioxidant series
based on (meth)acrylamide (Scheme 6.8, AO 33) and (meth)acrylate ester
hindered phenols (AO 34) has shown that the chain length had a dramatic
effect on both antioxidant series (minimal antioxidant activity for short
lengths (one CH 2); AO 33) and that chain branching in the acrylamide
antioxidant series (AO 34) had no appreciable effect on the antioxidant
activity [68].
Two approaches can be broadly identified that utilise reactive antioxidants in the production of 'permanently' stabilised polymer systems.
6.4.1
Copolymerisation of reactive antioxidants during polymer manufacture
The copolymerisation of reactive antioxidants with various monomers

during the polymer synthesis to give polymers with in-built antioxidant
functions (see III, Scheme 6.7b), appears to be a logical route to achieving
antioxidant permanency in polymers. The majority of Rv-AOs utilised in
this approach have been chosen so that they are suitable for free-radical
copolymerisation, hence the attachment of polymerisable reactive groups
(e.g. acrylate, methacrylate, vinyl, isopropenyl, allyl) to the antioxidant
R'
LCHr~lLCH;I -1
-(CH~~CHz.cj
"\ RM
~Jy N
ROO
~N~
OH
\N~
(~OH
~N ~/N~
~,
N
OH
N\~
N
Antioxidant-modified polymers: Hydroxy benzotriazole-based antioxidants
R = H, CH 3 (antioxidants with vinyl or isopropenyl reactive groups):

R' =CsHs Roo = H (Styrene): R' =COCH3 Roo =CH3 (Methyl methacrylate):
R' = COOCH 3 Roo = H (nbutyl acrylate)
t.t ,
-{CHz-CHz
9H-CHz
C=O
Antioxidant-modified polymer:
Hydroxy benzophenone-based antioxidant copolymerised with ethylene
o
I
f~
HO>=\-O
r!
Scheme 6.9
281
function. A variety of monomers, e.g. styrene, styrene-acrylonitrile, methyl

methacrylate, n-butyl acrylate and ethylene, have been exploited in antioxidant copolymerisation reactions [56,57].
Extensive work has been documented on the synthesis and successful
copolymerisation of a large number of polymerisable UV -absorbers containing one UVA function which is based either on the 2-hydroxybenzophenone
or the 2-hydroxybenzotriazole type [69-74]. Further progress was made in
the synthesis of polymerisable antioxidants containing two UVA functions
(of the same or different types) in the same Rv-AO molecule [56,75] by
applying more sophisticated synthetic routes (Scheme 6.9 shows selected
examples). The use of such bifunctional antioxidants is beset by high
synthetic costs, though it no doubt could lead to more effective stabilised
polymer systems.
The use of phenolic (hydroxy group) and amino-based antioxidants
(thermal-stabilising moieties) by this approach has been limited because of
a major, though expected, problem of interference with the free-radical
polymerisation process (polymerisation inhibition), leading to lower efficiency. Furthermore, the nature of the free-radical initiator used in the
copolymerisation process has also been shown to affect both the antioxidant
activity and the copolymer yield. In contrast to peroxides and hydroperoxides, non-peroxidic initiators, such as azo-bis-isobutryonitrile (AIBN), are
generally preferred because of their inability to abstract hydrogen from the
antioxidant moiety [69]. To overcome the reactivity problem of the phenolic hydroxy group, a different solution was adopted, albeit economically
unattractive, in which the phenolic hydroxy group is protected first, followed by a copolymerisation process and the final removal of the protecting
group to regenerate the antioxidant function [76].
One of the few commercial products available is based on the polymerisable chain-breaking antioxidant (AO 35 (shown in scheme 6.10, a methacrylamide aromatic amine) designed for nitrile rubbers (NBR) (Chemigum
HR 665). This is prepared by emulsion copolymerisation with acrylonitrile
(AN) and butadiene BD:
Scheme 6.10
282
100
1:
~c:
.2
1ii
01
c:
.Q
S-OPA control Copolymerised AO 35 Masterbatch AO 35
Figure 6.1 Retention of elongation of sequence-aged NBR vu1canisates with AD 35copolymerised NBR or AD 35-BD (Butadiene) masterbatch blends with NBR (1.6 phr) alone
o and with the thioester AD14 used as a synergist. (at 8 phr). Comparison is made with a
control containing styrenated diphenylamine (S-DPA) as a conventional antioxidant analogue.
Ageing conditions: 16h/149C in oil followed by 16h/163C air [78].
It offers superior antioxidant performance, especially under aggressive (hot
oil, high temperature) conditions compared with a low molar mass conventional aromatic amine antioxidant such as AO 8 (Table 6.1) [77]. Similarly,
AO 35 was prepared as a masterbatch (high antioxidant concentration) by
emulsion copolymerisation (e.g. with butadiene). The masterbatch antioxidant was then blended with conventional polymers (e.g. NBR) to provide
the desired end-use level (e.g. 1.6 phr) of antioxidant functionality. Figure 6.1
shows the superior performance of such a bound antioxidant system
(including both the copolymerised AO 35-NBR and the AO 35-butadiene
masterbatch) compared with conventional styrenated diphenylamine (unbound) antioxidant [78]. Much less success has been accomplished, however, with the use of hindered phenols in rubber-modified polymers [54].
In spite of the successful synthesis and copolymerisation of a large
number of reactive antioxidants there is a lack of major commercial
development and production of bound antioxidant systems based on this
approach. This is almost certainly because of both low efficiency of polymerisation in the presence of certain antioxidant functions and, more
importantly, to the high costs generally involved in the synthesis and
production of tailor-made 'speciality' materials for each specific application.
However, this approach may be utilised in certain target applications where
performance reliability, especially under a demanding environment, is the
ultimate design requirement, e.g. in space and military applications.
6.4.2
Chemical grafting of reactive antioxidants post polymer manufacture
Various chemical routes have been exploited to achieve grafting of reactive antioxidants onto preformed commercial polymers. The different
routes available vary, depending on the way by which the free-radical
283
initiation process for the antioxidant grafting reactions is achieved: during

vulcanisation, by decomposition of free-radical initiators (FRI); peroxides,
hydroperoxides, AIBN), by UV- or y-irradiation of polymer surfaces, by
mechanical scission and during melt processing in the presence of added
FRI. An important prerequesite for the success of anyone of these routes is
that the reaction leading to the chemical attachment of the antioxidant
should be achieved without adversely influencing the overall polymer
properties or affecting the basic processes involved, e.g. vulcanisation in the
case of rubbers or melt processing or fabrication of plastics. The different
routes, their limitations and merits, are briefly discussed below.
(a) Reactions with functional and functionalised polymers

Functional polymers. Unsaturated rubbers (e.g. natural, butyl, styrene
butadiene and nitrile rubber (NR, BR, SBR and NBR, respectively)) are
examples of functional polymers as the reactivity of the double bonds (or
the active methylene group attached to the double bond) in the polymer
backbone can be exploited for promoting chemical reactions on the rubber
backbone by reactive antioxidants. Generally, chemical attachment of antioxidants has been achieved either in rubber latex or in solid rubbers during
the vulcanisation process.
The earlier work on chemical attachment of antioxidants during rubber
vulcanisation was based on the use of a variety of aromatic mononitroso
compounds, e.g. 4-nitrosodiphenylamine [79]. The nitroso antioxidant is
compounded with the unsaturated rubber and a complex grafting reaction
takes place during the vulcanisation process. The chemistry involved is
not too dissimilar from that associated with the well known quinone
dioxime vulcanisation (activated by lead oxidants) involving a nitrosoareneolefin 'ene' addition reaction. This occurs via the formation of an oxidation
product, p-dinitrosobenzene, which becomes responsible for the subsequent
cross-linking reaction pathways through the intermediacy of alkenylhydroxylamine linkages [80]:
o
N-O-~-o
N-O-C-o'
o
II
NO
Pb30 ,
(Oibenzoylquinone dioxime)
AA
--......
AA
NO
Scheme 6.11
~
NOH
~
.&
Further reactions
NOH
Similarly, the binding of mononitroso compounds (e.g. AO 36 in scheme

6.12) during vulcanisation of unsaturated rubbers was shown to occur
through the intermediacy of the hydroxylamino derivative. This is thermally
284
decomposed during high temperature vulcanisation to form a polymerbound phenylenediamine, AO 37, and a bound nitrone, AO 38 [79]:
~
NOH
~
+
NO
Thermal
decomposition
(A036)
6
NH
NH
NH
+~
~
NH
N-O
(A037)
I
Scheme 6.12
6
NH
(A038)
Rubber-bound antioxidants
Like the commercial low molar mass phenylenediamine analogue, AO 9

(Table 6.1), the bound phenylenediamine, AO 37, imparts very effective
antioxidant properties owing to the antioxidant chain-breaking activity of
the amine function, but, unlike the former, the bound antioxidant retains its
effectiveness after solvent extraction of the rubber [79]. The overall antioxidant effectiveness of the bound system may also have been boosted by a
contribution from any bound nitrone, AO 38, formed during vulcanisation;
nitrones are known to be very effective radical traps [81].
The advantages gained by the high permanency of antioxidants which
become attached to rubbers during the vulcanisation process are more than
offset by enormous practical problems often encountered as a result of the
interference of the reactive antioxidant with the vulcanisation process (both
ingredients and conditions) [79], hence its limited use.
A practical solution to this problem is to carry out the antioxidant grafting
reaction on rubber latex before the vulcanisation process. A number of reactive
hindered phenols and aromatic amines have been successfully grafted in this way
(using radical initiators) to produce effective bound antioxidants [54, 82-84]:
RqR'
OH
+ Rubber latex
I~
radical initiators
0
II
(CH2)n-O- C-CH = CH 2
(A039)
AO 39: (a)
(b)
(c)
(d)
(e)
n = 1,
n = 0,
n = 1,
n= 1,
n = 2,
R' = R' = t-Bu (OBBA);

R' = R' = t-Bu;
R' = R' = Me;
R' = t-Bu, R" = Me;
R' = R' =t-Bu.
Scheme 6.13
(6.11)
285
The performance of latex-grafted antioxidants, e.g. the hindered phenol

AO 39(a) (DBBA), was shown to be superior to that of the control (with no
antioxidant) as well as for a macromolecular antioxidant derived from the
same structure (poly-DBBA) [84]. The reason for the low activity of polyDBBA is the unfavourable distribution of the antioxidant and limited
compatibility. Latex grafting has also been achieved with thiol-containing
antioxidants; different rubbers (e.g. acrylonitrile butadiene styrene (ABS),
NBR, SBR, NR) in the latex forms were utilised for grafting reactions giving
rise to bound antioxidants which are highly efficient especially under
extractive conditions [55]. The chemistry involved in the grafting reaction
is discussed later.
Functionalised polymers. Conventional polymers may be function ali sed
via grafting reactions with monomers containing reactive groups. The
resultant reactive pendent groups can then be used as reactive sites for
promoting further grafting or functionalisation reactions. Unsaturated rubbers as well as inert hydrocarbon polymers, e.g. saturated polyolefins, can
be modified in this way. Examples of some reactive functions of the pendent
groups in function ali sed polymers include epoxides, alcohols, aldehydes,
carboxylic acids, anhydrides, acid chlorides, chlorides, sulphonyl chlorides
and amines. Reactive antioxidants having a chemical function capable of
reacting with the active moiety in the pendent group will lead to grafted
antioxidant structures (II, in Scheme 6.7b). This approach, therefore,
broadens the scope and increases the flexibility of antioxidant grafting on
preformed polymers. However, the penalty in most cases would be an
increased cost of the product because of the additional functionalisation
step, unless this is carried out simultaneously with the antioxidant grafting
reaction during the manufacture or processing or fabrication steps at no
additional cost (see later).
In addition to the methods discussed in previous sections for attaching
antioxidants on rubbers, antioxidant grafting can also be achieved by
co-reactions of function ali sed rubbers with reactive antioxidants. For
example, epoxidised rubbers, in which the epoxy function has been introduced either by direct epoxidation or by reaction with a suitable comonomer, such as glycidyl methacrylate, have been reacted with aromatic
amines and hindered phenols containing suitable reactive functions, such as
amino or hydroxy groups, to give rubber-bound antioxidants [85-87]
(reaction a of Scheme 6.14). Similar antioxidant grafting reactions have been
achieved with rubbers functionalised with acid chloride groups [88] (reaction b of Scheme 6.14). The practical success of this approach depends
ultimately on the additional cost involved in the functionalisation of the
rubbers.
Saturated hydrocarbon polymers, e.g. PP and polyethylene (PE), can also
be functionalised in a similar fashion by using a variety of reactive
286

OH
I
JV"CH 2 CH-CHCH;zJV'
~H-o-Ntt-O
"""CH 2CH-CHCH;zJV'
'0/
Epoxidised rubber
CH 3
"""f-CH 2./V'
C=O
I
yH
b
J"VV'C-CH~
I
C=O
tBu
OCH 2 -Q-OH
tBu
CI
Acid chloride
functionalised rubber
Scheme 6.14
monomers, e.g. maleic anhydride, glycidyl methacrylate, acrylamide and

(meth)acrylic acids, to generate polymers with reactive pendent groups
capable of further reactions with suitable reactive antioxidants. The chemistry of functionalisation (e.g. maleinisation and epoxidisation) of such
polymers has been discussed earlier (ch. 1). A number of patents appeared
in the late 1960s [89-92] covering the grafting reactions of different
antioxidant functions (e.g. hindered phenol, thiopropionamide) with functionalised polyolefins (e.g. epoxidised, maleinised, amidised then treated
with HCI; reactions a, b, c and d of Scheme 6.15A). The polymer-bound (e.g.
PP-bound) antioxidants were shown to offer superior thermal stability and
resistance to extractive and aggressive conditions of dry cleaning. For
example, functionalised polypropylene yarns grafted with hindered phenol
and thiopropionamide antioxidant moieties (Scheme 6.15, reactions d and
e) performed 5-10 times better than PP yarns containing the free form of
these antioxidants in ageing test carried out at 140C after treatment in
scouring and dry cleaning bath [90,91,93].
More recently, maleinised hydrocarbon polymers, e.g. PP, ethylenepropylene-diene terpolymer (EPD M), poly( styrene-co-acrylonitrile) (SAN),
acrylonitrile-EPDN-styrene terpolymer, have been reacted with HALS
containing different reactive functions (e.g. hydroxy, amino, hydrazine) to
give bound HALS formulations [94,95] (Scheme 6.15, reaction f). One of
the main advantages of grafted antioxidants in the case of multiphase
polymer systems is the ability selectively to enrich the more oxidisable phase
with antioxidants to achieve maximum stabilisation. Indeed, superior
weathering performance of grafted HALS compositions have been demonstrated especially when the HALS was both bound to the rubber phase and
melt blended into the product [94].
287
~PP
(A) PP functionalisation
H,y
CH 2-CH(CH 3 )
/0,
~=O
CH,;C - C-O-CI+-CH,
/0\
0-CH 2-CH- CH 2
(Glycldyl methacrylate)
a
CH 3
Oy_O
_ '),,0
I
bJ
JV'CH 2CHJV' "'b_ _
= ___-~..
I
(Maleic anhydrrde)
PP
---------H20
0" 0"'0
"-./'- ~ PP
I
fH - ~H2
HOOC
COOH
oII
~ ~ PP
"--_---'C"'H"-,;--=C.:..cH---=C...:.,N"'H"-,I...:.H:..:C-'--1_
(Acrylamlde/HCI)
CH2-?HC=O
I
CI
(8) Grafting reactive antioxidants on functionalised PP
~PP
t-8u
CH 2-CH(CH 3 )
CoO
+ HOOC(CH 2),Q-OH
't-8u
/ \
I Epoxidised PP
0-CH2-CH - CH 2
I
CH2-?H-
'-'-''1''-'''- PP
'-./'--~PP
II
HO-CH2-NH-C-(CH 212-S-C'2H25
CI
Acid chloride- f -PP
~PP+
0,9"'0
Maleinised PP
-5
H
CH2-PH-
CO
CoO
~PP
~~
-L-
CH - CH 2
O=C
OH
C=O
HN
-H,O
.n
o9
.... ~
Scheme 6.15
(b) Radiation-induced grafting on polymer surfaces. One of the main

consequences of high energy radiation (e.g. electron beam or y radiation)
and UV radiation is the formation of free radicals in the irradiated substrate
(ch.8). This has been exploited in initiating grafting pathways of reactive
antioxidants on polymer surfaces. Gamma radiation-induced surface grafting of reactive UV absorbers on oxazolated PP and PE films has been
reported [93].
288

o
CH3
CH3?H
o-~-O + .nrcH26HJV' ~ .nrCH2~JV' + o-~-O
/0:
benzophenone
(uv-sensitiser)
I o-t-O
~
~
'" C=CH 2
&
C H 2 )"O-C-
OH
Reactive AO
OH
~ &-O~
o- I -
o-~ II
o~
c-_
Reactive Antioxidants:
tBu
-Q-OH
; R
=H
n = 1: @(BBA)
1-Bu
8= -QH
R=CH 3 n=0:@(MOTP)
R=H
n = 0:
(AOTP)
Scheme 6.16
UV-induced grafting of reactive monomers has been used to modify

surface properties of polymers, e.g. dyeability and wettability [96-98]. The
same principles have been extended to photograft polymerisable antioxidants, in the presence of photoinitiators, on polymer surfaces. For example,
the acryloyl-hindered phenol AO 39 (DBBA), has been successfully grafted
on polypropylene by exposing thin PP films in a solution (benzene) of the
antioxidant and benzophenone (BP) to UV irradiation [99]. The photosensitiser, BP, abstracts a hydrogen from the polymer chain to form a
polymer radical which, in turn, adds to the reactive antioxidant to form a
PP-grafted antioxidant (Scheme 6.16, reaction a). It was shown that grafting
conditions affect antioxidant performance: increasing BP concentration
enhances the performance of the surface-grafted antioxidant. This was
attributed to the favourable formation of a larger number of shorter grafts
(owing to termination of graft chain length as well as initiation by BP;
Scheme 6.16) rather than few long antioxidant grafts [99]. Similarly,
methacryloyl-containing HALS, AO 40 (MOTP), has been photografted on
the surface of PP films (Scheme 6.16) [100]. Table 6.5 shows the superior
performance offered by grafted HALS to PP film compared with an
ungrafted analogue, which was attributed to a high level of permanency of
grafted antioxidant on UV exposure. It was also demonstrated that the
289
Table 6.5 Comparison of the induction (IP) and embrittIement (ET) times to photooxidation
of polypropylene (PP) films containing AO 40 (MOTP) incorporated either by photografting
or blended and used as a conventional hindered amine light stabiliser (HALS). Blended
poly-MOTP in PP was used for comparison and all HALSs used had the same concentration
PP film sample
Control (no antioxidant)
Blended with po!y-MOTP (macromolecular HALS)
Blended with MOTP (low molecular weight HALS)
Photografted with MOTP
IP (h)
ET (h)
13
53
95
345
50
116
300
889
Source: Mingbo, H. and Xingzhou, H., Polym. Deg. Stat., 18, 321, 1987.
performance of the grafted HALS was much higher than that of a polymerised analogue, poly-MOTP: this was attributed to poor compatibility
and dipersion of macromolecular HALS [100]. Similar trends were also
observed in the performance of the photografted thermal antioxidant DBBA
[99].
( c) Grafting in polymer melts by reactive processing methods. Grafting of
reactive antioxidants on polymer backbones during melt processing (reactive processing) is a very attractive approach to polymer stabilisation.
Polymer grafting reactions can easily be carried out in conventional processing equipments, e.g. extruders and mixers. The utilisation of reactive
processing methods is not specific to stabilisation reactions but is a very
general route to polymer modification which has been used extensively in
recent years to graft functional monomers to polymer melts (ch. 1).
A major problem associated with the use of reactive processing approaches is the occurrence of a number of energetically feasible but
undesirable chemical reactions, e.g. homopolymerisation of the reactive
antioxidant, cross-linking or chain scission of the polymer, which are in
constant competition with the targeted antioxidant grafting reaction. The
extent of contribution of each of these reactions would ultimately determine
the efficiency of the melt grafting reaction. The practical success of this
approach for polymer stabilisation depends, therefore, on choosing chemical
systems and processing parameters which will lead to minimum contribution of all side reactions to give optimum antioxidant grafting levels. An
equally important factor is that the in situ chemical grafting process should
not affect polymer characteristics, e.g. molar mass, morphology and physical
properties, so that stabilisation by this approach would be no different from
the conventional blending of antioxidants with polymers.
Two routes can be identified for the utilisation of reactive processing
methods for grafting antioxidants on polymer melts. This is based on the
way by which the initiation of the grafting reaction occurs: mechanochemically or by added free-radical initiators.
290
REACTIVE MODIFmRS FOR POLYMERS
Reactive processing: mechanochemical initiation. This approach utilises

free radicals induced by the mechanical action of shearing forces during melt
processing (i.e. no added free radical initiators). The mechanochemicallygenerated radicals will initiate the chemical grafting of suitable reactive antioxidants on polymer melts. The polymer reactive function of the antioxidant
molecule which has been exploited successfully in this approach is based
mainly on the thiol (-SH) group. The reason behind this choice was based
on the known reactivity of thiyl radicals (formed from the parent thiolcontaining antioxidant) towards double bonds [101-104]. This method is
therefore particularly suitable for unsaturated polymers but is of no practical use in saturated polymers. Polymer radicals generated mechanochemically during the early part of a melt processing operation are responsible for
the formation of the antioxidant thiyl radicals which would subsequently
lead to grafting of the antioxidant moiety on the polymer backbone during
further processing.
A number of thiol-containing antioxidants with different antioxidant
functions, e.g. hydroxybenzophenone, aromatic amine and hindered phenol,
have been grafted on unsaturated rubbers and rubber-modified thermoplastics, and, to a lesser extent, on saturated hydrocarbon polymers during
polymer processing, e.g. NBR, SBR, NR, EPDM, ABS (Scheme 6.17) [101].
This method was successfully employed to obtain bound antioxidant concentrates (masterbatches) which were subsequently used as conventional
additives, either in the same or in different polymers, during normal melt
processing in both rubber latex (first part of section 6.4.2(a)) and in solid
rubbers. Tables 6.6 and 6.7 show the superior performance and the perma-
Polymer
AS-SA
disulphlde (by-product)
hear
Thlol-contalning AO
mechanochemically
grafted AO
"
JV - CH 2 -CH=CH-CH 2-JV'
_ _---'-A..;cS_ _
.. JV-CH 2-CH-CH-CH 2 -JV'
unsaturated rubber
S-@
Where =-CH2CHN-ONI+D; -CH2-C-O-(CH2h-
e-d~-c-O~ ;
'I
0H 0
(AO@(MADA
(AO@(EBHPT))
Scheme 6.17
I-Bu
CH 2 -v.:OH
~BU
(AO@(BHBM))
291
Table 6.6 Comparison of ultraviolet stability (induction (IP) and embrittlement (ET) time) of
acrylonitrile butadiene styrene (ABS) containing a bound (mechanochemically grafted) combination of antioxidants (at 1% wt:wt of each antioxidant (AO)) with that of commercial
unbound analogues
Antioxidant in ABS
Control (no AO)
BHT (AO 1) + UV531 (AO 23) + Irg PS800 (AO 14)
(low molar mass commercial antioxidants)
g-BHBM (AO 44) + g-EBHPT (AO 43)
(grafted antioxidants, unextracted)
g-BHBM (AO 44) + g-EBHPT (AO 43)
(grafted antioxidants, extracted)
IP (h)
ET (h)
22
25
85
80
380
50
220
Source: Scott, G., ch. 5 in Developments in Polymer Stabilisation, vol. 8 (ed. G. Scott); published
by Applied Science Publishers, London, 1987 with permission.
Table 6.7 Comparison of stress relaxation at 150C of black-filled nitrile rubber (NBR)
vu1canisates containing 2 phr of mechanochemically grafted antioxidant, reduced from 20%
masterbatches prepared either in the same polymer (NBR) or in different polymers (ethylenepropylene-diene terpolymer (EPDM)) or cis-butyl rubber (cis-BR))
Grafted MADA (AO 42) masterbatches
in polymer X
Control (no AO)
X = EPDM (Vistalon 6630)
X = cis-BR (Buna CB 10)
X = NBR (Krynac 800)
Binding (%)
Time to 50% stress

decay (h)
78
75
70
6
22
15
16
Source: Scott, G., ch. 5 in Developments in Polymer Stabilisers, vol. 8 (ed. G. Scott); published
by Applied Science Publishers, London, 1987 with permission.
nence of mechanochemically grafted sulphur-containing antioxidants, e.g.

AO 42, AO 43, AO 44, in ABS and NBR when compared with unbound low
molar mass commercial analogues [101].
The success in achieving high grafting levels of thiol-containing antioxidants to unsaturated polymers by this method, however, depends on a
number of interrelated parameters: the nature and viscosity (at the melt
reaction temperature) of the chosen polymer, processing temperatures,
oxygen concentration, antioxidant concentration, and the extent of competing side reactions involving the antioxidant [101]. Reactive functions other
than thiols, e.g. methacryloyl, have also been used to melt graft antioxidant
moieties (e.g. hydroxybenzophenone) on saturated polymers, e.g. PP, using
mechanochemically generated free radicals, albeit to very low antioxidant
grafting levels ( < 20%) [105,106]. Similarly, thiol-containing antioxidants
grafted by this method onto PP led to much lower grafting levels by
comparison with unsaturated rubbers [107,108] and highlights the limitations in applying this method to saturated polymers.
292
Reactive processing in presence of added initiators. A much broader and

more useful approach, which can be implemented both in unsaturated and
in saturated polymers, is to graft reactive antioxidants on polymer melts in
the presence of a small concentration of a free-radical generator. The majority of the antioxidant grafting reactions have been performed in polyolefins
and their copolymers. The different routes to antioxidant grafting, which will
be discussed below, are classified according to the type of the reactive moiety
of the antioxidant molecule used, and the presence or absence of other
co-monomers in the system.
Monofunctional polymerisable antioxidants. The majority of the reported examples in the literature exploit this route which utilises polymerisable
monofunctional antioxidants (one reactive group per antioxidant molecule).
These antioxidants are grafted on polyolefins, e.g. PP, LDPE, HDPE,
poly(4-methyl-1-ene), in the presence offree-radical initiators, e.g. peroxides,
in a single or twin screw extruder or in an internal mixer [93, 109-115].
However, it has been demonstrated that the efficiency of the chemical
attachment of such antioxidants is relatively low [93, 112, 114]. This is
mainly because of the process of homopolymerisation of the reactive
antioxidant which is a major competing reaction (Scheme 6.18). For
example, reactive processing of two mono-acyloyl antioxidants containing
hindered phenol (DBBA, AO 39) and hindered amine (AOTP, AO 41; see
Scheme 6.16 for structure) antioxidant functions with PP resulted in grafting
efficiency of less than 50% [112,114]. The homopolymerised antioxidant
formed during reactive processing was found to be incompatible with the
host polymer and readily extractable by solvents, hence its poor performance as an antioxidant when used as an additive.
.,.,.;.,... pp
..!l!!..!!!get Reaction
Polymer-grafted antioxidant
CH2=q-R
C=O
I
Non-extractable
Non-volatile
Compatible
Highly effective
I Monofunctional antioxidant I
Main Competing Reaction
AO Homopolymerisatlon
Extractable
Incompatible
Not effective
Scheme 6.18
293
In an attempt to overcome problems of homopolymerisation and low

efficiency of grafting of monomeric polymerisable antioxidants in polyolefins, three alternative reactive processing routes have been developed and
are briefly discussed below.
Monofunctional non-polymerisable antioxidants. In this method nonpolymerisable (e.g. maleate group) monofunctional antioxidants are used in
order to limit the contribution of competing self-reactions of the antioxidant.
Bis-(2,2,6,6-tetramethylpiperidin-4-yl) maleate (BPM, AO 45) and N-(4anilinophenyl) maleimide (APM, AO 46),
o
0
~
u~
II
11-1),
N~O-C-CH=CH-C-O
L/-H
(AO@(APM))
(AO@(BPM
are two examples of such antioxidants. The reaction of BPM and APM on
PP during reactive processing was shown to lead to a high grafting efficiency
(up to 75% for the former and more than 90% in the case of the latter)
which is a result of the non-polymerisable nature of the maleate (maleimide)
function [115-117]. The performance of these antioxidants, especially under
leaching organic solvent conditions, is far more superior than conventional
antioxidants with similar antioxidant functions. Table 6.8 shows the advantages of the grafted aromatic amine AO 46 in PP film samples and in
glass-fibre-reinforced PP thick (3 mm) samples under extractive and thermoxidative conditions [108,115].
Table 6.8 Thermoxidative stability (at 150C) of polypropylene (PP) without and with 30%
glass fibre (GF) in the absence and presence of antioxidants. Soxhlet extraction with
chloroform and acetone
Antioxidant
g-APM (AO 46)

Irg 1010 (AO 3)
Irg 1076 (AO 2)
Control (no AO)
Induction period,
PP films, no GF (h)
Days to craze formation,

PP plaques (1 mm)
with 30% GF
Unextracted
Extracted
Unextracted
Extracted
2250
1200
350
1
2400
5
5
1
55
42
22
2
60
5
3
2
Source: Al-Malaika, S. and Quinn, N., unpublished work.
294
Bifunctional polymerisahle antioxidants. This route involves the utilisation of reactive antioxidants containing two polymerisable polymer reactive
functions in the same antioxidant molecule. Careful choice of the processing
parameters and the type and amount of the free-radical initiator can lead to
very high antioxidant grafting levels [9,116].
For example, melt grafting of concentrates (e.g. concentration of 5%20%) of the di-acrylate-hindered piperidine AO 47, AATP, on PP in the
presence of small concentration of a peroxide initiator has led to almost
100% grafting. This exceptional grafting efficiency of AA TP is in marked
contrast with the much lower grafting levels achieved with the monofunctional HALS analogues, e.g. AOTP (A041), MyATP (A048) and
AMyTP (AO 49) (Table 6.9) [112]:
@
@
@
(AATP)
Bi-functional
(MyATP) ] Mono-functional
(AMyTP)
Examination of the mechanisms involved in the grafting process of such

bifunctional antioxidants has shown that the grafting reaction occurs
through the intermediacy of a cross-linked structure involving the polymer
and the reactive antioxidant leading finally to an antioxidant-grafted polymer product which is completely soluble and has similar characteristics, e.g.
crystallinity and molar mass, to a conventionally stabilised sample
[112,116]. This subject will be described further in the next section.
Monofunctional polymerisahle antioxidants in presence of a coagent.
Generally, the synthetic routes for the production of monofunctional antioxidants (containing a reactive double bond) are easy and straightforward
leading to high yields of the antioxidant. Exploitation of such compounds
Table 6.9 Grafting efficiency of 10% concentrates

(masterbatches) of bifunctional and monofunctional
hindered amine light stabiliser antioxidants in polyproplyene reactions conducted during reactive processing in the presence of 0.005 molar ratio of
dicumyl peroxide (initiator)
Antioxidant
AATP (AO 47)
MyATP (AO 48)
AMyTP (AO 49)
AOTP (AO 41)
Grafting (%)
100
32
14
48
295
in reactive processing methods would, therefore, constitute a broad, versatile, efficient and economically attractive method for the production of a
variety of polymer-grafted antioxidants and antioxidant concentrates.
However, it is clear from the discussion above that such antioxidants suffer
from a major drawback: ease of homopolymer formation and the associated
problems of incompatibility, extractability and inefficiency of the homopolymerised antioxidant.
To address this problem, a novel reactive processing (NRP) route has
been developed which leads to a substantial level of attachment of the same
monofunctional antioxidants (and other additives) in polymers [10]. Generally, grafting efficiency can be improved from as low as 10%-40% to in
excess of 80%-90%. The key to this approach is the in situ co-grafting of a
small amount of di- or poly-functional co-monomer used as a reactive
co-agent. The success of this method lies in achieving a delicate balance
between the composition of the chemical system (antioxidant, co-agent,
free-radical initiator) and the processing conditions (e.g. temperature,
speed).
The use of monomers containing more than one polymerisable group has
been exploited previously for chemical cross-linking reactions on polymers,
i.e. used as cross-linking agents [118,119]. The novelty of this approach,
therefore, lies in the fact that co-grafting of the same polyfunctional agents,
e.g. the trimethylol propane triacrylate, Tris:
o
II
[CH2 = CH -c -0- CH2
+ C - CH CH
2
(Tris)
with monovinyl antioxidants (and other additives) in an extruder or an

internal mixer leads to the production of highly grafted antioxidants in
completely non-cross-linked polymer products without detriment to the
physical characteristics (e.g. crystallinity) of the polymer. Highly grafted and
'permanently fixed' antioxidant concentrates (masterbatches) can also be
produced, and subsequently blended at the required normal (low) concentration, with commercial polymers in the same way as conventional antioxidants.
The underlying chemistry of grafting of such multifunctional systems was
examined both in the polymer and in high temperature model hydrocarbons
using a variety of analytical methods (e.g. extraction and fractionation of the
polymer followed by solid state nuclear magnetic resonance (NMR), Fourier
transform infra red spectroscopy (FTIR), gel and molar mass determination)
and was found to be similar to the chemistry of the grafting of bifunctional
296
l PP + Rv-AO + Tris
E"I--------'
.9
Q)
J5
:l
"d;
c:
Q)
Processing time (min)
~40
Cii
Ol
w:
3
20
100 ~
~
a..
a..
"
50
After 3 min processing

Transient cross-link
22% xylene-insoluble
c:
0
Ol
~
After 10 min processing
Highly-grafted antioxidant
100% xylene-soluble polymer
Figure 6.2 Changes in torque during melt processing of DBBA with PP in the presence of Tris
and a small concentration of peroxide as radical initiator. Amount of gel formed and
antioxidant grafting efficiency is also shown.
antioxidants such as AATP [112,114,116,120]. For example, the grafting

reaction of the monofunctional antioxidant DBBA, AO 39, in the presence
of the coagent (Tris) in PP (carried out in the melt by means of an internal
mixer) is accompanied by an initial rise in torque during the early stages of
melt processing, followed by a gradual decrease on further processing to
reach the level normally observed during compounding using a conventional method of polymer stabilisation (Figure 6.2). The point of maximum
torque is associated with a transient cross-linked antioxidant-polymer
material (about 20% xylene-insoluble) based on a graft antioxidant-Tris
copolymer in a cross-linked PP (Scheme 6.19). Further melt mixing at high
temperatures appears to initiate preferential chain scissions of the graft
copolymer leading to restructuring of the cross-link and further grafting.
This restructuring process continues with further processing to yield ultimately a fully xylene-soluble polymer with highly grafted (90%) antioxidant
moieties (Scheme 6.19).
This co-grafting method (NRP) can be applied to a wide range of
antioxidant functions, e.g. HALS, UV A, hindered phenols, aromatic amines,
leading to outstanding levels of antioxidant grafting. Table 6.10 shows an
example which illustrates the superior performance, especially under extractive conditions, of a highly bound synergistic antioxidant system (hindered
phenols plus UV absorber) produced by this method in PP compared with
a conventional (unbound) commercial antioxidant system.
Stage 1: Formation of graft AO copolymer

with a cross-linked structure
r-------------------------------j
Stage 3: Structure of a cross-linked

graft-AO, gel-free polymer
C-FF
.Ii.
--- --
~".
~ ~\.::::
-'J
*~TI
Termlnar-ti_o_n_0....1_-'-:-:-..z..,.~
. ,
Scheme 6.19
Table 6.10 Comparison of the antioxidant performance (accelerated UV ageing) of synergistic polymer bound mixture of
DBBA and HAEB 1: 1) before and after solvent extraction
(melt grafted in presence of Tris) with conventional antioxidant
mixture based on the same antioxidant functions used at 1: 1
ratio
Antioxidant
(0.4% in PP films)
None
DBBA #
HAEB #
PP-g(DDBA/HAEBh,;,
Irg
1010
(A03) + UV531
(A023)
UV embrittlement time, h
Unextracted
Extracted
75
205
330
70
1160
1130
1750
70
80
70
# unbound, processed alone (no Tris) as a conventional

antioxidant
297
298
6.5
Concluding remarks
Compared with conventional antioxidants, reactive antioxidants which are

capable of becoming chemically attached to polymer backbone have been
shown to be much less readily (or to be not) lost from polymers during
fabrication and in service. There is now a large volume of evidence to
demonstrate the highly improved practical performance (polymer protection) of 'immobilised' antioxidants, especially when polymer products are
subjected to demanding environments, e.g. exposure to high temperatures,
UV light and leaching solvents. This clearly illustrates the fact that the high
mobility of low molar mass antioxidants is not an imperative prerequesite
for achieving stabilisation as had been previously thought, and attachment
of antioxidants on polymers can be industrially exploited to advantage.
The various approaches to the binding of antioxidants discussed in this
chapter have widely different degrees of success and practicality. For
example, the main drawbacks of the two approaches leading to macromolecular antioxidants and antioxidant copolymerisation during polymer
synthesis are associated with complications and the high costs involved in
their synthesis as well as incompatibility in, and migration from, the host
polymer. This often leads to an unfavourable cost-performance scenario
and is reflected in limited commercial developments. Reactive processing
approaches, on the other hand, which utilise the processing machine as a
chemical reactor for the grafting reaction, are more versatile and attractive
alternatives to stabilisation, with high permanence.
Reactive antioxidants grafted on polymer melts behave in a similar way
to low molar mass conventional antioxidants but offer many additional
advantages. The polymer-linked antioxidants (especially those with high
grafting efficiency) do not suffer from the problem of compatibility and are
non-volatile and non-migratory and hence cannot be physically lost from
the polymer even under highly aggressive and extractive environments. Such
antioxidant systems would be much more risk-free and environmentally
friendly than other systems. Another major advantage is that they can be
located in the most oxidatively sensitive part of the polymer system, e.g. in
the rubber phase of rubber-modified polymer products, where stabilisation
is most needed. The ability to produce highly grafted antioxidant concentrates (masterbatches) which can be used in conventional (the same or
different) polymers as 'normal' additives extends the flexibility for using
reactive antioxidants.
The demands for high chemical efficiency, physical retention and safety
of antioxidants in polymers is increasing, especially for the more demanding
applications. The enforcement of more stringent regulations and legislations
for certain applications of stabilised polymers such as in food, toys, medicine
and other health-related areas would ensure a higher level of industrial
interest and development in the use of reactive antioxidants for producing
'permanently' stabilised polymer compositions.
Appendix 6.A
6.A.l
6.A.l.l
Abbreviations
Polymers
Acrylonitrile butadiene styrene
Butyl rubber
Ethylene-propylene-diene terpolymer
Nitrile rubber
Natural rubber
Polyethylene
Polypropylene
Styrene butadiene rubber
ABS
BR
EPDM
HDPE
LDPE
NBR
NR
PE
PP
SBR
6.A.l.2
Miscellaneous
AO
BP
CB-A
CB-D
FRI
FTIR
HALS
MD
NMR
NRP
PD
PD-C
PD-S
Rv-AO
UVA
Antioxidant
Benzophenone
Chain-breaking acceptor antioxidant
Chain-breaking donor antioxidant
Free-radical initiator
Fourier transform infra red spectroscopy
Hindered amine light stabilisers
Metal deactivators
Nuclear magnetic resonance
Novel reactive processing
Peroxide decomposer antioxidant
Catalytic peroxidolytic agents
Stoichiometric peroxide decomposers
Reactive antioxidant
Ultraviolet absorber
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82. Kularatne, K.W.S. and Scott, G. (1978) Europ. Polym. J., 14, 835.
83. Amarapathy, A.M.A. and Scott, G. (1977) J. Rubb. Res. Inst. Sri Lanka, 54, 520.
84. Scott, G. (1977) Plast. Rubb. Processing, p.41.
85. Kirpichev, V.P., Yakubchik, A.I. and Maglysh, G.N. (1970) Rubber Chem. Technol.,43,
1225.
86. Kirpichev, V.P. and Yakubchik, A.I. (1969) Polym. Sci. (USSR), 11,2640.
87. Lorenz, o. and Parks, C.R. (1971) British Patent 1221595.
88. Blatz, P.S. and Maloney, D.E. (1969) US Patent 3441 545.
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90. Nakatsuna, K., Ide, F., Kamata, K. and Hasegawa, A. (1968) Japanese Patent 68.16396.
91. Ide, F., Oseki, T., Itoh, K. and Kimura, K. (1968) Japanese Patent 68.16397.
92. Nakatsuna, K., Ide, F., Itoh, K. et al. (1969) Japanese Patent 69.02718.
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98. Tazuke, S. and Kimura, H. (1978) Makromol. Chem., 179,2603.
99. Evans, B.W. and Scott, G. (1974) Europ. Polym. J., 10, 453.
100. Mingbo, H. and Xingzhou (1987) Polym. Deg. Stab., 18, 321.
102. Ghaemy, M. and Scott, G. (1981) Polym. Deg. and Stab., 3, 253.
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104. Scott, G. and Tavakoli, S.M. (1982) Polym. Deg. and Stab., 4, 279.
105. Sharma, Y.N., Naqvi, M.K., Gawande, P.S. and Bhardwaj, I.S. (1982) J. App. Polym. Sci.,
27,2605.
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Symposium on Macromolecules, Institute of Macromolecular Chemistry, Prague, p. 331.
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p.501.
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1287-96.
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120. Al-Malaika, S. and Suharty, N., unpublished work.
Synthesis of polyolefin graft and block copolymers

by reactive borane reagents and applications
in polyolefin blends and composites
T. C. CHUNG
7.1
Introduction
Polyolefins, especially polyethylene (PE), polypropylene (PP), poly(lbutene) and their copolymers, are used in a wide range of applications as
they incorporate an excellent combination of mechanical, chemical and
electronic properties, processibility, recyc1ability and low cost [1]. Nevertheless, the lack of reactive groups in the polymer structure may limit some of
their end uses, particularly where adhesion, dye ability, paintability, printability or compatibility with other functional polymers is paramount.
Accordingly, the chemical modification of polyolefins has been an area of
increasing interest as a route to higher value products, and various methods
of functionalization [2-5] have been employed to alter their chemical and
physical properties.
It is well-known that the transition metal coordination polymerization,
involving Ziegler-Natta and metallocene catalysts, is the most important
method for preparing linear polyolefins [6], but the direct polymerization
of functional monomers by this method is normally very difficult because of
catalyst poisoning and other reactions [7]. The Lewis acid components (Ti,
V, Zr and AI) of the transition metal catalyst tend to complex with
non-bonded electron pairs on N, 0, and X of functional monomers in
preference to complexation with the n-electrons of double bonds. The net
result is the deactivation of the active polymerization sites by formation of
stable complexes between catalysts and functional groups, thus inhibiting
polymerization. Some attempts by using post-polymerization processes,
modifying the preformed polyolefins, suffer from other problems, such as the
degradation [8] of polymer backbone.
An established technique for improving the interfacial interaction between polymers and other materials is the use of block and graft copolymers
as compatibilizers [9-11]. It is very desirable to prepare polyolefin block
and graft copolymers containing functional polymer segments, such as
poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PV A) and polycaprolactone (peL) polymers, in the side chains or chain end. The functional groups are concentrated in one or few segments, which not only
dramatically increase the interaction between polyolefins and a broad range
of materials containing polar groups, but also preserve most of the physical
Chapman & Hall 1997
304
properties of the polymer, such as crystallinity, melting point and hydrophobicity. Unfortunately, the chemistry to prepare polyolefin graft and block
copolymers is also limited, basically for the same reasons - the inert nature
of polymers and catalyst poison by functional groups. Numerous methods
have been employed in forming graft copolymers with polyolefins. Ionizing
radiation (x-rays, y-rays, and electron beams) in the presence of air or ozone,
and ultraviolet light with accelerators and free-radical initiators, have all
been used to form polymeric peroxides [12,13]. When heated in the
presence of monomers the polymeric peroxides can initiate graft polymerization. Typically, these high-energy reactions lead to side reactions such as
cross-linking and chain cleavage resulting in diminished mechanical properties (see ch. 8 for detailed discussion). In most cases, the structure and
composition of copolymers are difficult to control with the considerable
amounts of ungrafted homopolymers.
It is clear that there is a fundamental need to develop new chemistry
which can address the challenge of preparing functionalized polyolefins with
block and graft structures. In this chapter, recent advances in the preparation of polyolefin block and graft copolymers by borane-containing polymer
intermediates and the consequent radical chain extension reaction are
reviewed. Scheme 7.1 illustrates the general synthetic schemes in the preparation of such graft copolymers. The borane-containing polymers, prepared
both by direct and by post-polymerization processes, are very versatile
intermediates which are not only amenable to interconversion to various
functional groups but also can easily be oxidized to produce 'stable'
polymeric radicals for promoting radical polymerization. In the presence of
R
I
- (CHz - CH). - (CHz - CH), I
(CHZ)4
I
i)
c ii)
n-BuLi H
E~AICI
iii) E-CI
R
I
- (CH z - CH). - (CH2 - CH), I
IV
;~:zl4
~
Scheme 7.1
POLYOLEFIN GRAFf AND BLOCK COPOLYMERS
305
free-radical polymerizable monomers, many block and graft copolymers

have been prepared in the author's laboratory; examples include PE-gPMMA, PP-g-PMMA, PP-g-PVA, PP-g-PCL, EP-g-PMMA, PIB-gPMMA, PP-b-PMMA, PP-b-PVA and PP-b-PS (for abbreviations, see
Appendix 8.A). Most of these copolymers are otherwise very difficult to
prepare by other existing methods. The block and graft copolymers synthesized via borane modification are very effective compatibilizers to improve the compatibility between polyolefin and other materials, including
glass fiber, metals and engineering polymers.
7.2 Synthesis of borane-functionalized olefinic polymers
7.2.1
Borane monomers
The initial idea to use borane monomers [14, 15], w-alkenylboranes

in Ziegler-Natta polymerization was based on three considerations:
CH2
= CH
I
(CH
I
v. .
n~3,
Borane monomer (9BBW)
the stability of borane to transition-metal catalyst - because trialkylborane is a Lewis acid it has a very good chance of coexisting with the
catalyst; in addition, the boron atom is relatively small, so steric protection can be effectively applied if needed;
the solubility of borane monomers and polymers in the hydrocarbon
solvents (hexane and toluene) used in Ziegler-Natta polymerization - a
soluble growing polymer chain is essential to obtain high molecular
weight polymers;
the versatility of borane groups - these can be transformed to a
remarkably fruitful variety of functionalities, as shown by Brown [16].
The easiest way to prepare borane monomers is by monohydroboration
of appropriate dienes. For example, the hydroboration of symmetrical
dienes with dialkylboranes, such as 1,5-hexadiene, with 9-borabicyclo[3,3,I]norane (9-BBN) proceeds in an essentially statistical manner. To
decrease the extent of dihydroboration reaction, a large excess of diene at
ambient temperature is used. After sufficient time to complete the reaction,
the excess diene and solvent is recovered by reducing the pressure, followed
by distillation of the pure borane monomers at a higher temperature.
306
7.2.2
Direct copolymerization of boranes with olefin monomers
To synthesize borane-group-containing polyolefin copolymers via the direct

polymerization route, a solution of lX-olefinjborane containing lX-olefin is
used in the presence of a transition metal catalyst which is either based on
a heterogeneous Ziegler-Natta type, such as TiCI 3 AA/Et 2AICI and
MgCI2/TiCl4/ED-AlEt3 or based on a homogeneous metallocene type, such
as CP2ZrCl2 and Et(IndhZrCl2 with methylalumin oxane (MAO) [17-19].
Scheme 7.2 illustrates the general copolymerization.
These reactions were found to be very effective in producing the boranefunctionalized polyolefins with a broad range of compositions and microstructures. In a typical reaction (Scheme 7.2, reaction a) a toluene solution
of borane reagent (e.g. B-5-hexenyl-9-BBN) and MAO (30 wt% in toluene)
is purged with the olefin monomer (ethylene gas). A toluene solution of the
catalyst (e.g. Et(Ind)2ZrCI2) is then added with the pressure in the stainless
autoclave reactor at 45 p.s.i. during the whole course of the copolymerization. After a predetermined reaction time, the reaction was terminated by
addition of isopropanol (IPA) (dry and with 02)' The copolymer (V in
Scheme 7.2) was isolated by filtration and washed with IPA before drying
under vacuum [17-19].
It is interesting to note that the resulting borane-containing copolymers
synthesized by such a direct copolymerization route, e.g. poly(ethylene-coB-5-hexenyl-9-BBN), poly(propylene-co-B-5-hexenyl-9-BBN) and poly(1butene-co-B-5-hexenyl-9-BBN) (9-BBN: 9-borabicyclonornane) were found
to contain low concentrations of borane monomers 10 mol%), and are
R
I
CHz
= CH
I
NaO~/H202
Transition-metal
catalyst
(CHz).
I
(CHZ)4
- (CHz - CH) - (C'" - CH)
'"2
'
(CHz)4
CHz = CH
I
- (CHz - CH). - (CH z - CH)y -
VI
Nal/Chlo~
T-hydrate
CH 3COONa
R
I
- (CH z - CH). - (CHz - ~H)y (CHZ)4

I
VII
R = H. CH 3 C2Hs CeH13
Transition-metal catalyst
=TiCI~EtAICI2' Cp~rCl~MAO and C2H4[lndI2ZrCl~AO

Scheme 7.2
POLYOLEFIN GRAFT AND BLOCK COPOLYMERS
307
insoluble in common organic solvents at room temperature, but soluble at

higher temperatures. However, the copolymers of poly(1-octene-co-B-5hexenyl-9-BBN) (PO-B) in all compositions were found to be soluble in
most hydrocarbon solvents at room temperature. The borane concentration
can be measured by solution 11 B nuclear magnetic resonance (NMR)
spectroscopy. By using a known amount of triethylborate (chemical shift at
19 ppm) as a reference, and comparing the integrated peak areas, the borane
content in the copolymer can be determined quantitatively.
7.2.3
Post-copolymerization of borane reagents with preformed polymers:

hydroboration reaction
Alternatively, borane-containing polyolefins were prepared by hydroboration of unsaturated polyolefins, such as poly(propylene-co-1,4-hexadiene)
[20], poly(ethylene-co-propylene-co-1,4-hexadiene) (EP rubber) [21] and
poly(isobutylene-co-isoprene) (butyl rubber) [22]. The internal double bond
of the unsaturated polymer was reacted with dialkylborane, such as 9-BBN.
The reaction is very effective in both homogeneous and heterogeneous
solutions under mild reaction conditions. The concentration of borane
groups in the polyolefin was controlled both by the amount of 9-BBN used
in the hydroboration reaction and by the concentration of unsaturation in
the copolymers. In a typical hydroboration reaction, a tetrahydrofuran
(THF) solution of the borane reagent (e.g. 9-BBN) was added to a toluene
suspension of the unsaturated polymer (e.g. inhibitor-free poly(propyleneco-1,4-hexadiene) containing 1.7% l,4-hexadiene units). The suspension was
heated to 65C in a flask equipped with a condenser. After stirring for 5 h
the polymer was precipitated into 150 ml dry, degassed isopropanol and
isolated by filtration (in dry box). The borane-containing polymer was then
placed in a suspension of THF for further oxidation reactions.
It is interesting to note that in the case of polyolefins (e.g. PP) copolymers, direct copolymerization usually produces a primary borane group:
CH 3
I
- (CH2 - CH)K
CH2 - CH)y I
CH2
I
CH 2
I
CH 2
I
CH2
I
J>v
whereas post-polymerization results in secondary borane groups:
308
CH 3
I
- (CH 2
CH)x
CH 2
CH)y I
CH2
I
CH2
~-C-B<t
CH 3
7.3 Utilization of borane-functionalized polymers in graft and block

copolymer formation
7.3.1
Autoxidation of alkyl-9-BBN
The selective oxidation of borane moiety in the borane-functionalized

polymers plays a major role in the subsequent grafting reactions with other
polymers. In general, the autoxidation of the borane group in alkyl-9-BBN
takes place at room temperature. Owing to the unfavorable ring strain
which increases by inserting oxygen into the C-B bonds in the bicyclic ring
(this destroys the stable double-chair-form structure), the oxidation reaction
preferentially takes place at C-B bond in the linear alkyl group to produce
peroxyborane (C-O-O-B), as shown in Scheme 7.3, reaction a.
The oxidative selectivity of the linear alkyl group was usually between
90%- 70% [23] at ambient temperature, which was very dependent on the
oxygen administration. The best results were realized when the O 2 was
introduced slowly so that the amount of oxygen was very much less than the
amount of boron at any time. The peroxyborane (Scheme 7.3) behaves very
- - - _c ___ ..
R _ CH2 0
(allyl radical)
R-CH2 -Oo
(allioxyl radical)
00-8
(borinate radical)
Scheme 7.3
00 - 0 - 8
(peroxyborane radical)
309
differently from regular benzoyl peroxides and consequently decomposes by

itself even at ambient temperature. The decomposition reaction follows the
homolytical cleavage of peroxide to generate an alkoxyl radical (C-O)
and a borinate radical (B-O) (Scheme 7.3) which is relatively stable owing
to the back-donating of electron density to the empty p-orbital of boron:
(Borinate)
It is interesting to compare borinate with nitroxide radicals [24], such as

2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical. These possess the
opposite stabilization mechanism - electron donation of the lone-pair
electrons in p-orbital of nitrogen to the free radical:
(Nitroxide)
An alternative reaction could involve an asymmetric cleavage of peroxide to

produce alkyl radical (C) and peroxyborane radical (Scheme 7.3); both are
very unstable. This unfavorable reaction may only occur at high temperatures.
The in situ formation of a stable borinate radical (Scheme 7.3) is very
interesting; it not only promotes the selective peroxy cleavage at ambient
temperature but also forms the 'dormant' radical species which are essential
for 'stable' radical polymerization [25]. With the coexistence of radical
polymerizable monomers, such as methacrylates, styrene, acrylamide, vinyl
acetate and acrylonitrile, polymers with relatively well-defined structures
can be obtained at room temperature.
7.3.2
Free-radical reactions for graq1ft formation
The borane-functionalized polyolefin (Scheme 7.1, reaction a) acts as a

polymeric free-radical source under certain oxidation conditions to initiate
graft-from polymerization. The free-radical polymerized graft polymer segments are therefore chemically bonded to the side chains of the poly olefin.
Some interesting polymers [26-28], such as PE-g-PVA, PP-g-PMMA,
310
PP-g-PMMA, PP-g-PVA, EP-g-PMMA and butyl-g-PMMA (for abbreviations, see Appendix 7.A), have been synthesized with controllable
compositions and molecular microstructures. Most of them would be
otherwise very difficult to prepare by other existing methods. In a typical
example for the production of graft copolymers, e.g. PP-g-PMMA, a
reaction between the borane-containing copolymer (with 0.5 mol% of
borane groups) and dry uninhibited monomer, e.g. MMA, is initiated by
injecting dry O 2 (about 0.5 ml of oxygen was added hourly). After 12 h of
stirring at room temperature the reaction was terminated by removal of
MMA and oxygen under vacuum. The graft copolymer (white solid) was
then refluxed in methanol before isolating by filtration and drying. The
polymer was fractionated by acetone extraction in a Soxhlet apparatus
for 24 h. Both insoluble and soluble fractions were isolated by vacuum
removal of solvent and the fractions were analyzed for homopolymer
content [29].
Table 7.1 summarizes the experimental results of PP-g-PMMA
copolymers [29] which are obtained from both polymers, from runs A1-AS
and from runs B1-B2, respectively, containing primary and secondary
alkyl-9-BBN, respectively. The comparison among runs (A1-A4) shows the
sensitivity of the graft efficiency to oxygen addition. Even though the final
stoichiometry of oxygen: boron should be 1: 1, the best results in this
heterogeneous reaction system are realized when the O 2 is introduced slowly
so that the amount of oxygen compared with boron is very small at any
time. Excess 02 is not only a poison for free-radical copolymerization but
also leads to over oxidation, to boronates and borates, which are poor
free-radical initiators at room temperature. The polarity of solution also
affects the graft reaction. THF is a very good solvent in this reaction. A
non-polar solvent, such as benzene, slows down the graft-from reaction,
which may be a result of the solubility of 02 in the solvent. In run AS the
oxygen was introduced by diffusion of air through the rubber septum which
Table 7.1 A summary of PP-g-PMMA copolymers. For abbreviations, see Appendix 7.A
Run
Al
A2
A3
A4
A5
Bl
B2
Borane
in PP
(mol%)
O2
(mljh)
Monomer/
solvent
Reaction
time (h)
MMAin
polymer
(mol%)
0.5
0.5
0.5
0.5
0.5
1.7
1.7
1.5/12
3.0/1
1.4/3
6 (at once)
Diffusion
Diffusion
1/12
MMA (neat)
MMA (neat
MMA/THF
MMA (neat)
MMA/THF
MMA (neat)
MMA/benzene
48
2
12
48
48
24
12
66
6
52
1.5
12
18
13
311

Table 7.2 A summary of EP-g-PMMA copolymers. For abbreviations, see Appendix 7.A
Run"
9-BBNj
olefin b
in EPDM
MMA
(g)
Hexane
solvent (g)
Acetone
solvent (g)
Insoluble"
fraction (g)
PMMA
in graft
(mol%)
C1
C2
C3
C4d
C5
D1
D2
D3
2:1
2:1
1:1
1: 1
0.5: 1
2:1
2: 1
1: 1
14
7
7
7
7
14
7
7
0.038
0.041
0.112
0.060
0.119
0.138
0.083
0.092
0.473
0.142
0.243
0.487
0.246
1.194
0.118
0.216
2.001
1.229
0.992
0.993
0.889
1.259
1.016
0.957
52
35
28
32
28
51
28
25
"Runs C1-C5 were started from poly(ethylene-co-propylene-co-1,4-hexadiene) (Du Pont

EPDM) and runs D1-D3 were started from poly(ethylene-co-propylene-co-5-ethylidene-2norbomene) (Exxon EPDM). Both EPDM copolymers contain about 1.5 mol% of diene units.
bOlefin units in EPDM copolymer.
"Soluble in THF.
dThe graft reactions were carried out at 55C.
was tightly installed on the top of the reactor. Insufficient O 2 in this process
leads to a low percentage of PMMA graft formation.
Similar graft-from reactions have been extended to various polyolefin
backbones. Satisfactory results were obtained in both homogeneous (EP
and butyl rubber cases) and heterogeneous (PE, PP and PB cases) reaction
conditions. In one homogeneous case, the commercial ethylene-propylenediene terpolymer (EPDM) rubbers, such as poly(ethylene-co-propyleneco-1,4-hexadiene) and poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene), were used to prepare EP graft copolymers [21]. Table 7.2
summarizes some experimental results.
The hydroborated EPDM rubbers were usually mixed with methyl
methacrylate in THF solution. Upon exposing to oxygen, the graft-from
reaction took place at room temperature (Scheme 7.1, reaction a). The total
oxygen used was only 50% (compared with borane groups) to ensure the
selective oxidation reaction as discussed before. The graft-from reaction was
terminated by precipitating the resulting polymer in MeOH. Some unreacted B--C bonds were further oxidized by NaOH/H 2 0 2 (Scheme 7.2,
reaction b). The product, isolated by filtration and washed with MeOH, was
then extracted with hexane and acetone, respectively, for 24 h. The hexane
soluble fraction is usually a very small quantity (Table 7.2) and was shown
to be almost identical to pure EPDM rubber by 1 H NMR. On the other
hand, the acetone-soluble fraction contains both PMMA and EP with a
significantly high PMMA concentration. These results imply that the
acetone-soluble fraction contains either the EP-g-PMMA copolymer with a
high concentration of PMMA or a mixture of graft copolymer and some
312
..",.Jv.... ..
(e)
(b)
(a)
8:5 8:0
i5 io
)f.~9
6:5 6:0 5.5 5.0 4:5 4:0 3:5 3:0 2:5

ppm
Figure 7.1 The IH NMR spectra of (a) EP rubber, poly(ethylene-co-propylene-co-l,4-hexadiene), and EP-g-PMMA graft copolymers, containing (b) 28 mol% (run C3, Table 7.2) and
(c) 52 mol% (run Cl, Table 7.2) of PMMA. For abbreviations, see Appendix 7.A.
313
PMMA homopolymer. The major portion is insoluble in both hexane and

acetone but soluble in THF and is EP-g-PMMA copolymer with a PMMA
concentration less than 60 mol%.
The overall graft efficiencies by this method are very high, with less than
10% unreacted EPDM rubber remaining. The graft copolymers exist mainly
in the insoluble fraction, and some in the acetone-soluble fraction. Comparing run C3 with run C4 (Table 7.2), there is no significant difference in the
graft-from reaction by using moderately higher temperature (55C). The
temperature insensitivity implies the ready decomposition of C-G-O-B
at room temperature, which is very different from traditional thermal
initiators, such as benzoyl peroxide, which are usually used above 65C.
Figure 7.1 compares the 1H NMR spectra of the resulting EP-g-PMMA
copolymers and the starting EPDM rubber, poly(ethylene-co-propylene-col,4-hexadiene). The chemical shift at 3.6 ppm in Figures 7.1(b) and 7.1(c)
corresponds to methyl groups (CH30) in PMMA. The chemical shifts
between 2.1 ppm and 0.7 ppm include all protons in EP and five protons in
the methyl group located on the PMMA backbone. The copolymer composition was calcalated by the ratio of the two integrated intensities at 3.6 ppm
and 2.1-0.7 ppm and the number of protons both chemical shifts represent.
Figures 7.1(b) and 7.1(c) indicate the presence of 28 mol% and 52 mol% of
PMMA in EP-g-PMMA copolymers, respectively.
Figure 7.2 compares the differential scanning calorimeter (DSC) curves
between EP-g-PMMA copolymer and starting EPDM rubber and PMMA
-0.65
(a)
-0.90
Cl
(b)
~ -1.15
1ii
CD
::I:
-1.40
(c)
-1.65+--~--.---~-'-------'-~---r-~-~-I
-100
-50
50
100
150
Temperature (OC)
Figure 7.2 DSC curves: comparison between (a) EP rubber and (b) EP-g-PMMA copolymers
containing 52 mol% (run Cl, Table 7.2) of PMMA and (c) PMMA homopolymer. For
abbreviations, see Appendix 7.A.
314
homopolymer (Mw' 80.000 g/mol; Mw/Mn' 2.8) which was prepared by a

control reaction using B-2-hexyl-9-BBN/0 2 initiator under similar freeradical polymerization conditions. Two glass transition temperatures (~),
-47 DC and + 130DC, exist in EP rubber-g-PMMA copolymer [21] with
50: 50 composition.
The uneven baselines between ODC to lOODC in both graft copolymer and
EPDM rubber are reproducible in all samples. They may be the result of
some small crystalline domains existing in EPDM rubber, which are the
result of the inhomogeneous distribution of ethylene and propylene monomers in the polymer backbone. Basically, two values of ~ are very close to
those of the two corresponding homopolymers. This result indicates clear
phase separation between the EP backbone and the PMMA side chains.
The copolymer backbone must have enough consecutive sequences of EP
backbone units to form separate domains. The side chain must be of a high
molecular weight polymer with a microstructure similar to PMMA
homopolymer. The clear phase separation with hard (polar) and soft
(non-polar) domains is a very interesting molecular structure. In fact, some
of the graft copolymers behave like thermoplastic elastomers.
7.3.3
Ring-opening reactions for graft formation
Borane-containing polymers (I of Scheme 7.1) can also be used to synthesize

polyolefin graft copolymers containing polyolefin backbone and condensation polymer graft segments (IV) on the side chains. The chemistry is based
on the anionic ring-opening reaction with the appropriate functional groups
(e.g. OH group) in polyolefin (II). The latter is obtained by interconversion
of borane-containing polymer (I). One example is PP-g-PCL [30], which
was obtained from hydroxylated PP and ring-opening reaction of e-caprolactone (e-CL). In a typical example of such synthesis a fine powder form of
hydroxylated PP (Mv = 183 000 g/mol, containing 1.4mol% hexenol units)
is metallated with excess n-butyllithium to form the lithium alkoxide. A
toluene slurry of the powdery solid was then reacted with a 3-molar
equivalent of diethylaluminum chloride for 12 h to form the PP-aluminum
alkoxide. The monomer, e.g. caprolactone, was then added to a slurry of the
PP-OAlEt2 in toluene. The reaction was terminated (after 24 h, room
temperature) by the addition of MeOH, and the polymer was isolated by
precipitating into acidified MeOH. The polymer mass was extracted with
hot acetone in a Soxhelet apparatus under N2 for 48 h to remove any e-CL
homopolymer [30]. Results from such reactions to produce PP-g-PCL
copolymers are summarized in Table 7.3.
Runs El through E4 all started with the same PP-OH copolymer (II of
Scheme 7.1) containing approximately 1.4% hexenol monomer units. The
weight percent PCL in the resulting graft copolymer increased linearly with
increasing e-CL in the feed. The relatively long reaction time can be
315
Table 7.3 A summary of PP-g-PCL copolymers and reaction conditions. For abbreviations,
see Appendix 7.A
Reaction conditions
Products
Run
PP-OAlEt 2
(g)
e-CL
(g)
Reaction
time (h)
Acetone
soluble (g)
Acetone
insoluble (g)
e-CL in
graft" (wt%)
El
E2
E3
E4
E5 b
2
2
2
2
2
2.169
4.299
8.243
4.571
6.525
24
24
24
60
24
0.366
0.430
2.581
2.102
1.387
2.252
2.763
3.922
4.120
3.603
16.8
32.9
56.8
59.5
45.4
"Determined by lH NMR.
bFrom unsaturated PP-hexadiene.
explained by the heterogeneous reaction conditions. The diffusion of e-CL

into the PP matrix would be the rate-limiting step for the reaction. In fact,
runs E2 and E4 differ in reaction time - 24 hand 60 h respectively - but
resulted in copolymers with 33 wt% and 59 wt% PCL, respectively. The
amount of homo-PCL produced, i.e. the acetone-soluble fraction, also
increased with e-CL feed. Any residual aluminum alkyl not covalently
bound to the polymer could easily initiate the homopolymerization of e-CL.
Excess aluminum alkyl associated with the bound AI-O may not be
completely washed out by the nonpolar solvents. Run E5 started with
commercial-grade propylene and 1,4-hexadiene copolymer containing approximately 1.6% unsaturated monomer units. The polymer was hydroborated with 9-BBN and oxidized to give functionalized PP with the
secondary alcohols on either the 4 or 5 position of the hexadiene branch.
The secondary alcohol can also be converted to the secondary aluminum
alkoxide which is approved to be an active initiator in the graft-from
reaction of e-CL.
Figure 7.3 shows the IH NMR spectra of three PP-g-PCL copolymers in
dlo-a-xylene at 120e. The chemical shifts at 4.1 ppm and 2.3 ppm
correspond to methylene groups (CH 2-O) and (CH 2 -C=O), respectively,
in PCL. The chemical shifts at 1.9 ppm, 1.6 ppm and 1.1 ppm correspond,
respectively, to methine, methylene and methyl groups in polypropylene.
The quantitative analysis of copolymer composition was calculated by the
ratio of two integrated intensities between () = 4.1 ppm and () = 2.0 ppm to
1.0 ppm and the number of protons both chemical shifts represent. Figures
7.3(a)-(c) indicate 17wt%, 33wt% and 57wt% of PCL, respectively, in
PP-g-PCL copolymers. High concentrations of PCL can be incorporated in
the side chains of polypropylene despite the heterogeneous reaction conditions.
Figure 7.4(a) shows the DSC curves of three PP-g-PCL copolymers
containing 17 wt%, 33 wt%, and 57 wt% of PCL. All samples were given the
316
UiJ
,)
(e)
(b)
JJJ
N------,-
~t'ft.o
l --_......_-
(a)
5'.5
5.0
4.5
4.0
3.5
3.0
2.5
ppm
2.0
1.5
1.0
0.5
,
0.0
Figure 7.3 The IHNMR spectra of PP-g-PCL graft copolymers. containing (a) 17wt%,
(b) 33 wt% and (c) 57 wt% of PCL. For abbreviations, see Appendix 7.A.
317
-0.6
-0.8
-1.0
~
C)
-1.2
~ -1.4
~ -1.6
iii
CJ) -1.8
;;::::
-2.0
-2.2
-2.4
-2.6
50
100
Temperature (ec)
150
75.0
100.0
125.0
Temperature (ec)
150.0
(a)
200
40.0
35.0
'
30.0
.. 25.0
(i)
~ 20.0
;;::::
iii
15.0
CJ)
(iii)
10.0
5.0
0.0
(b)
50.0
175.0
Figure 7.4 DSC curve comparisons (a) among three PP-g-PCL copolymers, containing
(i) 17 wt% (run E1, Table 7.3), (ii) 33 wt% (run E2, Table 7.3) and (iii) 57 wt% (run E3,
Table 7.3) of PCL, and (b) between (i) i-PP and (ii) PP-g-PMMA copolymers containing
5 mol% of PMMA and (iii) 66mol% of PMMA. For abbreviations, see Appendix 7.A.
same thermal treatment by heating in a Mettler hot stage at 180a C for 15

minutes before cooling quiescently.
Two distinctive crystalline structures are formed in all graft copolymers.
It is clear that the high melting peak at about 150a C is due to the
polypropylene segments in the backbone and the low temperature peak at
about 50 a C-60 a c is due to the PCL segments in the side chains. Both
phases are clearly separated. In fact, a slight increase in the melting point
(Tm) and heat of fusion (.1.H) of PCL with the increase of the PCL content
318
may be due to the increases in its molecular weight and crystallinity. Figure
7.4(b) compares DSC traces of pure i-PP (curve (i), AH = 62 Jig), PP-gPMMA with 5% MMA (curve (ii), AH = 52 Jig), and PP-g-PMMA with
67% MMA (curve (iii), AH = 22 Jig). The melting point is almost unchanged despite the high percentage of PMMA in the copolymer. The polypropylene segments in both graft copolymers preserve their crystallinity, the
heat of fusion per gram of PP is almost the same in the three samples. The
branch density in the graft copolymer must be relatively low, and polypropylene segments have enough consecutive sequences to form crystalline
domains as pure PP.
7.3.4
Chain extension via diblock polymer formation
Further utilization of the borane functionalized polyolefins is in the synthesis of polypropylene diblock copolymers. The overall reaction (Scheme
7.4) includes three steps: the preparation of polypropylene with chain end
un saturation (VIII), the hydroboration by borane reagent (reaction a), and
oxidation and subsequent free-radical chain extension (reaction band
structure X). The chemistry involves only one borane group per polymer
chain, which provides an ultimate test for examining the efficiency of borane
reagent in the chain extension process. In addition, the molecular structure
of diblock copolymer will offer valuable information about the reaction
mechanism of this new radical polymerization.
Polypropylene with chain end unsaturation was prepared by using a
homogeneous Et(IndhZrCI2/MAO catalyst. Both internal and external
double bonds were observed, which are formed as a result of the p-proton
elimination from 1,2- and 2,l-inserted propagating chain ends, respectively.
The higher the reaction temperature the higher the olefin concentration and
the lower the molecular weight. This temperature-molecular weight relationship was confirmed by 1H NMR and gel permeation chromatography
(GPC) results. It is very interesting to note that the ratio of external to
internal olefins is very dependent on the reaction temperature. At an
~ pp"",,-
fH
=CHz
H-B<;.
a
VIII
""""""" PP"""- CH - CHz - 0 """"""" PMMA """X
Scheme 7.4
319
elevated temperature (such as 80C), the external double bond is the major
product.
The chain end unsaturated polypropylene (Scheme 7.4, structure VIII)
was used as the starting material for the preparation of diblock copolymers.
The hydroboration reactions were carried out under heterogeneous reaction
conditions by suspending the powder form of polypropylene in THF.
Slightly excess 9-BBN was used to ensure complete reaction. Usually, the
reaction mixture is stirred at 55C for 5 h before removing the polymer
powder from solution by filtration. To examine the efficiency of reaction,
some of the hydroborated polymer (Scheme 7.4, structure IX) was oxidized
to hydroxylated polymer by using NaOHjHzO z reagents at 40C for 6 h.
The olefinic chemical shifts between 4.7 ppm and 5.6 ppm disappear to the
limit of NMR sensitivity. Apparently, both hydroboration and oxidation
reactions were not inhibited by the insolubility of polypropylene. On the
other hand, most of 9-BBN terminated polypropylene (PP-9-BBN) (structure IX) was subjected to the oxidation reaction by oxygen in the presence of
free-radical polymerizable monomers, such as methyl methacrylate (MMA),
ethyl methacrylate (EMA), vinyl acrylate (V A), butyl acrylate (BA) and
styrene (Scheme 7.4, reaction b). The in situ formation of polymeric radical at
the polymer chain end initiates radical polymerization. The radical polymerization was terminated by precipitating the polymer mixture in MeOH. The
product, isolated by filtration and washed with MeOH, was then subjected
to fractionalization. In the PP-b-PMMA case, the sample was extracted with
refluxing acetone and heptane, respectively, in a Soxhlet apparatus for 24 h.
Figure 7.5 compares the 1H NMR spectra of three fractions.
The heptane-soluble fraction shown in Figure 7.5(a) is basically pure PP,
which has three multiple peaks around 1.09 ppm, 1.39 ppm and 1.75 ppm,
corresponding to CH 3 , CH z and CH protons, respectively. On the other
hand, the acetone-soluble fraction shown in Figure 7.5(b) contains only
PMMA. The peak at 3.58 ppm corresponds to methoxyl groups (CH 3 0) in
PMMA. The major fraction (> 60%), insoluble in heptane and acetone but
soluble in toluene at elevated temperatures, is PP-b-PMMA diblock
copolymer. The IH NMR spectrum of PP-b-PMMA in Figure 7.5(c) shows
45 mol% of PMMA. Figure 7.6 compares the GPC curves between the
starting PP homopolymer and the resulting PP-b-PMMA diblock
copolymer.
The molecular weight increases more than twofold, from Mn = 13000 gj
mol to M n = 29000 gjmol and the molecular weight distribution increases
slightly, from 1.48 to 1.69. The GPC results are consistent with the 1 H NMR
measurement which show about 1: 1 mole ratio between PP and PMMA in
the block copolymer. During the propagation step, the resting state of
growing chain end forming a week bond with the borinate radical (Scheme
7.3) may minimize the undesirable chain transfer and termination reactions,
namely, radical coupling and disproportionation reactions between two
320
(a)
(b)
(c)
7.5
7.0
6.5
6.0
5.5
5:0
4:5
4.0
ppm
3:5
3:0
i5
2:0
1:5
1:0
0.5
Figure 7.S IH NMR spectra of three fractionalization products: (a) heptane-soluble fraction,
(b) acetone-soluble fraction and (c) both-solvent-insoluble fraction. * = d-xylene.
growing chain ends. In fact, these results are consistent with the control
reactions using alkyl-9-BBN as the radical initiator, which showed 'stable'
radical polymerization of MMA under similar reaction conditions.
The detail experimental conditions and results are summarized in Table
7.4. All reactions were started from the same PP sample with Mn =
321
0.642~
0.6400.6380.636.l!l
::>
(5
0.634-
0.6320.630-
0.6250.620.. 36:00' 38:00' 40:00' 42:00' :00' 46:00 -48:00' 50:00' 52:00' 54:00' 56:00' 58:0'0' 60:00' .
Minutes
Figure 7.6 GPC curves of (a) PP and (b) the corresponding PP-b-PMMA copolymer. For
abbreviations, see Appendix 7.A.
13 000 g/mol and Mw/Mn = 1.48. The reactions were carried out at ambient
temperature for 16 h.
The overall yield of diblock copolymer is between 80%-60%, which is
very encouraging considering there is only one borane initiator in each
polymer chain and some polymer chains without any borane group (up to
20%). All three reactions involved - hydroboration, oxidation and radical
polymerization - must be very effective despite the heterogeneous conditions. The mol% of MMA in the copolymer can be controlled by monomer concentration and reaction time. Slightly better results, with fewer
Table 7.4 A summary of PP-b-PMMA diblock copolymers. For abbreviations, see Appendix
7.A
Fractionalization products
Reaction conditions
PP
(g)
0.5
0.5
13.3
MMA
(g)
Solvent/
amount (ml)
Oxygen
(ml)
Acetone
(g)
Heptane
(g)
Insoluble
(g)
5
5
80
THF/5
benzene/5
THF/80
0.44
0.44
10.8
0.25
0.16
0.18
0.08
0.72
0.90
MMA
in diblock
copolymer
(mol%)
33
28
45
322
(c)
*
*
(b)
**
(a)
i5
7.0
6.5 6:0
5.5 5.0
4:5 4':0
3.5
ppm
3.0 2:5
2.0
1 :5 " 1 :0
0:5
Figure 7.7 IHNMR spectra of (a) PP-b-PEMA with 27mol% of EMA (* = d-toluene),
(b) PP-b-PBA with 34 mol% of BA (* = d-toluene) and (c) PP-b-PS with 11 mol% of styrene
(* = d-benzene). For abbreviations, see Appendix 7.A.
323
homopolymers, are obtained by using benzene solvent perhaps because of

the slow diffusion of oxygen in reaction media, which offers better selectivity
in the oxidation of PP-9-BBN.
The same radical chain extension was also applied to other free-radical
polymerizable monomers, including ethyl methacrylate (EMA), vinyl acrylate (VAc), butyl acrylate (BA) and styrene. The products were subjected to
the same vigorous fractionalization processes. Figure 7.7 shows the
IH NMR spectra of PP-b-PEMA, PP-b-PBA and PP-b-PS copolymers,
containing 27 mol%, 34 mol% and 11 mol% of radical polymerized
monomers, respectively.
All reactions were run under similar reaction conditions, ambient temperature and THF solvent. The significantly lower incorporation of styrene
monomers may be associated with the acidic nature of borane initiator. The
acid-base interactions between borane and monomers containing basic
oxygen, such as MMA, EM A, VAc and BA, may provide a 'cage' effect, with
surrounding monomers next to the catalyst, which leads to effective initiation
and polymerization. Styrene monomers without any specific interaction with
borane may have more difficulty in approaching the reaction center,
especially in the polar solvent (THF) which forms a borane/THF complex.
7.4 The use of graft and block copolymers prepared via boranefunctionalized polymer intermediates in the compatibilization
of polymer blends
The polyolefin block and graft copolymers synthesized via polyolefinfunctionalized borane intermediates are very effective compatibilizers for
improving interactions between the corresponding polyolefins and other
materials, including functional polymers, engineering plastics and substrates.
Three polypropylene blends will be used to demonstrate the results.
7.4.1
PP/PMMA blends
Optical microscopy was used to evaluate the ability of the graft copolymers
to act as phase compatibilizers [29] for blends of PP and PMMA
homo polymers (Figure 7.8). Polymer solutions were prepared in BHT
inhibited a-xylene at 135e. The polymer films were then solution cast onto
glass microscope slides. After evaporating the xylene under N 2 purge, the
films were covered with a slide cover. The polymer films were then melted
in a hot stage at 180C for 15 min. The samples were then allowed to cool
quiescently in the hot stage to room temperature for 20 min. The magnification on the microscope was 100 times. The blend shown in Figure 7.8(a)
is a 70: 30 wt% mixture of PP and PMMA homopolymers that were
blended in solution. Two distinct phases are visible, the crystalline PP phase
324
(a)
(b)
Figure 7.8 Optical micrographs of polymer blends: (a) two-homopolymer blend with 70 : 30
i-PP/PMMA and (b) two homopolymers with PP-g-PMMA containing 30% MMA and
70 : 10: 30 i-PP/PP-g-PMMA/ PMMA. For abbreviations, see Appendix 7.A.
325
and an amorphous PMMA phase. Within the PP domain, the spherulite

size varies greatly with a few extremely large crystallites and predominantly
small spherulites. The blend shown in Figure 7.8(b) is a sample of that
shown in Figure 7.8(a) to which 10 wt% of PP-g-PMMA has been added in
solution. The added graft copolymer was also 30 wt% PMMA so as not to
change the overall composition. The graft copolymer, behaving as a polymeric emulsifier, increases the interfacial interaction between the PP amorphous region and the PMMA to reduce the domain sizes. The most
noticeable change in the micrographs is the disappearance of the visibly
distinct PMMA domains. The large phase-separated PMMA domains are
now dispersed into the interspherulite regions and cannot be resolved by the
optical microscope. The mode of nucleation within the polypropylene
crystalline phase has changed, as evidenced by the now relatively homogeneous spherulite size.
7.4.2 PP/PCL blends
A scanning electron microscope (SEM) operating with secondary electron
imaging was used to observe the surface topography of cold fractured film
edges. The polymers were blended in chlorobenzene and precipitated into
hexane. The samples were dried under vacuum before being melt pressed to
form the films. The films were cryrofractured in liquid N2 to obtain an
undistorted view representative of the bulk material. Figure 7.9 shows the
micrographs [30] of 70: 30 PP/PCL homopolymer blend and 70: 10: 30
PP/PP-g-PCL/PCL copolymer blend. In the homopolymer blend, the
polymers are grossly phase separated, as can be seen by the minor
component PCL which exhibits non-uniform, poorly dispersed domains and
voids at the fracture surface as shown in Figure 7.9(a). This 'ball and socket'
topography is indicative of poor interfacial adhesion between the PP and
PCL domains and represents PCL domains that are pulled out of the PP
matrix. Such pull out indicates that no stress transfer takes place between
phases during fracture. The compatibilized blend shown in Figure 7.9(b) no
longer displays the distinct PCL globules. Rather, a flat mesa-like fracture
surface is observed similar to that seen on a fractured PP or PP-g-PCL
surface. Both PP and PCL phases are mechanically tied and the interface is
bridged by the graft copolymer extending into both phases tying them by a
covalent bond.
7.4.3 PP/PC blends
It would be extremely advantageous if inexpensive, commodity PP could be
effectively compatibilized in blends with the more costly engineering resin

polycarbonate. Bisphenol-A polycarbonate (PC) has excellent high- and
low-temperature physical properties even up to 140C. Use of PP as the
(a)
(b)
Figure 7.9 SEM micrographs of (a) two-homopolymer blend with 70 : 30 i-PP/PCL and
(b) two homopolymers with PP-g-PCL and 70 : 10 : 30 i-PP/PP-g-PCL/ PCL (magnification
x 1000). For abbreviations, see Appendix 7.A.
(a)
(b)
Figure 7.10 Optical micrographs of (a) two-homopolymer blend with 70: 30 i-PP/PC and
(b) two homopo\ymers with PP-g-PCL and 70: 10 : 30 i-PP/ PP-g-PCL/PC (magnification
x 90). For abbreviations, see Appendix 7.A.
328
matrix material with a compatibilized PC dispersed phase could greatly

improve the mechanical properties, creating a toughened plastic. As PCL
and PC form a miscible blend the graft copolymer PP-g-PCL should behave
as an emulsifier for PP and PC blends. Blends of polypropylene and
polycarbonate (Mn 24800 g/mol and a polydispersity of 2.2) were mixed in
chlorobenzene solution. Optical microscope samples were solution cast
directly from chlorobenzene solution onto a glass slide and heated in a hot
stage for 10 min at 200C and allowed to cool quiescently. A 70: 30 blend
of PP/PC [30] observed by polarized optical microscopy (Figure 7.10(a))
shows gross phase separation of the spherulitic PP and the amorphous PC
phases.
The PC phases vary widely in both size and shape owing to the lack of
interaction with the PP matrix. A blend containing 70: 30 : 10 of PP/PC/PPg-PCL, where the graft contains 57 wt% PCL, was used to evaluate the
effect of the polymeric compatibilizer on the morphology of the blend.
Figure 7.10(b) shows the micrograph of the compatibilized blend. Only
small distorted spherulites are observed and only a few very small distinct
PC phases can be found. The PP-g-PCL is clearly proved to be an effective
compatibilizer for PP and PC blends.
It should also be noted that the films of the compatibilized blends formed
in the melt press were optically clear. This is unlike pure i-PP which forms
hazy, translucent films. The lack of large spherulites in both the blend and
the graft must minimize scattering.
7.5 Conclusions and future trends

It is both a scientific challenge and of industrial importance to develop a
facile method to prepare polyolefin graft and block copolymers, especially,
containing functional groups and having relatively well-defined molecular
structures. The unique combination of transition-metal catalysis and borane
chemistry provides a valuable and effective route to prepare polyolefin block
and graft copolymers, with a broad range copolymer composition. They
would be very difficult to prepare by other existing methods. Most of the
block and graft copolymers prepared in this way act as interfacial reagents
which can improve the interactions between polypropylene and other
materials. Some physical properties and applications, such as mechanical
strength, adhesion and PP blends and composites, are currently under
investigation.
Acknowledgement
The author would like to acknowledge the financial support received
through the Polymer Program of the National Science Foundation.
Appendix 7.A
7.A.l
BA
9-BBN
e-CL
DSC
EMA
EP
EPDM
GPC
IPA
MAO
MMA
NMR
PC
PCL
PE
PIB
PMMA
PO-B
PP
PS
PVA
SEM
TEMPO
THF
VA
VAc
Butylacrylate
9-Borabicyclo [3,3,1] borane
e-Caprolactone
Di1ferential scanning calorimeter
Ethyl methacrylate
Poly(ethylene-co-propylene)
Ethylene-propylene-dieneterpolymer
Gel permeation chromatography
Isopropanol
Methylalumin oxane
Methyl methacrylate
Nuclear magnetic resonance
Polycarbonate
Polycaprolactone
Polyethylene
Polyisobutylene
Poly( 1-octene-co-B-5-hexenyl-9-BBN)
Polypropylene
Polystyrene
Poly(vinyl acetate)
Scanning electron microscope
2,2,6,6-Tetramethyl-1-piperidinyloxy radical
Tetrahydrofuran
Vinyl acetate
Vinyl acrylate
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2.
3.
4.
5.
6.
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Electron beam radiation graft modification of

preformed polymer architecture
B. SVARFVAR
8.1
Introduction
Most polymer materials can be modified by grafting to produce copolymers

with a covalently bound side chain that may consist of a different polymer
material than the main branch. Figure 8.1 illustrates schematically the
difference between graft polymerized copolymers and conventional
copolymers.
There are three main grafting methods discussed in the literature:
chemical grafting [1], plasma induced grafting [2], and radiation induced
grafting [3].
Chemical grafting can be achieved in the polymer melt (see chs 1-6), as
well as in solution, e.g. via addition of a second monomer to a partially
polymerized emulsion of the main monomer in water. The second monomer
will then react almost exclusively on the surface of the polymerized backbone.
Plasma-induced grafting is performed by introducing a suitable organic
vapor into the plasma of inorganic gases, polymerization of the vapor takes
place and a polymeric film is deposited. The benefits of plasma-induced
grafting are the excellent mechanical, chemical and optical properties that
can be obtained for ultrathin highly-cross-linked polymeric coatings. A
drawback, from an academic point of view, is centered around the large
number of reactive species formed in the plasma which makes chemical
characterization of the system extremely difficult.
Radiation-induced grafting can be performed using different radiation
sources. The graft copolymer will have slightly different characteristics
depending on the type of radiation used. Three different types of radiation
have been used: y-rays and electrons and ultraviolet (UV) rays. There are
mainly two different methods of radiation-induced grafting: the simultaneous and the pre-irradiation methods.
In the simultaneous method the polymer is irradiated in the presence of
the monomer to be grafted. This procedure has drawbacks in that the extent
of grafting is difficult to control and that a considerable amount of
homopolymer is formed. Work has been carried out to improve this method,
for instance addition of Mohr's salt [4,5] or FeCl 3 [6,7] have been shown
to reduce the formation of homopolymer.
Chapman & Hall 1997
332

Homopolymer
A-A-A-A-A-A-A-A-A-A-A
Graft polymer
A-A-A-A-A-A-A-A-A-A-A
I
I
B
I
B
I
B
I
I
B
I
B
Alternating copolymer
A-B-A-B-A-B-A-B-A-B-A
Block copolymer
A-A-A-B-B-B-A-A-A-B-B
Random copolymer
A-B-A-A-B-B-B-A-B-A-A
Figure 8.1 Schematic presentation of different types of copolymers.
With use of the pre-irradiation method, on the other hand, homopolymer

formation can be greatly reduced. Pre-irradiation can be performed either
in the presence of oxygen, in which case peroxides are formed and can be
stored for a considerable period of time before activation by, for instance,
UV-light, or an inert atmosphere in which case radicals are formed which
will react immediately upon contact with monomers that are capable of
polymerizing by a radical mechanism.
8.2 Principles of pre-irradiation electron-beam grafting in inert atmosphere

The electron beam (EB) technique uses high-energy electrons to initiate
chemical and structural changes in polymers. The radiation is the source of
radical formation on the chains of the irradiated polymer. The radicals can
lead to chain scission, react with each other causing cross-linking, or they
may remain as trapped macroradicals. The relationship between the competing reactions was defined by Charlesby and Pinner in 1959 [8], who
derived the Charlesby-Pinner equation based on the solubility behavior of
irradiated polymers:
s+s
1/2
G(s)
=--+
2G(x)
k
G(x)M nr
ELECTRON BEAM RADIATION GRAFT MODIFICATION
333
Table 8.1 G-values for various polymers

Polymer
Polypropylene
Polyisoprene
Polyisobutylene
Polystyrene
Poly(dimethyl siloxane)
Poly(methyl acrylate)
Cellulose
Poly(methyl isopropenyl ketone)
G(s)
G(x)
0.2
1.7
1.8
0.5
0.6
1.2
5
0.04
o
o
0.5
0.76
2.5
10
1.1
0.02
2.5
o
o
o
where s is the soluble fraction of the polymer, G(s) and G(x) are the G values
of scission and cross-linking respectively, r is the radiation dose and k is a
constant. The G value is defined as the number of events that happen upon
absorption of 100 eV of energy. The G values give an indication of how the
irradiation will affect the base material when grafting polymers, whether
chemical and mechanical properties are improved by cross-linking or
deteriorated by chain-scission. Gas permeability through EB-irradiated
polymers is reported to be affected only when higher doses are used [9].
OH
:)=0
~
nAA
Figure 8.2 Schematic presentation of the initiation and propagation when grafting AA onto
PVDF.
334
REACTIVE MODlFlliRS FOR POLYMERS
G-values for a number of polymers can be found in the literature (Table 8.1)
[10].
Grafting can be initiated from the trapped macroradicals by exposing the
irradiated polymer to a solution containing a monomer that polymerizes by
a radical mechanism. The procedure is depicted schematically in Figure 8.2
for acrylic acid (AA) grafting from a poly olefin.
Most of the monomers that polymerize by a radical mechanism can be
grafted onto polymers that form radicals upon irradiation. This makes
radiation-induced grafting, using the electron-beam technique, a convenient
method for modifying a large number of polymers.
8.3
Parameters affecting electron-beam grafting
One major limiting factor with EB grafting is the miscibility of the monomer
and the polymer. There are, however, other factors which have to be taken
into account when polymers are EB graft-modified. Table 8.2 shows a
number of relevant parameters for radiation-induced grafting and gives
examples of how these parameters affect the reaction.
The influence of different parameters can clearly be seen from Figures
8.3-8.8 where different grafting systems are compared. Figure 8.3 shows the
effect of the irradiation dose on the extent of grafting of AA on polyvinylidene fluoride (PVFE). The dose affects not only the rate of the graft
reaction but, as the number of reactive sites is also increased, the extent of
saturation grafting will increase too. Saturation grafting means that the
reaction is allowed to proceed until no further grafting can take place. Aside
from the effect on the extent of the graft reaction, the dose has also a great
influence on the properties of the grafted polymer; an increased dose also
leads to increased chain-scission and cross-linking of the irradiated polymer.
Table 8.2 Different parameters for radiation-induced grafting and the reason for their influence
on the graft reaction
Parameter
Dose
Polymer
Monomer
Solvent and solvent
concentration
Temperature
Structure of the
polymer
Influence on graft reaction

Number of reactive sites, swelling (increased cross-linking will lead to
reduced swelling)
Crystallinity, density, surface energy, swelling, hydrophilicity/
hydrophobicity
Miscibility with polymer, reactivity, miscibility with solvent, polarity
Swelling, overcoming surface energy, concentration of monomer,
reduction of homopolymerization
Swelling, mobility of polymer chains, increased reactivity, increased
termination
Surface area
335
600r-------------------------------,
500
g> 400
~
e;, 300
(J)
X
w
200
100
100
200
300
400
500
600
Reaction time (s)
Figure 8.3 The influence of the irradiation dose when grafting AA (AA content = 30%;
solvent = water; ambient temperature) onto PVDF membranes with a pore size of 0.22 jlm .
= 25 kGy; = 100 kGy.
The influence of the nature of EB-irradiated polymers on the extent of

grafting reaction of styrene is shown in Figure 8.4. The difference in the rates
of grafting of styrene on PVDF, polyetheretherketone (PEEK) and polytetafluoroethylene (PTFE) polymer films cannot be attributed to anyone
parameter but rather to a number of different factors such as swelling,
crystallinity and surface properties. Swelling of the polymer and graft
copolymer in the graft solution determines the accessibility of the reactive
sites to the monomer. Crystallinity influences the stability of the trapped
~
Ol
.5
~Ol
'0
55
x
w
180
160
140
120
100
80
60
40
20
00
60
120
180
240
Reaction time (min)
Figure 8.4 The rate of grafting of styrene onto PVDF, PTFE and PEEK. The different
polymers were grafted under identical conditions. Styrene content = 80%; solvent = THF;
temperature = 70C, irradiation dose = 100 kGy. D = PVDF; = PTFE; 1::" = PEEK.
336
300r-------------------------------,
;:g
~
c:
250
200
150
E 100
~
UJ
50
O~----~------_+------~------~
120
180
240
Reaction time (min)
Figure 8.S The rates of reaction when grafting PVDF membranes (pore size = 0.22 tim) with
styrene (styrene content = 100%; ambient temperature; irradiation dose = 25 kGy) and AA
(AA content = 30%; solvent = water; ambient temperature; irradiation dose = 25 kGy).
<> = AA (water content = 70%); 0 = styrene.
radicals in the irradiated polymers. Surface properties influence wetting of

the polymer and the contact between the polymer and the monomer.
The nature of the monomer also influences the grafting efficiency of
EB-irradiated polymers. Figure 8.5 shows that the monomers styrene and
AA graft to a very different extent on PVDF membranes. Both polymer
polarity and the nature of the monomer, as well as the ability of the graft
solution to swell the polymer and graft-copolymer play an important role
in the extent of grafting achieved. The rate of grafting reaction of acrylic acid
on PVDF membranes is about 50 times faster than the rate of styrene
grafting on the same polymer. This is a result of the swelling power of
poly acrylic acid (PAA) in water, which will increase the accessibility of the
trapped macroradicals to the monomer, as well as of the high reactivity of
the AA monomer. Neither of these graft solutions swells the unmodified
PVDF polymer.
An optimization of the grafting conditions often includes choosing an
appropriate solvent and determining at what concentration this solvent
contributes most favorably to the grafting system. Addition of a solvent will
dilute the monomer in the graft solution, which in turn will reduce
homopolymerization. A solvent is sometimes needed to bridge the differences in polarity between the polymer and monomer. This is necessary to
enable wetting of the polymer surface and subsequent initiation of the graft
reaction.
The addition of a solvent does not always result in a reduction in the rate
of grafting. In some reaction systems, however, the swelling of the graft
copolymer can be increased by the addition of an appropriate solvent. An
ELECTRON BEAM RADIATION GRAFf MODIFICATION
337
600
~ 500
Cl
~ 400
I!!
Cl
'0 300
'E
~ 200
100rd~-_--------
200
400
600
800
Reaction time (min)
1000
Figure 8.6 Influence of solvent concentration when grafting AA from PE. The initial AA
concentrations used were 10%, 30%, 50%, 70% and 90%. Temperature = 70C; irradiation
dose = 200 kGy; solvent = water. <> = 90 vol% AA; 0 = 70 vol% AA; ... = 50 vol% AA;
= 30 vol% Aft.; 0 = 10 vol% AA.
example of this is the addition of water to the graft solution during grafting
of AA onto polyethylene (PE) (Figure 8.6). Addition of water initially
reduces the extent of homopolymerization of the monomer and increases
swelling of the graft copolymer. The increased swelling leads to improved
accessibility of the reactive sites on the irradiated PE chains for the
monomer containing graft solution, thereby increasing the rate of the
graft reaction. The reactivity reaches a peak around 30% water content
in the graft solution. The use of higher amounts of water decreases the
rate of grafting, as it will not increase the swelling any further, but it
will decrease the monomer concentration. Monomers that are in the solid
state at the reaction temperature must be dissolved in a solvent before
grafting.
For some systems the reaction temperature plays a critical role, mainly
when the mobility of the polymer chains is insignificant. In this case the graft
reaction cannot proceed further than the absolute surface of the polymer
and there will be no diffusion of monomer to the reactive sites inside the
polymer. This was illustrated by the work of Niemoller and Ellinghorst [11]
where N-vinylpyrrolidone was grafted onto PVDF, as depicted in Figure
8.7. For this grafting system, the increase in temperature increases grafting
from less than 5% in 1 h at 40C, to more than 30% in 1 hat SOC. If the
temperature is increased even further the rate of the grafting reaction
increases whereas the extent of saturation grafting decreases [11]. These
workers have shown that a maximum degree of saturation grafting is
reached when the temperature is adjusted at a level which will allow swelling
of the graft copolymer which in turn allows diffusion of the monomer to the
338
40
'0'
Cl
30
c:
==Il!
Cl
20
~
w
10
'0
1:
30
60
90
Reaction time (min)
120
Figure 8.7 Grafting of N-vinylpyrroJidone (50%; solvent = water; irradiation dose = 17 kGy)
onto PVDF film . = 40C; D = 50C; .. = 59C; D. = 69C; = 78%. Reprinted, with
permission, from: A. Niemoller, G. Ellinghorst, Angew. Makrornol. Chern., 148 (1987).
reactive sites. If the temperature is raised from this value the degree of
saturation grafting will decrease owing to bimolecular termination of
growing macro radicals (dependent on mobility of the macroradicals and
monomer/solvent concentration).
When comparing rates of the graft reactions of different systems, the
surface area of the polymer to be grafted must be considered. The three
membranes depicted in Figure 8.8 have porosities of about 70% and average
pore diameters of 0.22 flm, 0.45 flm and 0.65 flm. A reduction in pore size
240
Cl
~ 180
Cl
'0 120
1:
60
100
400
200
300
Reaction time (sec)
500
600
Figure 8.8 Grafting PVDF membranes with the same porosity and different pore sizes with
AA (AA content = 30%; solvent = water; ambient temperature; irradiation dose = 25 kGy) .
= 0.22 Jlm; D = 0.45 Jlm; D. = 0.65 Jlm.
339
Figure 8.9 An energy dispersive X-ray analysis of the cross-section of PVBC-grafted PE film.
The chlorine distributions are plotted beneath the SEM micrograph of the samples in question.
The extents of grafting and the reaction times are (a) 15% (1 h), (b) 47% (5 h), (c) 88% (10 h)
and (d) 167% (24 h).
(increase of surface area) leads to an increase in the rate of grafting. For

systems where the graft solution does not swell the polymer to be grafted
the reaction is diffusion-dependent as shown in Figure 8.9. Consequently,
the rate of reaction will be dependent of the surface area in all systems where
the graft solution does not swell the polymer to be grafted and generally
follows the order membranes> fibers> films.
In addition to these parameters there are certain conditions e.g. exclusion
of solved oxygen and absence of radical poisons from the graft solution,
which have to be met in order to achieve grafting. The irradiated samples
can be stored in air for considerable lengths of time between irradiation and
grafting without losing their potential for initiating graft reactions. Ellinghorst, Niemoller and Vierkotten report that the activity of an irradiated
PVDF sample is reduced to half the initial value after being stored in air for
5 h [3]. If, however, the graft solution is not purged of solved oxygen no
graft reaction will take place.
Figure 8.9 depicts the penetration of the graft monomer into the polymer
when grafting vinylbenzyl chloride (VBC) onto a PE film. By analyzing the
340
cross-section of the film for chlorine the extent of grafting required to graft
the film throughout can be determined. For this reaction system an extent
of grafting in excess of 100% is needed to achieve grafting throughout. This
value is dependent on parameters such as swelling of the polymer and the
graft copolymer in the graft solution and the thickness of the polymer film.
This offers several possibilities for tailoring the grafted product, with regard
both to the extent of grafting and the distribution of the grafted chains.
8.4 Differential polymer architectures suitable for electron-beam grafting

The physical form of the polymers grafted by EB methods is generally rather
thin, to allow for electron penetration of the material. Though the depth of
penetration can be altered by varying the operational voltage of the
accelerator the best-suited materials are films, fibers and membranes of
various kinds.
The term 'membranes' does not actually describe the architecture of the
polymer material, only that the application in which it is used utilizes its
properties as a porous material. The pores can be macropores that allow
convective flow or they can be micropores that allow only specific ions to
permeate through. The architecture can be sheet, hollow fiber or microcapsule. In some cases the membrane properties appear only as a result of the
graft modification. This can be explained by a phase separation between the
base polymer and the graft copolymer upon subjecting the material to a
solvent that is a non-solvent to the other entity.
Pre-formed macroporous membranes have a polymer architecture which
is the most sensitive to graft parameters of all the polymer structures
mentioned in this review. The rate of the graft reaction is extremely rapid
compared with the rate of reaction when grafting films, owing to the large
surface area of the membranes. When the extent of grafting is increased, the
porous structure changes. When a PVDF membrane with a pore size of
0.45 pm is grafted with AA the initial effect will be a reduction of the pore
diameters. As the extent of grafting is increased, and the pore walls are
grafted throughout the core, there will be a partial collapse of the original
pore structure (Figure 8.10). This is caused by an increased mobility of the
polymer chains in the graft copolymer as the water-swelling PAA graft
chains will penetrate the hydrophobic PVDF regions, and the hydrophobic
core is lost.
8.5
Applications of electron-beam grafting
PE cross-linking using high-energy radiation was discovered in the 1950s

[12,13]. Since then a large number of vinyl monomers, such as AA,
acrylates, styrene and styrene derivatives have been grafted to different
341
Figure 8.10 SEM micrographs depicting the change in the pore structure of AA-grafted PVDF
membranes with a pore size of 0.45 JIm as a function of the extent of grafting. The micrographs
are taken of dry membranes. The extents of grafting are (a) 0%, (b) 7%, (c) 25%, (d) 85%,
(e) 170% and (f) 386%. The initial structural effect of the graft reaction will be a thickening of
the pore walls (parts (a)- (d)). As the graft reaction is allowed to proceed further, the pore
walls will be grafted through the core, replacing the supporting hydrophobic PVDF core
with a homogeneous PVDF - AA graft copolymer. The effect of swelling in the graft solution
before drying can be seen in the collapse of the original porous structure (parts (e) and (f)).
polymers. The main purpose of early studies was modification of fibers for
the textile industry. Nowadays, however, the most interesting topics are
immobilization of biocomponents [14], immobilization of stabilizers [15],
immobilization of catalysts [16] and preparation of radiation-grafted membranes and hollow fibers [17- 19].
342
8.5.1
Adhesion
EB grafting improves the adhesion properties of a polymer material. If the

extent of grafting is low, the bulk of the material remains unchanged yet the
surface will have the adhesion properties of the graft polymer.
An example of this is AA grafting of polypropylene in order to improve
bioadhesion. The polypropylene film is grafted with AA and placed between
two mucin-coated surfaces. The adhesion force is reported to increase with
the extent of grafting of the film [20].
Another application where grafting can be used to improve the adhesive
properties of polymers is in the modification of fibers for reinforcement of
glass-ionomer cements [21]. Unmodified polyolefin fibers possess a high
tensile strength so they are potentially well-suited for reinforcement of
glass-ionomer cements. The main problem, however, was the hydrophobic
nature of the fibers, which prevented adhesion to the cement. This problem
was overcome by grafting acrylic acid onto the fiber. As a result the flexural
strength of the glass-ionomer cements was improved.
8.5.2
Textiles
Graft modification of textile fibers can impart a number of different

properties. By grafting ethyl acrylate onto rayon fibers the elasticity of the
fibers was improved; this means that after stretching the grafted fibers
recovered their original state whereas the ungrafted fibers did not [22]. The
tensile strength, however, decreased owing to cellulose chain-scission caused
by the EB treatment.
Cotton and rayon fibers have been grafted with vinyl phosphonate
monomers to improve the flame retardancy of these fibers. It was found that
permanent press could be obtained beside good flame-retardancy properties
[23].
8.5.3
Supports for catalysts and reagents
Grafting of polymers can also be aimed at supplying a support for

functional monomers that serve as or that can form complexes with reagents
or catalysts.
By grafting a polymer film through the core it is possible to use it in
membrane applications. Owing to the dense nature of this membrane it can
be made selective to certain species in the surrounding media. Another
approach is to graft a functional monomer onto the pore walls of a
pre-formed membrane. This will result in a membrane through which
convective transport may be possible and that has graft chains of functional
monomers stretching out into the pores. As a consequence, the transport of
reactive species to immobilized reactive sites will be extremely rapid.
343
Fibers are also well-suited as catalyst supports [24,25]. The combination

of easy handling, easy separation from reaction media and ability to
withstand high-flow applications makes them a serious alternative to
conventional catalyst supports such as carbon. Grafted copolymers show
higher activities than conventional polymer supports such as Nafion for
esterification of acetic acid by primary alcohols [26]. In Nafion the
catalytic sites are distributed evenly throughout the bulk, and, as the
swelling is minimal, the accessible capacity will be limited. EB-grafted fibers,
on the other hand, will have non-cross-linked graft chains extended in
various directions, supplying easy accessibility to the catalytic sites.
8.5.4 Ion-exchange
Hydrogel ion-exchangers can potentially be replaced by fiber-supported
hydrogels as such gels combine accessibility with improved mechanical
properties. If a fiber is grafted with, for instance, AA then the surface area
of the system is enormous in an aqueous system where the graft chains are
in the swollen state; this means that chemically the grafted fiber behaves
almost like a hydrogel. The mechanical properties, however, are much better
than those of a hydrogel system owing to the supporting effect of the
hydrophobic fiber-core. Furthermore, a fiber-supported hydrogel is much
easier to separate from solution by, for instance, filtration and it is better
equipped to withstand pressures in high-flow-rate applications without
collapsing, as is the case with a hydrogel system.
An important application of grafted ion-exchange fibers is metal recovery
from waste waters and sea-water. An example of this is uranium recovery
from sea water, which has been performed with PE and polypropylene fibers
EB-grafted with acrylonitrile and functionalized with hydroxylamine [27].
8.5.5 Separations
Composites made of polyelectrolytes grafted on the surface of porous
hydrophobic membranes are of special interest for the construction of
separation and purification systems. The composites will function as valves
that open and close depending on external signals modifying the forces of
interaction between the charged graft chains [28].
Dense membranes are also used, for instance, in separation and pervaporation applications [29]. By grafting a polymer film or membrane the
solubility of various species can be increased in this polymer material. There
are several examples where plasma graft polymerization has been used for
the preparation of pervaporation membranes [30-32]. The principles of
improved separation based on solubility control in graft copolymers described in these references can be applied to separations as well as pervaporations and the graft modification can also be performed by EB grafting.
344
8.5.6 Fuel cells

In a fuel cell chemical energy is converted to electrical energy in a process
whereby hydrogen is oxidized to water. The requirement for the fuel cell
membranes is to allow proton transport but not gas diffusion. There are
several polymeric fuel cell membranes on the market today. One of these,
Raymion, is prepared by pre-irradiation EB grafting of the copolymer of
C l H 4 and ClF 4 with rl,p,p-trifluorostyrene [33]. As the degradation of
polymer electrolyte membranes seems to be a result of the formation of
HO l radicals at the anode it is imperative that the oxygen permeability of
the membrane is minimized without loosing proton conductivity [34]. The
alternative approach is the one used with Raymion where the hydrogens
most susceptible to degradation are substituted by fluorine.
8.5.7 Membrane reactors

Membrane reactors are recognized as possessing some unique capabilities
[35]. The three most significant are:
reactants and products can be transported to and from the catalyst by
convection, which is more efficient than the diffusion process which
controls transport of the compounds in conventional supports;
membranes can compartmentalize the reactor, providing an interface for
a second process stream;
in multilayer composites, membranes can provide highly selective control
over reactant flux.
The limitations are presently that polymer materials generally tolerate only
relatively mild reaction temperatures.
Hollow fibers are frequently used in membrane reactors where minimal
reactor volume is desired. The main drawback is that they are extremely
sensitive to fouling and clogging caused by particles in the feed stream [36].
8.5.8
Controlled release of drugs
The most studied application is pH-sensitive porous membranes that

possess a self-regulating insulin release in response to the pH of the
surroundings [37].
8.6
Concluding remarks
Radiation-induced grafting is a convenient way of modifying a number of

polymer materials. The method makes it possible to prepare a variety of
solid architectures with chemical properties normally found only in gel-like
345
or highly-cross-linked materials. A major difference when compared with

conventional copolymerization is the high accessibility and capacity obtained.
The electron-beam pre-irradiation method offers certain benefits compared with other methods of radiation grafting, especially in the case of thin
materials. High dose rates make scale-up viable. No additives or initiators
are needed, which leads to low operating costs. Copolymers formed consist
of only two components: supporting polymer backbone, and graft chains
that are covalently bound to the backbone.
The main disadvantages with EB grafting, however, are the cost of the
electron accelerator and the limited depth of penetration of electrons. This
means that EB grafting is only suited for relatively thin materials.
The anchoring of functional groups onto polymer backbones offers
several benefits: easy separation from reaction media, physical support
enabling high-flow applications, and potential control of the microenvironment surrounding the functional group.
A number of applications have been suggested for radiation-grafted
materials. Despite this, there are relatively few commercial applications in
which these materials are used. One reason for this may be problems with
scale-up, or simply an unwillingness on the part of industry to invest in new,
potentially better, but yet insufficiently proven, technologies. Problems
arising with scale-up differ from method to method. This problem is
probably smallest when using EB grafting. One solution might therefore, in
some cases be to attempt to prepare novel materials with EB grafting that
have previously been prepared by means of other grafting methods.
Appendix 8.A
8.A.1
AA
EB
GC
kGy
PAA
PE
PEEK
PE-g-VBC
PTFE
PVBC
PVDF
SEM
THF
UV
VBC
Acrylic acid
Electron Beam
Gas chromatography
Kilo Grey
Polyacrylic acid
Polyethylene
Polyetheretherketone
Poly(ethylene-g-(vinylbenzyl chloride))
Polytetrafluoroethylene
Polyvinylbenzyl chloride
Polyvinylidene fluoride
Tetrahydrofurane
Ultraviolet
Vinyl benzyl chloride
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19. Tsuneida, S., Saito, K., Furusaki, S., et al. (1991) Metal collection using chelating hollow
fiber membrane. J. Membr. Sci., 58, 221-34.
20. Ekman, K., Nasman, J. and Roskos, K.V. (1994) Method for screening new bioadhe~ive
functionalities, in Applied Radiation Processing of Polyolefins (ed. K. Ekman) thesis, Abo
Akademi University, Abo.
2l. Lindsjo, c., Ekman, K. and Nasman, J. (1995) Reinforcement of glass-ionomer cements
using graft modified polyethylene fibers. Unpublished manuscript, Department of Polymer
Technology, Abo Akademi University, Abo
22. Nakamura, Y., Arthur, J.C. Jr and Negishi, M., et al. (1970) Rheological properties of
elastomers based on cellulose fibers. J. Appl. Polym. Sci., 14, 929-5l.
23. Walsh, W.K., Bittencourt, E., Miles, L.B. and Rutherford, H.A. (1976) Electron-beaminitiated grafting of flame retardants to fabrics containing cellulose. I. Reaction rate studies.
J. Macromol. Sci. Chem., AI0(4), 695-707.
24. Nasman, J.H., Ekman, K. and Sundell, M. (1994) Process for the preparation of a graft
copolymer bound catalyst. US Patent 5326 825.
25. Peltonen, R., Ekman, K. and Nasman, J. (1994) Poly[propylene-graft-(4-vinylpyridinium
dichromate)]: a novel fibrous polymer-supported oxidizing agent. Ind. Eng. Chem. Res.,
33(2), 235-38.
26. Mislavsky, B.V. and Melnikov, V.P. (1993) Synthesis, properties, and applications of
composite materials based on grafted copolymers of perfluoropolymers and perfluorinated
monomers with functional groups. Polym. Prep., 34(1), 377-8.
27. Kabay, N., Katakai, A., Sugo, T. and Egawa, H. (1993) Preparation of fibrous adsorbents
containing amidoxime groups by radiation-induced grafting and application to uranium
recovery from sea water. J. Appl. Polym. Sci., 49, 599-607.
28. Casolaro, M. (1994) Redox and pH-sensitive polymer-grafted membranes: thermodynamic
characteristics in drug delivery. Top. Mol. Organ. Eng. (Prop. and Chem. of Biomol. Syst.),
11, 127-4l.
29. Nakagawa, T. (1992) Gas separation and pervaporation, in Membrane Science and
Technology (eds Y. Osada and T. Nakagawa), Marcel Dekker, New York, ch. 7.
30. Hirotsu, T. and Nakajima, S. (1988) Water-ethanol permseparation by pervaporation
through the plasma graft-copolymeric membranes of acrylic acid and acrylamide. J. Appl.
Polym. Sci., 36, 177-89.
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of the filling-polymerized membrane prepared by plasma-graft polymerization for pervaporation of organic-liquid mixtures. Ind. Eng. Chem. Res., 31,1914-19.
32. Yamaguchi, T., Nakao, S. and Kimura, S. (1993) Design of pervaporation membrane for
organic-liquid separation based on solubility control by plasma-graft filling polymerization
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348
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1008-14.
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FEP-g-polystyrene membranes as polymer electrolytes in fuel cells. Electrochimica Acta,
40(3),345.
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England.
36. Cabasso, I. (1987) Membranes, in Encyclopedia of Polymer Science and Engineering, vol. 9,
2nd edn, (ed. H.F. Mark), John Wiley, New York, pp. 509-80.
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with polyelectrolytes controlling solute permeability. Colloids and Surfaces, 77, 81-9.
Thermoplastic elastomers based on

elastomer/thermoplastic blends
dynamically vulcanized*
A.Y. CORAN and R.P. PATEL
9.1
Introduction
Elastomer-thermoplastic blends have become technologically useful as

thermoplastic elastomers in recent years [1-3]. They have many of the
properties of elastomers but are processable as thermoplastics [4]. They do
not need to be vulcanized during fabrication into end-use parts. Thus they
offer a substantial economic advantage with respect to the fabrication of
finished parts.
For many end uses, the ideal elastomer-plastic blend comprises finely
divided elastomer particles dispersed in a relatively small amount of plastic.
The elastomer particles should be cross-linked to promote elasticity (the
ability of the blend composition to retract forcibly from a large deformation). The favorable morphology should remain during the fabrication of the
material into parts, and in use. Because of these requirements for the ideal
case, the usual methods for preparing eastomer-plasic blends by melt
mixing, solution blending or latex mixing [5] are not sufficient.
The best way to produce thermoplastic elastomeric compositions comprising vulcanized elastomer particles in melt-processable plastic matrices is
by the method called dynamic vulcanization. It is the process of vulcanizing
an elastomer during its melt-mixing with a molten plastic [6-9]. This
chapter describes the dynamic vulcanization process and the products which
can be produced thereby. The scope of applicability of dynamic vulcanization is discussed. End-use applications of some of the products which can
be prepared by dynamic vulcanization are also described.
Dynamic vulcanization is a route to new thermoplastic elastomers which
have many properties as good as, or even in some cases better than, those
of elastomeric block copolymers. Yet the new materials are prepared from
blends of existing polymers. Thus, new, improved thermoplastic elastomers
can be prepared from 'old' polymers. Entirely new processes and materials
can be avoided. Moreover, high new-product 'entrance fees' (caused by such
barriers as environmental concerns, capital costs and the necessity for
*This contribution is based on a chapter entitled 'Reactive blending', by the same authors,
which appeared in the book Thermoplastic Elastomers (1996), Hanser Publishers, Munich and
New York.

Chapman & Hall 1997
350
high-volume polymerization units and competitive divisors) can also be

avoided.
This technology has led to a significant number of new thermoplastic
elastomeric products commercialized during the mid-to-Iate 1980s [10]. It
is important to note that the commercialization of the dynamic vulcanization technology was aided by the discovery [11] of preferred compositions
based on Lewis-acid-catalyzed methylol-phenolic dynamic vulcanization
systems for the new thermoplastic elastomers.
There has been much commercial interest in dynamic vulcanization since
the introduction of proprietary products (e.g. SANTOPRENE thermoplastic elastomer) prepared by the dynamic vulcanization of blends of olefin
rubber with polyolefin resin. If the elastomer particles of such a blend are
small enough and if they are fully vulcanized, then the properties of the
blend are greatly improved. Examples of the improvements are as follows:
reduced permanent set,

improved ultimate mechanical properties,
improved fatigue resistance,
greater resistance to attack by fluids, e.g. hot oils,
improved high-temperature utility,
greater stability of phase morphology in the melt,
greater melt strength, and
more reliable thermoplastic fabricability.
In short, dynamic vulcanization can provide compositions which are very

elastomeric in their performance characteristics. These thermoplastic vulcanizate compositions can be readily fabricated into finished parts in
thermoplastic processing equipment.
Because of the surprisingly beneficial effects of complete dynamic vulcanization (in contrast to prior and partial dynamic vulcanization [7]), the
work described in this chapter opens a broad new field of thermoplasticelastomer research.
As stated above, in some respects, the new materials can outperform
block-copolymer-type thermoplastic elastomers. This is because the particulate elastomeric domains consist of fully vulcanized elastomer. As a result of
this, the thermoplastic vulcanizates can perform well with respect to hot-oil
resistance, compression set (at elevated temperatures) and high-temperature
utility. A factor contributing to the greater high-temperature utility is that
during fabrication of a finished part many of the vulcanized rubber particles
physically interact with one another to form a 'network' of vulcanized
elastomer. When scrap is reground and reworked in the melt, the clusters of
touching, loosely bound particles disintegrate and melt-processability is
restored.
Thermoplastic vulcanizate compositions have been prepared from a great
number of plastics and elastomers; however, only a limited number of
THERMOPLASTIC ELASTOMERS
351
elastomer/plastic combinations give technologically useful blends, even after

dynamic vulcanization. The results of a study of 99 elastomer/plastic
combinations (based on 11 elastomers and 9 plastics) are also reviewed in
this chapter. The goal of this work was to define the practical scope of
compositions that can be prepared by dynamic vulcanization. This was
accomplished by an analysis which related mechanical properties of the
dynamically vulcanized blends to characteristics of their elastomeric and
plastic components. The conclusion of that work was that the best elastomer-plastic thermoplastic vulcanizates are those in which:
the surface energies of the plastic and elastomer are matched,
the entanglement molecular length of the elastomer is low, and
the plastic is at least 15%-30% crystalline.
Were it not for the large difference between the surface energy of acrylonitrile-butadiene copolymer (NBR) and that of polypropylene (PP), a blend
of dynamically vulcanized NBR with isotactic polypropylene might be a
good choice for an oil-resistant thermoplastic elastomer. In early work with
these materials only marginally good compositions were obtained. Now it
has been found that NBR/polypropylene-based thermoplastic elastomers,
which are resistant to hot oil and have excellent strength-related properties,
can be prepared.
This can be accomplished by the dynamic vulcanization of technologically compatibilized NBR/PP blends. Technological compatibilization of
the blend (before it is dynamically vulcanized) is brought about by the
presence of a small amount (about 1%) of compatibilizing agent in the
blend. The compatibilizing agent is a block copolymer containing segments
similar to each of the polymers which are to be compatibilized. It acts as a
macromolecular surfactant and its presence, during mixing, permits the
formation of very small droplets of the elastomer which later, during
dynamic vulcanization, become very small particles of vulcanized NBR.
Research results related to the dynamic vulcanization of technologically
compatibilized elastomer/plastic blends, which can lead to a wide variety of
new product development opportunities, are considered in this chapter. In
addition, it is even possible to use a mixture of two thermodynamically
incompatible plastics with two thermodynamically incompatible rubbers if
the plastics are compatibilized by the action of block copolymers and if each
of the rubbers can give a useful composition with one of the plastics in the
compatibilized blend.
9.2 The preparation of elastomer/plastic blends by dynamic vulcanization
Polymer blends, in general, have been prepared commercially by melt

mixing, solution blending, or latex mixing. Elastomer/plastic blends of the
352
type discussed here, containing rather large amounts of elastomer, have

generally been prepared by melt-mixing techniques. Melt-mixing avoids
problems of contamination, solvent or water removal, etc. In general,
Banbury mixers, mixing extruders and the newer twin-screw mixers are
suitable for melt-mixing elastomer with plastics. However, for the purposes
of this discussion, emphasis will be on laboratory melt-mixing techniques
that simulate mixing.
The procedures given below are based on the use of either a small
Brabender mixer or a Haake Rheomix. In each case the mixer was fitted
with cam-type rotors; optimum batch sizes were between 55 g and 75 g. In
a process, to which he gave the name of dynamic vulcanization, Gessler [6]
prepared 'semi-rigid' elastomer-plastic compositions containing minor proportions of partially vulcanized elastomer. Fischer [7] used a dynamic
vulcanization process to prepare compositions containing varying amounts
of partially vulcanized ethylene-propylene-diene monomer (EPDM) elastomer. Large proportions of elastomer were generally used and soft compositions could be obtained. An organic peroxide was used to cross-link the
elastomer in the presence of polypropylene, which was greatly damaged by
the action of the peroxide.
Later, it was found that very strong, elastomeric, compositions of EPDM
and polypropylene can be prepared by dynamic vulcanization, provided
that peroxide curatives are avoided [8,9]. If enough plastic phase is
present in the molten state, the compositions are processable as thermoplastics. Plasticizers or extender oils and fillers can be used to expand
the volume of the elastomer phase. In the molten state, a suitable plasticizer can expand the volume of the plastic or 'hard' phase. If the hardphase material is a crystalline material such as polypropylene, then,
upon cooling, its crystallization can force the plasticizer out of the hard
phase into the elastomer phase. Thus the plasticizer may act as both a
processing aid at melt temperatures and a softener at the lower temperatures
of use.
The dynamic vulcanization process has been applied to many elastomer/
plastic combinations. It can be described as follows: Elastomer and
plastic are first melt-mixed, e.g. in an internal mixer. After a well-mixed
blend has been formed, vulcanizing agents (curatives, cross-linkers) are
added. Vulcanization then occurs while mixing continues. The more
rapid the rate of vulcanization, the more intense the mixing must be to
ensure good fabricability of the blend composition. It is convenient to follow
the progress of vulcanization by monitoring mixing torque or mixing
energy requirement during the process. After the mixing torque or energy
curve goes through a maximum, mixing can be continued somewhat
further to improve the fabricability of the bend. After discharge from
the mixer, the blend can be chopped, extruded, pelletized, injection molded,
etc.
353
9.3 Properties of blends prepared by dynamic vulcanization

Dynamic vulcanization, as described herein, is the process of vulcanizing
elastomer during its intimate melt-mixing with a non-vulcanizing thermoplastic polymer. Small elastomer droplets are vulcanized to give a particulate vulcanized elastomer phase of stable domain morphology during and
after melt processing.
As stated earlier, the effect of the dynamic vulcanization of elastomer/plastic
blends is to produce compositions which have improvements in permanent
set, ultimate mechanical properties, fatigue resistance, hot-oil resistance,
high-temperature utility, melt strength and thermoplastic fabricability.
Permanent set of these compositions can be improved by only slight or
partial vulcanization of the elastomer. Such compositions can be produced
either by the partial vulcanization of the elastomer before its mixture with
plastic or by dynamic vulcanization (during mixing with plastic) [7].
However, the other improvements can only be obtained (at least in the case
of EPDM/polyolefin compositions) by dynamic vulcanization in which the
elastomer is technologically fully vulcanized. For EPDM, the term 'fully
vulcanized' refers to a state of cure such that the cross-link density is at least
7 x 10 - 5 mol/ml of elastomer (determined by swelling) or such that the
elastomer is less than about 3% extractable by cydohexane at 23C [8].
9.3.1
Polyolefin-based thermoplastic vulcanizates
(a) EPDM-polyolefin thermoplastic vulcanizates. The dynamic vulcanization of blends of EPDM elastomer with PP and with polyethylene (PE)
has been described [9]. Mechanical properties, hardness, tension set values,
and other parameters associated with unfilled compositions are given in
Table 9.1. The general recipe of the compositions was as follows:
EPDM (Epsyn 70A)

Polyolefin resin,
Zinc oxide,
Stearic acid,
Sulfur,
Tetramethylthiuram disulfide (TMTD),
2-Benzothiazolyl disulfide (MBTS),
100;
X;
5;
1;
Y;
Y/2;
Y/4;
where X, the number of parts by weight of polyolefin resin, and Y, the

amount of sulfur, were varied.
Not all of the compositions of Table 9.1 were prepared by dynamic
vulcanization, however. In the first four compositions, for comparison
PP/66.7
PP/66.7
PP/66.7
PP/66.7
PP/66.7
PP/66.7
PP/66.7
PP/66.7
PP/66.7
PP/66.7
PP/33.3
PP/42.9
PP/53.8
PP/81.8
PP/122
PP/233
Nonec/O
Ppd/oo
PE/66.7
PE/66.7
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
2.00
2.00
2.00
2.00
2.00
1.00
0.50
0.25
0.13
0.00
1.00
2.00
2.00
2.00
2.00
5.00
2.00
0.00
2.00
0.00
Sulfur
(phr)
D
D
D
D
D
D
S
S
S
S
S
D
D
D
D
D
Method
of preparation b
16.4
0.0
16.4
16.4
16.4
16.4
16.4
12.3
7.8
5.4
1.0
0.0
12.3
16.4
16.4
16.4
16.4
14.5
16.4
Crosslink
density
(l05 mol/ml)
dw
72
750
39
290
17
96
5.4
30
-1-2
dn
(pm)
Rubber
particle
size
app = Polypropylene, Profax;H' 6723; PE = Polyethylene, Marlex:[v EHM 6006.

bS = static (conventional) vulcanization; D = dynamic vulcanization.
cControl composition, purely of cured rubber.
dControl composition: polypropylene only.
Resin
type"
(phr)
Composition
number
Table 9.1 Properties of unfilled thermoplastic compositions
43
41
41
42
42
40
39
40
35
22
29
34
36
43
48
59
11
71
35
21
Shore
hardness
(D)
97
102
105
103
58
60
61
56
57
72
13
22
32
82
162
435
2.3
854
51
46
Young's
modulus
(MPa)
8.4
8.4
8.4
8.4
8.0
7.2
6.3
6.7
6.0
4.8
3.9
5.6
7.6
8.5
11.3
13.6
1.5
19.2
7.2
4.1
Stress
at 100%
strain
(MPa)
8.6
9.8
13.9
19.1
24.3
18.2
15.0
15.8
9.1
4.9
12.8
17.9
25.1
24.6
27.5
28.8
2.0
28.5
14.8
3.5
Tensile
strength
(MPa)
165
215
380
480
530
490
500
510
407
190
490
470
460
550
560
580
150
530
440
240
Elongation at
break
(%)
18
24
22
22
20
16
17
19
19
27
66
7
9
12
19
31
46
1
Tension
set
(%)
356
25.----------------------------------------------,
d =1-2 ~m
20
100
200
300
Strain (%)
400
500
600
Figure 9.2 The effect of vulcanized-rubber particle size on mechanical properties (x denotes
failure).
Mechanical properties and hardness measurements were carried out by

usual means.
The effect of the elastomer particle size on the tensile strength and
ultimate elongation is shown in Figure 9.2. This is a composite stress-strain
curve constructed from the data associated with compositions 1-5 of Table
30
20
25
15
20 -;
III
(jj
III
c:
0
iii
c:
10
en
15 ~
c:
.l!!
t!!!
Q)
10 1a
E
5
5
00
6
8
10
12
Cross-link density (10 5 mol/ml)
14
16
Figure 9.3 The effect of cross-link density on tensile strength and tension set.
355
Figure 9.1 Scanning electron microphotograph of OS04 stained sample of a 73 Shore

A hardness commercial grade of completely vulcanized EPDM- PP-derived thermoplastic
vulcanizate.
purposes, the elastomer was first press cured and then ground, by tight
roll-milling, to various particle sizes. The ground elastomer particles were
then mixed with molten PP. Compositions 5- 20 of Table 9.1 were obtained
by dynamic vulcanization.
Particle sizes were determined by optical microscopy. However, the
particles of the dynamic vulcanizates were so small that their diameters
could only be determined to be in the range 1- 2,um. (More recently,
electron microscopy has revealed that the commercial grades of EPDM/
polypropylene-derived thermoplastic elastomer contain elastomer particles
in the range 1-2,um. An example is given in Figure 9.1.) For the measurement of the cross-link density of the elastomer, samples of the elastomer
alone were press cured under conditions selected to simulate the conditions
of dynamic vulcanization. Cross-link densities of the press-cured samples
were then determined on the basis of solvent-swelling measurements by
using the Flory- Rehner equation [12]. It may be argued that the presence
of polyolefin might change the cross-link density, especially in the case of
the dynamically cured compositions. However, we have determined that the
polyolefin is essentially completely extractable from the cured elastomer by
boiling decalin or xylene. This would indicate that there is little or no
interaction of the thermoplastic resin with the sulfur-based curing system.
357
30
as
a.
e
.s::
0,
c:
25
20
'lii
~
0
c:
Q)
1U
E
""
5
15
10
5
00
50
100
150
2501
200
Concentration of P (phr)
Figure 9.4 The effect of polypropylene (PP) content on EPDM - PP thermoplastic vulcanizate
properties. + = ultimate tensile stress (MPa); = Young's modulus (MPa); * = tension set (%).
9.1. Each cross denotes a stress and strain at rupture or failure. From Figure
9.2, ultimate strength, ultimate elongation and energy to break (area under
curve from origin to an appropriate data point) are apparent. The average
elastomer particle, size, d, associated with each cross is noted. The ultimate
properties are an inverse function of elastomer particle diameter. The best
0.1L-__ __-L____L-__ __-L____

-100 -50
o 50 100 150 200
~
L-~
250
Temperature (OC)
Figure 9.5 The effect of temperature on the stiffness of EPDM/PP blend compositions.
- = vulcanized; --- = unvulcanized.
358
REACTIVE MODIFffiRS FOR POLYMERS
compositions were prepared by dynamic vulcanization. There appears to be

no other means of producing rubber particles of such small size.
Major effects of changes in cross-link density are shown in Figure 9.3.
Only a small amount of cross-link formation is required for a large
improvement in tension set. Tensile strength improves rather continuously
as the cross-link density of the elastomer phase increases, but the compositions remain fabricable as thermoplastics even at high elastomer cross-link
densities. However, only small changes in the stiffness of the compositions
occur with great changes in the extent of cure.
As the proportion of polypropylene to elastomer increases, the compositions become less elastomeric and more like the plastic (Figure 9.4).
Modulus, hardness, tension set and strength increase. The shape of the plot
of strength against the proportion of polypropylene is interesting. Strengths
are low until at least 30 parts of polypropylene per 100 parts of elastomer
are used. Then, as the amount is further increased, strength rapidly increases
until the PP content is about 50 phr. Further addition of polypropylene
increases the strength only slightly.
Dynamic modulus both in vulcanized and in unvulcanized states is
shown as a function of temperature in Figure 9.5. The composition is that
of composition 5 of Table 9.1. The dynamic shear moduli were determined
by means of a torsion pendulum [13]. An effect of dynamic vulcanization is
to prevent a complete loss of elasticity and strength at the melting point of
the resin, PP. Provided that there is enough cross-linked rubber in the
composition, it continues to exhibit sufficient strength for the torsion
pendulum modulus measurements even after the plastic phase melting point
has been surpassed.
Another effect of dynamic vulcanization, indicated by the results of
Figure 9.5, is a smaller decrease in modulus as the temperature is increased.
The unique performance of the thermoplastic vulcanizates, even above the
plastic melting points, suggests a variety of high-temperature applications.
The data given for compositions 19 and 20 of Table 9.1 indicate that
EPDM/PE blends are also greatly improved by dynamic vulcanization.
However, on the basis of comparisons between compositions based on PE
with those based on PP one concludes that the best compositions are
prepared from PP.
The morphology of an EPDM-PP dynamic vulcanizate is that of a
dispersed-phase morphology. This morphology has been observed to be
independent of the elastomer-to-thermoplastic ratio or the molecular
weights of the constituent polymers. In contrast, a variety of morphologies
can be obtained for simple blends depending on polymer ratios, molecular
weights of the polymers or the mixing conditions [14]. These conclusions
are demonstrated by the photomicrographs of Figures 9.6(a) and 9.6(b).
The data of Table 9.2 demonstrate the effects of black loading and oil
extension. The compositions are variations of composition 15 of Table 9.1.
359
1 0KV
3 , 021~ :{
33TP
(iii)
(ii)
(i)
'"\.... ,l'
; .....
'-. 1."-'
. '. c
.. ,. f.t( ., : '.
'
.. .
",.
V '
' ",
'
" ~ ,i.j...o.",,~"
" ~I:'
,tC"
~ .' ,
to
'~,: ~ t ..,
~"
"C:'
~ c,
vi
r,
e.
t'"
~.' "-
'
,' .--"
.'
,..,. ..~,~~r.:~. ~,0 _.~

. .,.~, -,;;".4't :
;-r~' .- '
, . \ ,'" . "
'{
'. t'"
i~
.- ' ,
.,
~' r ~_ ~- . (
~"r
'"~.k'''
, .
: .7,"'"
:".,"'~' .' 'J ".{ ' ,e

(iv)
.. ..
'.
I: .
(
(v)
Figure 9.6(a) SEM photomicrographs of blends of various EPDM/PP proportions: (i) 80/20,
(ii) 60/40, (iii) 50/50, (iv) 40/60, (v) 20/ 50,
The effect of the filler is to strengthen the composition somewhat and to give
some stiffening (with respect to hardness and stress at 100% strain but not
with respect to the 'zero strain' or Young's modulus). Oil extension and
carbon black or other filler loading can give compositions of lower cost but
excellent quality. From data such as those in Table 9.2, and from measurements of hot-oil resistance, fatigue life, etc., it has been concluded that these
oil-extended, filled compositions will perform similarly to conventional
elastomer vulcanizates.
As noted above, the commercialization of thermoplastic elastomers
prepared by dynamic vulcanization was greatly aided by the discovery [11]
that compositions based on Lewis-acid-catalyzed methyloljphenolic-resintype cure systems are surprisingly superior to those prepared from the
accelerated sulfur system used above. This is especially true with respect
360
(vi)
(vii)
....\::-. ...:..
"..,.,. .'J' .
II_J~ ' . ,
,... ~ -. ~. :' f~...
'.
-~'
, .~' ~
'4
-
1. ! If,""
(viii)
.,
~,:
i'~ .:~:.....'..:~
, ."f'I',
:,---"
. ~ .~ ,:
....~... , .4', . . :
.~ ........'
f'
. ' . l.. ...... "'~ .
t'':,~.'
~~ . r" .~ .:.;
... ..... ...: '" '.I
"' :
, -,' . .. ''Ii.''
.. '.., .\,'1
''!,
,I'
~.
"-
''r .......:
(ix)
(x)
Figure 9.6(b) SEM photomicrographs of 40:60 EPDM - polypropylene thermoplastic vulcanizates prepared with different curative levels: (vi) uncured blend; (vii) partially cross-linked;
(viii) partially cross-linked; (ix) fully cross-linked; and (x) fully cross-linked ...... = 10 kV;
..... = 2.01 kV.
to the fabricability of the compositions based on the phenolic cunng

systems.
(b) Diene rubber/polyolefin based thermoplastic elastomers. Thermoplastic
elastomers based on blends of polyolefins with diene rubbers such as butadiene rubber (BR), natural (isopropene) rubber (NR), NBR, styrene- butadiene rubber (SBR), etc. have been described elsewhere [15- 17]. These
Table 9.2 Effect of carbon black (N 327) and extender oil (SunparTM 2280)
Carbon
black
(phr)
0.0
80.0
0.0
80.0
80.0
Extender
oil (phr)
Tensile
strength
(MPa)
Stress
at 100%
strain
(MPa)
Young's
modulus
(MPa)
Elongation at
break
(%)
Shore
hardness
Tension
set (%)
0.0
0.0
80.0
80.0
160.0
27.5
31.0
15.2
23.0
15.2
11.3
14.3
6.4
7.2
4.8
162
120
47
23
11.5
560
410
550
530
490
48D
51D
29D
33D
74A
31
30
19
16
13
361
Table 9.3 Mechanical properties of different natural rubber/PP-based thermoplastic

elastomers
Property
Method
Shore hardness
Tensile strength (MPa)
Stress at 100% strain (MPa)
Ultimate elongation (%)
Tension set (%)
Tear strength (kN/m)
Compression set (22 (h:
at 23C (%)
at 100C (%)
Brittle point eC)
Ozone resistance at 40C
(l00ppm) of 0 3 '
Specific gravity
D2240
D412
D412
D412
D412
D624
D395
Method B
D746
D518
D297
60A
5.0
2.1
300
10
22
24
30
-50
70A
7.6
3.7
380
16
29
26
32
-50
10
1.04
10
1.04
90A
11.4
6.5
400
35
65
32
38
-45
50D
20.8
10.5
620
50
98
45
63
-35
10
1.02
10
0.99
'Ozone rating of 10 indicates no cracks after specified time.
compositions have fairly good initial tensile properties, and their thermal
stability is somewhat better than that of thermoset diene rubbers. Much of
the commercial development work has centered around thermoplastic
vulcanizates (TPVs) based upon NR/PP blends. Campbell, Elliott and
Wheelans [18] have prepared compositions of partially vulcanized NR.
Recently, Payne et al. [19] have reported improved mechanical properties
of fully vulcanized NR-PP based TPVs of different hardness. They found
that unlike thermoset natural rubber, these TPVs have very good resistance
to cracking induced by ozone (Table 9.3). The low-temperature brittle point
Table 9.4 Effect of hot-air aging on percentage retention of tensile properties of NR/PP-based
thermoplastic elastomers (TPEs)
Aging time (days at 100C)
TPE hardness
60A
70A
90A
50D
Property
99
104
98
100
100
98
103
107
92
101
108
93
15
30
91
65
110
87
90
110
91
103
93
95
109
93
80
80
126
76
86
113
86
104
93
80
102
91
40
68
85
43
80
56
66
99
60
66
103
70
362
increases as the NR content decreases. These compositions have fairly

good retention of tensile properties in hot air at 100C for up to one month
(Table 9.4).
(c) Butyl rubber/polypropylene-based thermoplastic elastomers. Butyl rubber and halogenated butyl rubbers have very low air and moisture permeability. This makes them well suited for use in tire, sporting goods and
medical applications. This also provides an opportunity to develop TPVs of
low air and moisture permeability.
In the early sixties, Gessler [6] first reported the preparation of
toughened (semi-hard-to-hard - not rubbery) PP compositions by dynamic
vulcanization. These compositions were prepared by melt blending a mixture of chlorobutyl rubber, PP and vulcanizing agent, zinc oxide. We later
expanded this work [20] by producing soft, rubbery thermoplastic compositions, with cross-linked particulate rubber phase (Figure 9.7). As the
Figure 9.7 Morphology of butyl-rubber/ PP-blend-based thermoplastic vulcanizate.
Table 9.S Air permeability of thermoset butyl rubber compared

with that of thermoplastic elastomers (TPEs). ASTM D1434 at
35C; sample thickness = 0.76 mm
Elastomer
ButyljPP TPE
EPDM/PP TPE
Thermoset butyl(inner liner)
Relative air permeability

1.45
4.44
1.00
363
11
10
~ 8
:cttl
Q)
Water
Air
E 6
CD
Cl.
Q)
II:
(j)
II:
~II:CO
COZ(/)
DVAs
Thermoset
elastomers
DVAs
Thermoset
elastomers
Figure 9.8 Comparison of permeability of thermoset rubbers with thermoplastic elastomers of

butyljPP- and EPDM/PP-blend-based thermoplastic vulcanizates. EP = EPDM/ polypropylene; NR = natural rubber; SBR = styrene- butadiene rubber; DVA = dynamic EPDM/
PP vulcanizate.
cross-linked rubber of such a composition is in the dispersed particulate

form, one would not expect typical butyl rubber impermeability from these
TPV compositions. However, by careful selection of compounding ingredients, it was possible to prepare butyl/PP-based or halobutyl/PP-based
TPVs of very low permeability (Table 9.5). The air and water permeabilities
(a)
(b)
(c)
Figure 9.9 (a) TEM image of elastomeric thermoplastic vulcanizate (TPV) showing micronsized cured rubber particles in a continuous PP matrix, (b) TEM image of a TPV containing
two elastomers, neoprene (large irregular particles outlined in black) and butyl (small dark-grey
particles) and (c) TEM image of a TPV with a cross-linked phase (lighter grey) surrounded by
an uncured phase (darker grey) in a continuous polymer phase (white).
364
Table 9.6 Synergism on combining elastomers in thermoplastic elastomers (TPEs). CR

chloropropene rubber; IIR = isobutyl ene-isoprene rubber
TPE property
Shore hardness (A)
ASTM no. 3 oil swell (70 h at lOOC) (%)
Tear strength (kN/m)
Compression set (22 h at 100C) (%)
Neoprene (CR)
Butyl (IIR)
4.7
170
58
21
12.3
66
7.1
220
60
75
19.3
47
CR
+ IIR (1:1)
7.5
250
66
44
24.5
52
of butyl-based dynamic vulcanizates are compared with those of conventional thermosets and of EPDM/PP-based TPVs in Figure 9.8.
Recently, Puydak and Hazelton [21] have prepared TPVs from rubber/
rubber/plastic triblends. In most of these compositions the best choice for
the plastic phase was PP. One of the elastomers is cross-linked under
dynamic vulcanization conditions during molten-state mixing with the
second elastomer and the plastic. Transmission electron microscopy (TEM)
micrographs of such compositions are shown in Figure 9.9. These TPVs
offer some advantages over two-component TPVs (Table 9.6).
9.3.2
NBR-nylon thermoplastic elastomer compositions
As in the case of the EPDM-polypropylene compositions, NBR-nylon

compositions were prepared by melt-mixing the polymers and other components in a (Brabender) laboratory-size mixer [22]. The temperatures for
mixing and molding varied with the melting point of the nylon used in each
composition.
Nitrile elastomers can be grouped into two categories: those which are
self-curing (i.e. cure at elevated mixing temperatures in the absence of curative), and those which are resistant to self-curing. (Self-curing at high temperatures is a result of thermal-oxidative instability.) To determine whether
or not an elastomer is self-curing, a sample can be mixed at 225C. Selfcuring elastomers generally gel and crumble (scorch) within 1-8 min whereas non-self-curing samples can be mixed for 20 min without crumbling.
(a) The effect of curatives. The effect of curatives such m-phenylenebismaleimide is complicated by the fact that some nitrile elastomers tend to
self-cure at the temperature of mixing. This is particularly true when
high-melting nylons are used with self-curing NBR. In such cases, the effect
of adding curative on the physical properties of the NBR-polyamide
vulcanizate is minimized as the properties of the composition are improved
by the cross-linking of the elastomer just from mixing. A much greater
365
curative effect is observed with the non-self-curing elastomer; however, the

best properties are obtained with the self-curing type of NBR.
It was found that the addition of a dimethylol phenolic compound also
substantially improves the properties of NBR/nylon blends. The curative
m-phenylenebismaleimide induces considerable gel formation in the elastomer phase and the improved product properties have been associated with
such gelation. However, it is surprising that, in the case of the dimethylol
phenolic curative, high-strength blends are obtained even when the gel
content of the NBR is as low as 50%. A portion of the dimethylol phenolic
compound is believed to react with the nylon to give chain extension or a
small amount of cross-linking. This could increase the viscosity of the
molten nylon to where it is more like that of the elastomer and thus mixing,
homogenization and elastomer particle size reduction are greatly improved:
In addition, some of the cross-linking m'llY be between the molecules of the
nylon and those of the elastomer, giVing nylon-NBR graft molecules. This
should improve homogenization and interfacial adhesion.
The effect of the curatives on .tension set is widely variable. This is
suggested by the data of Table ~9.7, where the various curatives give a wide
range of set values. This is in 'bontrast to what was observed with EPDMpolypropylene compositions Where curatives invariably reduced set values.
The reason for this variation 'of the effect of curative on tension set is not
understood, but it could relate to the extent to which the curatives promote
molecular linkages between the nylon and elastomer, rather than curing the
elastomer.
(b) The effect of elastomer characteristics. Elastomers of differing viscosities, differing nitrile contents and differing tendencies towards self-curing
were studied. There appears to be no simple relationship between the
strength of a composition and' the characteristics of its elastomer phase:
However, as mentioned above,' ~~lf-curing elastomers tend to give the best
strengths, and the effect of curative addition is greatest for the non-s~f~
curing elastomers. The effect of acrylonitrile content on hot-oil resistance'~s
similar to what is observed in the usual NBR vulcanizates, i:e:rhigh
acrylonitrile content gives low oil swelling. This is true both for the
self-curing and for the non-self-curing types of NBR. Oil-swell data for all
of the compositions are plotted in Figure 9.10.
( c) The effects of NBR.' nylon proportions. These effects are similar to

those obtained for the EPDM-polyolefin compositions. Increases in the
amount of elastomer in the compositions reduce stiffness and strength, but
improve resistance to permanent set. Also, extensibility can be increased
somewhat. If more than 50% of the composition is elastomer, compositions
Stress at 100%
strain (MPa)
2.5
7.4
3.7
6.1
Tensile strength
(MPa)
3.1
8.3
8.5
7.9
290
160
310
220
Elongation at
break (%)
72
15
51
31
Tension set
(%)
17
35
28
32
Shore hardness
(D)
12.3
21.7
34.9
25.3
True stress at
break (MPa)
"Blends comprise 40 parts of nylon 6,6-6,6,10 terpolymer (melting point 160C) and 60 parts Chemigum CHO N365 non-self-curing NBR (39% AN).
bAccelerated sulfur system contains 5 parts ZnO, 0.5 parts stearic acid, 2 parts tetramethylthiuram disulfide, 1 part morpholinothiobenzothiazole and 0.2
parts of sulfur per 100 parts of rubber.
'Activated bismaleamide is 3 parts of m-phenylenebismaleamide and 0.75 parts of 2,2-bisbenzothiazolyl disulfide per 100 parts of rubber.
dperoxide is 0.5 parts of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (90% active), Lupersol!)tL-101.
None (control)
Accelerated sulfurb
Activated bismaleimide c
Peroxided
Curative type
Table 9.7 Cured NBR/nylon blends" with different types of curatives
367
30.-~-----------------------------,
25
20
;;g
!!.....
"'ijj
15
.00
0
10
.0
0
20
30
40
50
60
AN content of rubber (%)
Figure 9.10 The effect of acrylonitrile (AN) content on hot oil (1S0C, ASTM no. 3) swelling.
D = Self-curing rubber; = non-self-curing rubber.
having tension set values less than 50% are obtained. However, excessive
amounts of elastomer can result in poor fabricability.
(d) The effect of plasticizers. Plasticizers can be added to compositions of
NBR and nylon. The effect is to soften the compositions and improve
fabricability. Surprisingly, the melting point of the nylon phase and its
crystallinity can either increase or decrease. The expected effect is to lower
the melting point for both [23,24]. However, another expected effect is for
plasticizer to decrease the viscosity of the nylon phase and this may promote
crystallization from the melt and enable formation of more perfect crystals.
In some cases these two effects tend to cancel. Plasticizer addition can either
increase or decrease ultimate elongation. Tensile strength generally decreases with the incorporation of plasticizer. Effects of plasticization are
indicated by the data in Table 9.8. Note that plasticizers which are more
compatible with the nylon phase tend to give compositions of better
mechanical integrity.
-25
-27
-28
-26
-34
6
0
0
Change in tensile
strength (%)
15
-31
-35
-38
-23
12
27
31
Peak
7
-3
-2
1
1
-7
-8
-3
Change in
hardness (D)
-7
-10
-9
-5
-10
-7
-7
-7
1
-7
-6
-4
-6
-12
-12
-6
Final
Change in
melting pointC (0C)
-18
-4
0
0
-11
-12
-22
-5
Change in
crystallinityc (%)
aRecipe: 50 parts nylon 6-6,6-6,10 copolymer (Zytel 63), 50 parts NBR (Hycar 1092-80), 10 parts plasticizer, 2.5 parts ZnO, 1.0 part tetramethylthiuram
disulfide and 0.50 part bisbenzothiazolyl disulfide. Properties without plasticizer: ultimate tensile stress = 11.6 MPa: ultimate elongation = 260%; Shore
hardness = 45 D; melting point = 152C (peak), 168C (final); heat of fusion (proportional to crystallinity) = 11.6 J/g of nylon.
~he symbol N or R indicates primary compatibility with nylon or rubber, respectively.
cMelting points and relative crystallinity were determined by differential calorimetry (Perkin-Elmer Differential Scanning Calorimeter DSC-lB, 10C/min,
20 mg sample).
Methyl phthalyl ethyl glycolate (R)

Butyl phthalyl butyl glycolate (R)
C 7 -C 9 trialkyl trimelitate (R)
Dioctyl phthalate (R)
Dibutyl sebacate (R)
N-Ethyl-o- and p-toluenesulfonamide (N)
2-Propyl-4,4' -bisphenol (N)
Nonylphenol (N)
Plasticizers (compatible phase b)
Change in
elongation
at break (%)
Table 9.8 The effect of plasticizers on the properties of nylon- NBR compositions a
369
(e) The effect offiller. Small amounts of clay have little effect on hardness,
stiffness or strength, though extensibility is reduced. Young's modulus
actually decreases. The effects are similar to those reported for carbonblack-filled compositions containing EPDM and PP. Again, it is thought
that the filler goes into the elastomer phase and it has the effect of both
stiffening this phase and increasing its volume. These effects are opposite and
largely cancel. Another effect of filler is to reduce severely the thermoplasticity and therefore to reduce the expected fabricability. To obtain the full
benefit of filler, plasticizers can be used to regain both thermoplasticity and
extensibility.
(f) Overall assessment of NBR-nylon thermoplastic elastomeric compositions.
The assessment is complicated by the large number of variations which are
possible. There are a number of types of nylon (polyamide (PA resins with
a wide range of melting points, polarities, etc. Also, the variations in the
types of NBR are great (nitrile content, viscosity, susceptibility to self-curing,
etc.). In addition, the effects of the different curing systems vary widely.
Nevertheless, conclusions can be drawn.
A variety of nylons of differing melting points and NBRs of differing
acrylonitrile contents can be used in broad ranges of proportions. The
compositions can be further altered by the incorporation of fillers and
plasticizers. Thus, a number of types of NBR/nylon-based elastomeric
materials, fabricable as thermoplastics and exhibiting fairly good strength
and excellent hot-oil resistance, can be produced in a range of hardnesses.
9.3.3
Other thermoplastic vulcanizates
A large number of elastomer/plastic combinations have been used in the

preparation of thermoplastic vulcanizates by dynamic vulcanization. In one
study, such compositions were compared in a systematic way [25]. Compositions were prepared as before, by vulcanization of blends during meltmixing. Various curative systems were used, and these were selected, for
each composition, following optimizational experimentation. Types of curative systems which were used are as follows:
dimethylol phenolic (P),

bismaleimide (M),
bismaleimide/2-benzothiazolyl disulfide (M/M),
bismaleimide/peroxide (M/O),
organic peroxide (0),
organic peroxide/coagent (O/C),
accelerated sulfur (S), and
soap/sulfur or soap/sulfur donor (SO/S).
P
S
P
P
M
P
0
SOlS
M/O
S
M/O
IIR
EPDM
PTPR
NR
BR
SBR
EVA
ACM
CPE
CR
NBR
P
S
S
M/M
M
M/M
M/O
SOlS
0
S
M/M
PE
P
M/O
P
M/M
M
M
M/O
SOlS
0
M/M
0
PS
S
S
P
M/M
M
M/M
M/O
SOlS
0
M/M
0
ABS
S
M/O
P
M/M
M
M/M
M/O
SOlS
0
M/M
0
SAN
P
P
S
M/M
M
M
M/O
SOlS
0
S
M
PMMA
P
M/O
M
M/M
M
M
0
SOlS
0
M
PBT
P
M/O
P
M/M
M
M
0
SOlS
0
P
M/O
M
M/M
M
M
0
SOlS
0
M/M
M
M/M
PC
PA
"Each composition is identified corresponding to a rubber-plastic (row-column) combination. There are 11 rubbers (rows) and 9 plastics (columns),
which give 99 (9 x 11) combinations.
PP
Rubber or plastic
Table 9.9 Curatives in rubber/plastic blends". For abbreviations see Appendix 9.A
371
In addition, thermal-oxidative stabilizers were used when appropriate.

All of the compositions contained elastomer and plastic in a weight
ratio of 60:40. The 60:40 ratio was chosen for screening [9] of elastomer-plastic pairs because when good compositions were obtained at this
ratio they were soft enough and elastic enough (tension set less than 50%)
to be considered elastomeric. The compositions studied are given in Table
9.9.
Ultimate tensile strength, ultimate elongation and tension set values of
the various compositions are given in Table 9.1O(a)-9.10(c). Those values
of tensile strength which are given in parentheses for chlorinated polyethylene/polybutyl terephthalate (CPE/PTB), chloropropene rubber/PTB
(CR/PTB) and CR/PA are in doubt because the elastomers (CPE and
CR) are insufficiently stable to withstand processing at the high melt
temperatures for PBT (polyester) and PA (high-melting nylon). The value
for ethylene vinyl acetate elastomer (EV A)/PBT is in doubt because
of the instability of the peroxide curative, which was probably used up
before its complete mixture with the molten blend. For similar reasons,
other tensile strength values may be low; however, for the purposes of
this work only the parenthetic values in Table 9.10 were removed from
consideration in attempts to correlate the measured properties of the
elastomer-plastic compositions with characteristics of the elastomer and
plastic components. Of course, the stability of a component in the presence
of the others is in itself a characteristic expected to correlate with blend
properties. In fact, one might say that an elastomer is technologically
incompatible with a particular plastic if the plastic must be processed at
temperatures higher than the temperature range in which the elastomer is
stable.
In the case of the ultimate elongation values given in Table 9.1O(b), the
parenthetic values are in doubt for the reasons stated above, and again such
values were not used in correlations between blend properties and characteristics of the components. Many of the tension set values are missing from
Table 9.10(c) because the measurement is impossible with compositions that
cannot be stretched to an elongation of at least 100%. Other values are
missing because the work was done early in the program before tension set
was routinely measured. The tension set value of 17% obtained for acrylate
elastomer-polycarbonate resin (ACM - PC) appears excessively low (high
elastic recovery). Young's modulus for this composition is also very low
(1.9 MPa). It appears that elastomer is the only continuous phase, yet the
composition is moldable as a thermoplastic. This behavior could be explained if the elastomer did not cure in the presence of molten PC resin, or
if the molten PC decomposed in the presence of the acrylate polymer,
possibly by transesterification. This would be another type of technological
incompatibility.
PP
21.6
24.3
22.7
26.4
20.8
21.7
17.8
4.0
12.3
13.0
17.0
Rubber or plastic
(a)
IIR
EPDM
PTPR
NR
BR
SBR
EVA
ACM
CPE
CR
NBR
14.9
16.4
12.1
18.2
19.3
17.1
18.9
4.2
10.5
13.8
17.6
PE
0.9
7.9
6.9
6.2
11.6
15.8
12.7
11.4
14.0
15.5
7.7
PS
1.7
3.2
11.0
5.8
9.9
10.8
9.6
9.4
13.7
12.8
13.6
ABS
4.3
5.6
13.4
8.4
8.3
8.1
12.9
7.7
17.9
12.5
25.8
SAN
5.4
6.0
4.7
1.8
3.5
5.7
9.3
6.2
17.0
8.9
10.8
PMMA
1.4
12.2
12.1
10.9
12.8
21.7
(3.4)
14.6
(13.0)
(13.5)
19.3
PBT
4.0
7.7
10.8
5.7
16.3
14.6
10.9
16.1
17.3
(3.2)
21.5
PA
1.3
15.7
2.5
6.7
2.1
7.3
9.6
5.2
20.8
14.7
18.2
PC
Table 9.10 Properties of 60:40 rubber-plastic thermoplastic vulcanizates (a) ultimate tensile strength (MPa), (b) elongation at break (%) and (c) tension
set (%). For abbreviations, see Appendix 9.A. Also, see Table 9.9, footnote a. Figures in parentheses were removed from consideration in attempts to
correlate the measurements of the elastomer-plastic compositions with characteristics of the elastomer and plastic components
IIR
EPDM
PTPR
NR
BR
SBR
EVA
ACM
CPE
CR
NBR
(c)
IIR
EPDM
PTPR
NR
BR
SBR
EVA
ACM
CPE
CR
NBR
(b)
55
33
31
23
16
20
24
27
30
36
380
530
210
390
258
428
319
18
314
141
204
58
37
36
27
28
312
612
280
360
229
240
349
20
221
390
190
70
3
69
35
85
73
89
166
20
140
67
20
65
18
18
15
56
64
70
102
144
197
96
164
55
91
7
5
10
14
12
12
109
18
151
7
196
82
6
6
10
58
5
15
59
21
146
5
56
26
56
59
44
25
34
30
60
42
121
201
160
163
160
(6)
320
41
40
156
102
47
62
52
102
(126)
135
(159)
65
350
17
85
161
66
5
21
5
19
81
140
135
91
130
374
9.3.4
Characteristics of elastomers and plastics for correlations

with blend properties
Properties of elastomer/plastic blends have been correlated with various

properties and characteristics of elastomers and plastics described below.
Values are given in Table 9.11.
(a) Dynamic shear modulus. The dynamic shear modulus, G', was taken as
a measure of stiffness. It was measured by means of a torsion pendulum with
specimens whose dimensions were selected to give test frequencies between
0.5-2 Hz. It was selected rather than Young's modulus because of convenience. When considering such widely varying materials as elastomers and
hard plastics, it is difficult to find a convenient test condition (rate of
loading) appropriate for both elastomers and plastics. The shear moduli of
the hard and soft phases (along with elastomer-to-plastic proportions) were
correlated with the shear moduli of blends.
(b) Tensile strength of the hard-phase material. This property was considered because it represents a limit for the strength of the elastomer/plastic
blend. Yield stress, rather than stress at break was used as tensile strength
for crystalline materials because breaking occurs only after necking and
drawing. (Generally, the elastomeric blends do not exhibit drawing-necking
behavior.) The values in Table 9.11 were determined in the same way as for
the elastomer/plastic blends, by using molded samples which had been
equilibrated against laboratory air. For nylon many of the literature values
relate to dried samples and are therefore somewhat higher than the values
shown here.
(c) Crystallinity. The weight fractions of crystallinity, ~, of many of the
plastics are also given in Table 9.11. The values in Table 9.11 are approximations based on the densities of the materials. The reasons for
considering crystallinity were empirical; however, interesting correlations
between hard-phase crystallinity and certain blend properties have been
obtained.
(d) Critical surface tension for wetting. This parameter, Yc, was originally
used as an estimate of polymer surface energy by Zisman [26]. It was
estimated by determining contact angles of various liquids against a given
polymer surface. The contact angles were plotted as functions of the surface
tension of the test liquids, and the surface tension of liquid corresponding
to an extrapolated contact angle of zero was taken as the critical surface
tension for wetting (or spreading). At one time, it was believed that Yc was
approximately the surface tension Ys of solid polymer. At any rate, we felt
that the difference between the critical surface tension for wetting (for the
30.0
31.7
42
58
58
61.8
53.3
46
66.5
0.99
0.32
0.17
0.52
0.93
909
510
860
0.46
0.97
520
760
1170
926
1130
Dynamic shear
modulus (MPa)
28
29
33
38
38
39
39
39
42
27
28
31
31
32
33
34
37
37
38
39
Critical surface tension

for wetting (mN/m)
570
460
417
454
416
460
342
778
356
350
290
Number of chain
atoms b
0.63
0.7
0.00
0.00
0.00
0.00
0.31
0.25
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Weight fraction of
crystallinity
"Determined by torsion pendulum at about 1 Hz. Rubbers were not vulcanized.

bCritical molecular length for entanglement.
CABS was considered as SAN containing BR particles: thus stress at break for ABS was considered to be the same as for SAN. The somewhat increased
elastomer concentration (over 60 wt%) should have only a small effect on the ultimate properties.
SBR
EVA
ACM
CPE
CR
NBR
BR
NR
PTPR
EPDM
IIR
PA
PC
PBT
PE
PS
ABS c
SAN
PMMA
PP
Stress at break
(MPa)"
Table 9.11 Approximate polymer characteristics. For abbreviations of polymers, see Appendix 9.A
376
elastomer and the plastic) might be a rough estimate of the interfacial

tension between the elastomer and plastic during melt-mixing. Interfacial
tension is a factor which determines, at least in part, the droplet size of one
liquid dispersed in another [27]. Lower surface tensions give smaller
droplets (which should result in smaller particles of one polymer dispersed
in the other after mixing and cooling).
The interfacial tension between two immiscible monomeric liquids is
approximated by the difference between the two surface tensions. Unfortunately, this is not the case for polymers. However, there is a hypothetical
surface tension Yx, which is characteristic of each polymer listed in Wu's
review of interfacial tension between molten polymers [28]. If the value of
Yx for one polymer is subtracted from that of the other, the interfacial
tension is estimated fairly reliably. The hypothetical values Yx correlate well
with the values of Ye. It is also interesting that the critical surface tension Ye
for wetting correlates with solubility parameter and that the differences
between solubility parameters (<5 1 - <5 2 ) of the polymers of a two-phase
system correlate with interfacial tension. Indeed, Helfand and Sapse [29]
have given a theoretical basis for this.
From all of this we conclude that L\Ye, the difference between critical
surface tensions for wetting of each of two polymers, may be at least a
qualitative estimate of the interfacial tension, Y12. The lower the difference
L\Ye (which we sometimes call the surface energy mismatch), then the smaller
should be the particles of one molten polymer dispersed in the other. Also,
a low surface energy mismatch should give better wetting, better interfacial
adhesion and increased diffusion of the polymers across the interface.
Some of the values of Ye listed in Table 9.11 were taken from the literature
[30]. Those values not available were estimated on the basis of the
correlation between solubility parameter (j and Ye.
(e) Critical entanglement spacing. The critical entanglement spacing, N e ,
is defined as the number of polymer chain atoms that corresponds to a
molecular weight sufficiently large for entanglements to occur between
molecules of undiluted polymer. It has been measured as the molecular
weight where the slope of a plot of In viscosity versus In molecular weight
changes from 1.0 to 3.4, the change being associated with intermolecular
entanglements.
The reason for considering entanglement spacing as a parameter to
correlate with blend properties was empirical. It was found that dynamically
vulcanized elastomers that have low values of Ne gave the higher quality
blends with plastics [25]. Although this was an empirical observation, one
might speculate why such elastomers give the best blends (with respect to
ultimate properties).
It has been observed that when polymers are blended together fibrous
structures appear which then break up into polymer droplets [31,32]. We
Rubber domain
Interface
377
Crystalline
plastic domain
Figure 9.11 Schematic diagram of adhesion promoted by interfacial entanglements of loops

between crystalline domains.
believe it likely that polymers whose molecules are more entangled might be
drawn into finer 'fibers', during the early phase of mixing, to give emulsions
of polymer droplets of smaller size. Of course, after dynamic vulcanization
these droplets would become very small vulcanized rubber particles.
Another explanation could be that a tendency for entanglement might
promote adhesion if some of the entanglement occurred across the interface
between the molecules of the different polymers. After vulcanization and
after cooling of the composition such entanglement-derived locked-in loops
should improve interfacial adhesion. A schematic visualization of this is
shown in Figure 9.11.
Values of Nc obtained under the same conditions, for all of the elastomers, are not available in the literature. However, it is possible to calculate
values of Nc from the chemical structure of the elastomer molecules by using
a modified method of Aharoni [33]. The calculated values appear in Table
9.11.
9.3.5
The correlation between blend properties and the characteristics

of blend components
The stress at break, UB' was correlated with the component characteristics
as a relative ultimate tensile strength, UB/UH where U H is the strength of the
hard-phase (plastic) material, believed to be a limiting factor.
The effects on relative tensile strength, UB/UH , ultimate elongation, SB' and
tension set, ss, are plotted according to regression equations in Figure 9.12.
In each case a property is plotted as a function of one of the three
378
60
I--
~
~
en
OJ
I--
----------
~~
0
600
~
~
OJ
1.0
J:
\:)
0
0
15 200
L1YSH
(mN/m)
800 0
Nc
0.6
Wc
Figure 9.12 The effect of pure-component characteristics on the properties of thermoplastic

vu1canizate compositions: (JB/(JH = the relative tensile strength; BB = ultimate elongation;
Bs = tension set; dYSH = the difference between the critical surface tension for wetting Ye of the
rubber and that of the plastic; Ne = the critical molecular length (number of chain atoms of
rubber molecules) for entanglement; We the weight fraction of crystallinity of the hard-phase
material.
characterizing parameters (~YSH' N e , or We) with the other two variables

held constant, each at a desirable level.
If we accept Figure 9.12 as an overall view of the effects, certain
conclusions can be drawn.
an increase in the crystallinity of the plastic material component improves
both mechanical strength and elastic recovery;
elastomers of lower Ne give compositions of greater mechanical integrity;
and
compositions, in which the surface energies of the elastomer and plastic
phases are closely matched, are strong and extensible.
As stated previously, matching of surface energies should give lower interfacial tensions, resulting in smaller elastomer particles which act as smaller
stress-concentrator flaws and so improve both high strength and extensibility.
Thus, based on a few characteristics of the pure elastomer and plastics,
elastomer/plastic combinations can be selected with a good probability of
success to give thermoplastic vulcanizates (by dynamic vulcanization) of
379
good mechanical integrity and elastic recovery. The best compositions are
prepared when the surface energies of the elastomer and plastic material are
matched, when the entanglement molecular length of the elastomer is low
and when the plastic material is crystalline. It is necessary that neither the
plastic nor the elastomer decomposes in the presence of the other at
temperatures required for melt-mixing. Also, a curing system is needed
appropriate for the elastomer under the conditions of melt-mixing.
9.3.6
Technological compatibilization of NBR/polyolefin blends by

elastomer- plastic graft formation
Were it not for their gross mutual incompatibility (in the thermodynamic
sense), a combination of a polyolefin resin with NBR might be a good choice
of materials from which to prepare oil-resistant thermoplastic elastomer
compositions by dynamic vulcanization. Early work with these materials
demonstrated only marginal success in obtaining good mechanical properties for such compositions [34]. This was probably because of the large
surface-energy difference between the two types of polymers. Mutual wetting
between the polymers appeared incomplete; relatively large particles of
cured elastomer dispersed in polyolefin resin formed during mixing and
dynamic vulcanization. An approach to technological compatibilization, in
addition to dynamic vulcanization, was thus sought [35, 36].
It is now generally accepted that a block copolymer can compatibilize
mixtures of the 'parent' homopolymers. The block copolymers act as macromolecular surfactants to promote and stabilize the emulsion of the molten
homopolymers [37- 39]. Figure 9.13 is an idealized visualization of this.
Interface
Figure 9.13 Idealized compatibilizing block copolymer molecule.
380
It has been found that a dimethylol phenolic compound (such as 'phenolic resin' curative SP-1045) can be used technologically to compatibilize a
mixture of polyolefin and NBR. This compatibilization could be the result
of the formation of a block copolymer of the type visualized in Figure 9.13.
Such a compatibilizing block copolymer could be formed by the following
reaction scheme:
OH
HOCH2-q CH 20H
-H 20
---+
~I
Lewis acid
R
Quinone methide
Dimethylol-phenoic compound
'C~
~fH2qR
CH,
C
II
CH
~
?' I
~
Phenoic-modified polypropylene
,~
~I
II
CH
CH20H
OH
/C-CH2- q C H2 -C
OH
C......... C-CH2- q
?' C H20H
h-
l~rO
,~
Polypropylene
~CH,
/CH2,
CH2-CH2
CH
I
CN
/CH20H~
CH CN
I
I
CH-CH2
Compatibilizing block copolymer

or
'
OH
~-CH2-qCH2-INBRI
?'I
~
Scheme 9.1
The scheme requires the presence of olefinic unsaturation in the polypropylene molecules. Indeed, to satisfy demands of strict polymerization stoichiometry, there is, on the average, one double bond per polypropylene molecule
unless hydrogen is used to control molecular weight. The scheme is similar
to that proposed long ago for the phenolic-resin curing of diene elastomers
[40-42].
In practice, the poly olefin resin is treated with about 1-4 parts of a
phenolic curative (e.g. SP-1045) per 100 parts of polyolefin resin (e.g.
polypropylene) in the presence of 0.1-0.5 parts of a Lewis acid (e.g. SnClz)
at a temperature of about 180C-190C. The phenolic-modified polyolefin
is then melt-mixed with NBR for a sufficient time for compatibilization to
381
occur with the formation of a blend of improved homogenization. Then,

with continuing mixing, curative for the elastomer is added. (This can be
additional dimethylol phenolic resin curative.) If the NBR contains a small
amount (c. 5%) of an amine-terminated liquid NBR, ATBN (e.g. Hycar
1300X16-B, F. Goodrich Co.) the properties of the compatibilized blend are
even better.
The formation of polymer-polymer grafts can be accomplished by a
number of other chemical means, in addition to the above use of dimethylol
phenolic derivatives. In some cases the results are even better. Such a case
is the use of maleic-modified PP to form the block-polymeric compatibilizing agent by reaction with the amine-terminated liquid NBR. In this case,
PP is modified by the action of either maleic acid or maleic anhydride in
the presence of decomposing organic peroxide [43,44]. During the process,
the molecular weight of the polypropylene becomes greatly reduced as the
molecules thereof acquire pendent succinic anhydride groups:
Polypropylene
Maleic-modified polypropylene
peroxide
or
I(COOH
COOH
Scheme 9.2
If part of the polypropylene in a NBR - PP composition is maleicmodified, and if part of the NBR is amine terminated, then compatibilizing
amounts of NBR - PP block copolymers form in situ during melt-mixing:
o
II
NHR 1NBRI_
C-OH
NR1NBRI
r:
II
o
Compatibilizing block copolymer
Scheme 9.3
Only a small amount of compatibilizing block copolymer is needed to

obtain a substantial improvement in the properties of a blend. The data of
3.75
0.50
0.00
3.75
0.50
0.00
25
11
10
1.2
209
19
12.0
12.0
200
110
8.8
50
45
5
50
50
399
215
67
483
25.5
12.3
188
440
40
138
64.1
2.5
1.25
22.0
12.3
185
400
40
110
54.9
45
5
37.5
12.5
3.75
0.50
45
5
43.75
6.25
3.75
0.50
15.2
12.0
223
290
40
59
34.6
0.62
45
5
46.88
3.12
3.75
0.50
12.4
12.1
212
170
45
33
18.4
0.16
45
5
49.22
0.78
3.75
0.50
461
25.7
12.5
184
430
42
136
61.7
45
5
25
25
3.75
0.50
686
26.7
12.9
237
540
45
171
86.5
10
50
3.75
0.50
45
5
"Parts by weight.
bPolypropylene = Profax 6723.
cSee text, section 9.3.6.
dNitrile rubber (NBR) = Hycar 1092-80 nitrile rubber.
'90% by weight of Hycar 1092-80, 10% by weight of Hycar ATBN 1300 x 16 liquid nitrile rubber.
'SP-1045 is a dimethylolphenolic vulcanizing agent.
gATBN = Hycar'" ATBN 1300 x 16 amine-terminated liquid nitrile rubber. A quantitative reaction is assumed between ATBN and maleic-modified
polypropylene (which is assumed to be present in excess).
hBreaking energy values were obtained from the stress-strain curves.
Properties:
Young's modulus (MPa)
Elongation at break (%)
Tension set (%)
True stress at break (MPa)
Breaking energy (J/cm3)h
Improvement in breaking energy as a result of
compatibilization (%)
Recipe":
Polypropylene b
Maleic-modified polypropylene C
NBR d
NBR masterbatch'
SP-I045'
SnCl z '2H zO
ATBN as percentage of NBR (rubber grafted to
polypropylene (%g
Stock
Table 9.12 Properties of compatibilized-blend dynamic vulcanizates as a function of the amount of rubber grafted to plastic
383
Table 9.12 relate to compositions in which 10% of the PP was modified by

the action of 5 parts of maleic anhydride in the presence of 0.87 parts of
Lupersol-101 peroxide per 100 parts of PP at 180C-190C. Varying
amounts of the NBR were replaced by amine-terminated liquid NBR. As the
maleic-modified PP was generally in stoichiometric excess, it can be assumed that essentially all of the amine-terminated elastomer was grafted to
some of the polypropylene. After each compatibilized blend was prepared it
was dynamically vulcanized and subjected to the usual treatment for
molding and testing.
The data of Table 9.12 indicate that improved blend properties are
obtained when as little as 0.16% of the elastomer is grafted to PP. Also, after
about 2%-3% of the elastomer is grafted to the polyolefin, additional graft
formation gives almost no further improvement. It should be noted that the
mechanical properties of the compatibilized dynamically vulcanized blends
of NBR and PP can be about as good as those of dynamically vulcanized
ethylene-propylene-diene monomer (EPDM) and PP.
(a) Resistance to hot oil and brittle point. The hot-oil resistance and brittle
point of a compatibilized NBR - PP thermoplastic vulcanizate prepared by
dynamic vulcanization are shown in Table 9.13 (stock 1). Though the hot-oil
resistance is excellent, low-temperature performance is somewhat lacking.
It has been found that the low-temperature brittle point can be reduced
with minimum sacrifice of hot-oil resistance by blending the compatibilized
Table 9.13 Compatibilized NBR-polypropylene composition blended with EPDM-polypropylene composition
Stock
NBR-polypropylene composition" (wt%)

EPDM-polypropylene composition b (wt%)
Properties:
Stress 100% strain (MPa)
Hardness (A)
Tension set (%)
ASTM no. 3 oil volume swelling (%)'
Brittle point (0C)
100
0
50
50
0
100
22.6
11.2
585
93
48
155
22
-24
15.9
7.9
510
87
23
97
32.5
-47
8.6
4.4
415
68
10
44.3
62.5
<-60
"Recipe for the NBR-polypropylene composition is: Profax 6723 polypropylene, 45 parts by
weight; maleic-modified polypropylene, 5 parts; Hycar 1092-80 NBR-Hycar ATBN 1300 x
16 liquid NBR (90: 10),50 parts; SP-1045 phenolic curative, 3.75 parts; SnCI 2 '2H 2 0, 0.50 parts;
Naugard 495 stabilizer (added after vulcanization), 1.0 part.
bCommercially available Santoprene(j( 201-73 (Advanced Elastomers Systems).
CHot-oil swelling, 70 h at 100C.
384
NBR-PP composition with a commercially available thermoplastic elastomer based on PP and vulcanized EPDM. The two thermoplastic elastomer compositions are mutually compatible, as they are both based on a
continuous phase of PP. The results given in Table 9.13 indicate that the
mechanical properties of the blend are about the average of the two
components, but, surprisingly, the hot-oil resistance is better than the
average.
(b) Overall assessment of compatibilized NBR-PP thermoplastic vulcanizates. The mechanical properties of these compatibilized blends can
approach those of dynamically vulcanized EPDM/PP blends and, in addition, excellent hot-oil resistance can be achieved. The NBR-based compositions may not have good enough resistance to low-temperature
embrittlement for some applications, but compositions based on EPDM
and PP can be blended with the NBR - PP composition to improve the
brittle point without causing severe losses of other attributes.
9.3.7 Blends of thermoplastic vulcanizates based on dissimilar plastics
In this section we describe thermoplastic elastomer compositions comprising technologically compatibilized blends of TPVs based on nylon and
on PP. The nylon- and the PP-based thermoplastic vulcanizates were
previously prepared by dynamic vulcanization. The compositions were
technologically compatibilized by the presence of chemically-modified PP
which presumably reacted with small portions of the nylon to form
compatibilizing amounts of nylon-PP graft-linked copolymer [35]. Components of the blends of thermoplastic vulcanizates are described below.
(a) Prepared components of the dissimilar-plastics compositions. A 50: 50
blend of EPDM and PP was dynamically vulcanized by 5 parts (per 100
parts of combined polymers) of SP-1045 dimethylol phenolic curative in the
presence of 1 part of SnCI 2 2H 2 0 at 180C-190C. The composition was
designated EPDM - PP TPV.
A 65:35 blend of NBR and nylon 6,6-6 copolymer (melting point 213C)
was treated with 1.3 parts (per 100 parts of combined polymers) of SP-1045
phenolic curative during its mixing at 215C. (Flectol H antidegradant was
used at a level of 2 parts per 100 parts of polymer.) The composition was
designated NBR - NY TPV.
A 50:50 blend of a millable, vulcanizable polyurethane rubber (AdipreneC) and nylon 6/6-6/6-10 terpolymer (melting point 163CZytel63) was dynamically vulcanized at 180C by the action of 1.0
m-phenylenebismaleimide in the presence of 0.5 parts of L-101 organic
peroxide per 100 parts of combined polymers. The product was designated
PU-NY TPV.
385
A 50:50 blend of Hydrin 400 rubber and the same nylon 6/6-6/6-10
terpolymer was dynamically vulcanized at 170C-180C by the action of
1.67 parts of zinc stearate, 1.0 part of bisbenzothiazole disulfide (MBTS),
and 0.4 parts of sulfur per 100 parts of combined polymers, in the presence
of 1.0 part of Flectol H antidegradant. The product was designated
ECH-NY TPY.
This functionalized polymer was prepared by melt-mixing 100 parts of
polypropylene with 5 parts of maleic acid in the presence of L-101 peroxide
(added after the acid and polymer were well mixed) at 180C for about
3 min. The product was designated MA-g-PP.
(b) Blends of thermoplastic vulcan iza tes. Blends of the various TPV s (with
and without the chemically modified, compatibilizing, functionalized polypropylene) were prepared by melt-mixing the ingredients in a Brabender or
Haake Rheomix internal mixer at about 10C above the melting point of
the nylon used in each case.
Properties of molded sheets of the mixtures of TPVs are given in Table
9.14. These test results indicate that nylon-based TPVs containing a variety
of different types of rubbers can be used in the compatibilized blends. A
substantial improvement in properties is obtained in each case. (Note the
comparison between the control stocks containing added unmodified PP
Table 9.14 Compatibilization of polypropylene-nylon compositions a

Stock
Recipe:
Dynamically vulcanized EPDM-PP
composition
Dynamically vulcanized NBR-nylon
composition
Dynamically vulcanized polyurethanenylon composition
Dynamically vulcanized epichlorohydrin
rubber-nylon composition
Polypropylene
Maleic-modified polypropylene
Properties:
Young's modulus (MPa)
Tension stress (%)
50
50
50
50
50
50
50
50
50
50
50
10
50
10
16.1
14.0
132
170
40
43
10
26.9
16.5
147
310
39
110
10
9.2
173
73
16
aComponent blends are defined in the text, subsection 9.3.7(a).
10
19.6
11.8
157
270
52
73
10
11.9
9.3
206
230
40
39
22.0
12.0
199
340
50
97
386
(stocks 1, 3 and 5) and the experimental stocks containing the maleicmodified PP (stocks 2, 4 and 6).)
It is believed that the maleic-acid-modified PP molecules contain pendent
succinic anhydride groups which react with amine groups in the nylon to
form compatibilizing amounts of a graft-linked nylon- PP block copolymer
[44]. It should be noted that a number of other chemical modifications of
PP have also given results similar to those obtained with maleic-acid
modified PP [35].
From this work, one can conclude that compositions which have excellent mechanical properties can be prepared by melt-mixing thermoplastic
vulcanizates that have been previously prepared by dynamic vulcanization.
Excellent mixed TPV compositions can be obtained even when the rubbers
and plastics are mutually grossly incompatible with respect to thermodynamic considerations. In such cases, however, it appears to be necessary
that a compatibilizing agent be present in the mixture to promote the
interaction between the thermoplastic materials.
The rubber associated with one of the thermoplastic components can
differ greatly from the rubber associated with the other thermoplastic
component. Thus compositions can be produced that have good mechanical
properties and that can obtain both differing thermoplastic resins and
differing rubbers. As a result, the possible combinations of components for
TPV compositions has been greatly expanded.
9.4
Technological applications
The elastomer/plastic blends discussed here are intended for use as thermoplastic elastomers. These are materials which have many of the properties
of conventional vulcanized (thermoset) elastomers but are processable and
can be fabricated into parts by the rapid techniques used for thermoplastic
materials.
Thermoplastic processing is far more economically attractive than traditional multistep elastomer processing. In the case of conventional thermoset
elastomer processing, the producer of elastomeric articles purchases elastomer, fillers, extender oils or plasticizers, curatives, antidegradants, etc.;
these ingredients must then be mixed and uniformly dispersed; after a stock
is mixed, it is then shaped by extrusion, calendering, etc.; the crudely shaped
preform is then vulcanized in its final shape by heating it in a mold
contained by a press and heated for vulcanization, which can take a long
period of time. Mold flash or overflow, as well as rejected parts, are not
economically reprocessable.
On the other hand, a part produced from a thermoplastic elastomer is
shaped or molded into its final shape in a single step. Mold flash and
rejected parts can simply be ground and reused. Detailed comparisons have
387
Table 9.15 Properties of various types of elastomer compositions
Property
Hardness (A)
Volume swelling in ASTM
no. 3 oil (74 h at 100C) (%)
Compression set (ASTM
method B, 22h at 100C (%)
Upper use temperature ("C)
Type of processinge
Partially
vulcanized
EPDM/PP
blend"
Completely
vulcanized
EPDM/PP
blend b
Neoprene
vulcanizate
Ester-ether
copolymer
thermoplastic
elastomerC
77
6.6
200
80
9.7
400
80
9.7
400
92
25.5
450
50
35
30
70
100
TP
39
125
TP
35
110
CV
33
125
TP
"TPR-1700 thermoplastic elastomer (Uniroyal).

bSantoprene thermoplastic elastomer (advanced elastomer systems).
CHytrel thermoplastic elastomer (duPont).
dSample disintegrated.
eTP = thermoplastic processing; CV = conventional vulcanization.
shown time and again that thermoplastic processing is more economical

than thermoset elastomer processing [4] and this provides the economic
incentive for the development of thermoplastic elastomers.
The commercial compositions based on melt-mixed blends of completely
dynamically vulcanized EPDM and PP, as described herein, have many of
the excellent properties of polyurethane and polyether-ester copolymer
thermoplastic elastomers. In addition, the properties of these commercial
grades of completely vulcanized EPDM - PP thermoplastic vulcanizate
materials compare favorably with those of conventional vulcanized
speciality rubbers (CR, EPDM, and chlorosulfonated polyethylene (CSM)).
With respect to fatigue life, the commercial EPDM-PP thermoplastic
vulcanizates outperform the conventional speciality elastomers. Comparisons between selected properties of three thermoplastic elastomers and
those of a conventional elastomer are given in Table 9.15.
9.4.1
Processing-fabrication technology
The processing of a rubber/plastic blend composition into a finished part is

a function of the melt rheology of the composition, the temperature and
shear rate. Processing is also a function of the strength of the molten
material under the strain resulting from its processing, i.e. a function of its
resistance to melt fracture. Melt fracture, during extrusion, can give rise to
very poor surface textures or even functionally useless parts.
The melt rheology of an elastomer/plastic blend composition is related to
that of the plastic material in the idealization given in Figure 9.14. At high
388
Rubber/plastic blend
Plastic
Shear rate (S-1) -
Figure 9.14 The relationship between viscosity and the shear rate for a plastic and its blend
with rubber.
shear rates, the viscosity-shear-rate profiles are similar for both products.
However, at very low shear rates, the viscosity of the blend can be very high.
In the case of dynamically vulcanized elastomer/plastic melt-mixed blends
containing high levels of elastomer, the viscosity can approach infinity when
the shear rate approaches zero (presumably owing to cured elastomer
particle-particle interference). Under the conditions of melt extrusion, the
molten material undergoes rapid flow in the die. Then, as the material passes
out of the die, the rate of deformation drops to zero and, because the
viscosity approaches infinity, little or no die swell is observed. The dimensions of extrusion profiles of such materials are thus easily controlled. This
shows that the melt viscosity of an elastomer/plastic blend is highly
shear-rate sensitive.
The effect of temperature on the viscosity of an EPDM - PP thermoplastic elastomer at high levels of elastomer is illustrated in Figure 9.15. The
viscosity of this type of blend is relatively temperature insensitive. (However,
compositions based on other types of thermoplastic show more temperature
sensitivity.) Figures 9.l4 and 9.15 indicate that, in processing certain
elastomer plastic blends by flow techniques such as extrusion and injection
molding, shear rates should be kept high enough to facilitate adequate flow.
The high melt viscosity of these products can be advantageous in
processing [4]. It can provide high melt integrity or 'green strength' and
permit the retention of shapes of parts produced by extrusion or blow
molding. The high melt viscosity and low die swell are also helpful in
calendering sheet and film products. For injection-molded parts, fast injection rates (under high pressure) give lower viscosities owing to the high
sensitivity of viscosity to shear rate. Thus, fast injection rates facilitate rapid
and complete mold filling. When the mold is filled, the shear rate is reduced
389
100
Shear rate (S-1)
1000
Figure 9.15 The effect of temperature on the EPDM - PP viscosity-shear-rated relationship for
a typical thermoplastic vulcanizate.
to zero. This increased viscosity, which can approach infinity, enables more
rapid extraction of the part from the mold. The overall effect is a faster
injection-molding cycle. In addition, the moderate temperature sensitivity of
the viscosity of such a composition gives a 'broad temperature window' for
processing. Typical injection-molding and extrusion conditions for an
EPDM/PP blend are given in Tables 9.16 and 9.17.
In addition to the above (injection molding, calendering, extrusion, and
blow molding), foaming, thermoforming, and compression molding of
olefinic elastomer/plastic blends have been reviewed [1]. However, it should
be noted that processing conditions vary widely with equipment mold
designs, specific blend compositions, etc. The best conditions for the
production of a given part must be confirmed by prototype runs in factory
equipment.
Table 9.16 Injection-molding conditions for EPDM/polypropylene-based
thermoplastic elastomeric blends
Rear-zone barrel temperature Cc)
Center-zone barrel temperature (DC)
Nozzle temperature Cc)
Melt temperature CC)
Injection pressure (MPa)
Hold pressure (MPa)
Back pressure (MPa)
Screw speed (rpm)
Injection speed
Injection time (s)
Hold time (s)
Total cycle time (s)
180-220
205-220
205-220
20-65
35-140
30-110
0.7-3.5
25-75
Moderate-fast
5-25
15-75
20-100
390
Table 9.17 Extrusion conditions for EPDMjpolypropylene-based elastomeric blends
Rear-zone barrel temperature caC)

Center-zone barrel temperature caC)
Front-zone temperature caC)
Adapter temperature (DC)
Die temperature (0C)
Melt temperature caC)
Screw speed (rpm)
9.4.2
175-210
175-210
190-220
200-225
205-225
205-235
10-150
End-use applications
New techniques of melt-mixing blends of elastomers and plastics, dynamically vulcanized, and employing compatibilizing agents have greatly expanded the number of useful thermoplastic elastomers. It is probable that
this expansion will continue and accelerate. Potential and proven applications of these more recently developed thermoplastic elastomers are:
for mechanical rubber goods applications: caster wheels, convoluted
bellows, flexible diaphragms, gaskets, seals, extruded profiles, tubing,
mounts, bumpers, housings, glazing seals, valves, shields, suction cups,
torque couplings, vibration isolators, plugs, connectors, caps, rollers,
oil-well injection lines, handles, and grips;
for under-the-hood automotive applications: air-conditioning hose cover,
fuel-line hose cover, vacuum tubing, vacuum connectors, body plugs,
seals, bushings, grommets, electrical components, convoluted bellows,
steering gear boots, emission tubing, protective sleeves, shock isolators,
and air ducts;
for industrial hose applications: hydraulic (wire braid), agricultural spray,
paint spray, plant air-water, industrial tubing, and mine hose;
for electrical applications: plugs, strain relief, wire and cable insulation
and jacketing, bushings, enclosures, connectors and terminal ends.
(a) Emerging applications. Because of the high level of product-development activity sustained by the industry, a number of new thermoplastic
elastomeric compositions are emerging. Efforts are directed towards the
development of thermoplastic elastomeric blend compositions which are
more resistant to hot oil, compositions which are more resistant to higher
temperatures, and, eventually, compositions which are more resistant to
both hot oil and higher temperatures. The combination of the two techniques discussed in this chapter have opened the door to many new product
opportunities.
As stated throughout this chapter, dynamic vulcanization greatly improves the properties of elastomer/plastic blends. However, in addition to
391
dynamic vulcanization, technological compatibilization by the incorporation of block-copolymer compatibilizers has greatly increased the number
of elastomer-plastic combinations which can give reliably good mechanical
properties. It is no longer necessary that the elastomer and thermoplastic be
of similar surface energy. Thus, combinations can be selected on the basis
of the properties of the individual elastomer and thermoplastic components.
For example, a high-melting crystalline plastic can, at least in principle, be
combined with an elastomer which has a very low brittleness temperature
to produce a thermoplastic elastomeric material with a very wide range of
end-use temperatures. Alternately, the high-melting crystalline plastic can be
combined with an oil-resistant elastomer of good thermal oxidative stability
to give a thermoplastic elastomeric material suited for applications in highly
aggressive environments.
Appendix 9.A
9.A.l
Abbreviations
9.A.1.1
ABS
ACM
BR
CPE
CR
CSM
ECH
EPDM
EVA
IIR
IR
NBR
NR
NY
PA
PBT
PC
PE
PMMA
PP
PS
PTPR
SAN
SBR
TPE
9.A.1.2
M
M/M
M/O
O/C
Polymers and rubbers
Styrene-acrylonitrile copolymer containing polybutadiene

Acrylate rubber
Butadiene rubber
Chlorinated polyethylene
Chloroprene rubber, i.e. neoprene
Chlorosulfonated polyethylene
Epichlorohydrin rubber
Ethylene-propylene-diene monomer rubber
Ethylene-vinylacetate elastomer
Butyl rubber (isobutylene-isoprene rubber)
Synthetic isoprene rubber, or NR
Nitrile rubber (acrylonitrile-butadiene copolymer)
Natural rubber (natural isoprene rubber)
Nylon
Polyamide, i.e. nylon 6,9
Polybutylene terephthalate
Polycarbonate
Polyethylene
Polymethylmethacrylate
Isotactic polypropylene
Polystyrene
Poly-trans-pentenamer rubber
Styrene-acrylonitrile copolymer
Styrene-butadiene rubber
Curative systems
Bismaleimide
Bismaleimide/MBTS
Bismaleimide/peroxide
Organic peroxide
Organic peroxide/coagent
Dimethylol phenolic
Accelerated sulfur
Soap/sulfur or soap/sulfur donor
S
SOlS
9.A.l.3
393
Other abbreviations
TMTD
MBTS
TEM
TPV
Tetramethylthiuram disulfide
2-Benzothiazolyl disulfide
Thermoplastic vulcanizate
References
1. Morris, H.L. (1979) in Handbook of Thermoplastic Elastomers (ed. B.M. Walker), Van
Nostrand Reinhold, New York, pp. 5-71.
2. Kresge, E.N. (1978) in Polymer Blends, vol. 2 (eds D.R Paul and S. Newman), Academic
Press, New York, p. 293.
3. Kresge, E.N. (1984) J. Appl. Polym. Sci.: Applied Polymer Symposium, 39, 37.
4. O'Connor, G.E. and Fath, M.A. (1981) Rubber World (December), 25; (1982), op. cit.
(January), 26.
5. Gesner, B.D. (1969) in Encyclopedia of Polym. Sci. and Technol., vol. 10 (eds H.F. Mark and
N.G. Gaylord), Interscience Publishers, New York, p. 694.
6. Gessler, A.M. (1962) US Patent, 3037954, June 5.
7. Fischer, W.K. (1973) US Patent, 3758643, September 11.
8. Coran, A.Y., Das, B. and Patel, R.P. (1978) US Patent, 4130535, December 19.
9. Coran, A.Y. and Patel, R.P. (1980) Rubber Chem. Techno!., 53, 141.
10. Abdou-Sabet, S. and Patel, RP. (1991) Rubber Chem. Technol., 64, 769.
11. Abdou-Sabet, S. and Fath, M.A. (1982) US Patent, 4311628.
12. Flory, PJ. (1953) Principles of Polymer Chemistry, Cornell University Press, Ithaca, NY,
p.576.
13. Nielson, L.E. (1951) Rev. Sci. Instr., 22, 690.
14. Abdou-Sabet, S. and Patel, R.P. (1990) Paper presented at the American Chemical Society,
Rubber Division, Washington, DC, October 9-12.
15. Coran, A.Y. and Patel, RP. (1978) US Patent, 4104210, August 1.
16. Coran, A.Y. and Patel, (1980) US Patent, 4183876, January 15.
17. Coran, A.Y. and Patel, RP. (1981) US Patent, 4271 049, June 2.
18. Campbell, D.S., Elliott, D.J. and Wheelans, M.A. (1978) NR Technology, 9, 21.
19. Payne, M.P., Wang, D.S.T., Patel, R.P. and Sasa, M.M. (1990) The expanding technology
of thermoplastic elastomers. Paper 34, presented at the Rubber Division, American
Chemical Society meeting, Washington, DC, October 10-12.
20. Coran, A.Y. and Patel, R.P. (1978) US Patent, 4130534, December 19.
21. Puydak, R.C. and Hazelton, D.R (1988) Plastics Engineering, 44,37-9.
22. Coran, A.Y. and Patel, R.P. (1980) Rubber Chem. Techno!., 53, 781.
23. Wagner, H.L. and Flory, P.J. (1952) J. Am. Chem. Soc., 74, 195.
24. Flory, P.J. (1953) in Principles of Polymer Chemistry, Cornell University Press, Ithaca, NY,
see p.568.
25. Corao, A.Y., Patel, RP. and Williams, D. (1982) Rubber Chem. Techno!., 55, 116.
26. Zisman, W.A. (1964) Advances in Chemistry Ser., 43, 1.
27. Mikami, T., Cox, RG. and Mason, S.G. (1975) Int. J. Multiphase Flow, 2, 112.
28. Wu, S. (1978) Polymer Blends, vol. 1 (eds D.R Paul and S. Newman), Academic Press, New
York, p. 244.
29. Helfand, E. and Sapse, A.M. (1975) J. Chem. Phys., 62, 1327.
30. Crocker, G.I. (1969) Rubber Chem. Technol., 42, 30.
394
31. Avgeropoulos, G.N., Weissert, F.e., Biddison, P.H. and Boehm, G.G.A. (1976) Rubber
Chem. Techno!., 49, 93.
32. Hamed, G.R. (1982) Rubber Chem. Technol., 55, 151.
33. Aharoni, S.M. (1979) J. Appl. Polym. Sci., 21, 1323.
34. Coran, A.Y. and Patel, R.P. (1978) US Patent, 4104210, August 1.
35. Coran, A.Y. and Patel, R.P. (1982) US Patent, 4355139, October 19.
36. Coran, A.Y. and Patel, R.P. (1983) Rubber Chem. Technol., 56, 1045.
37. Paul, D.R. (1978) Polymer Blends, vol. 2 (eds D.R. Paul and S. Newman), Academic Press,
New York, p. 35.
38. Olabisi, 0., Robeson, L.M. and Shaw, M.T. (1979) Polymer Miscibility, Academic Press,
New York, p. 321.
39. Gaylord, N.G. (1975) Adv. Chem. Ser., 142, 76.
40. Van der Meer, S. (1943) Rev. Gen. Caoutch. Plast., 20, 230.
41. Thelamon, e. (1963) Rubber Chem. Technol., 36, 268.
42. Giller, A. (1966) Kant. Gummi. Kunstst., 19, 188.
43. Veda Minoura, M., Mizunuma, S. and Oba, M. (1969) J. Appl. Polym. Sci., 13, 1625.
44. Ide, F. and Hasegawa, A. (1974) J. Appl. Polym. Sci., 18, 963.
Index
Adhesion promoters 202, 249

Alkoxyl radicals p-scission and Habstraction, see Peroxides
Antioxidants 206, 207, 216, 225, 266
aromatic amines 123, 225, 269, 271, 281,
284, 293, 294, 296
hindered amines 271, 286, 288, 292
hindered phenols 268, 274, 281
284, 288, 292, 296
macromolecular 276-7, 285, 298
metal deactivators 272
phosphite(s) 98, 115, 271, 272
quinones 271
sulphur compounds 271, 290
uvabsorbers 123, 273, 281, 287, 296
see also Reactive antioxidants
Antioxidant classes 268-73
Antioxidant mechanisms 268-73
Antioxidant permanence
antioxidant distribution and morphology
274
chemical effects 274
compatibility 275
diffusion, volatility and leachability 275
physical effects 274
Aromatic amines, see Antioxidants
Autoclave reactors 230
Autoxidation mechanism 267
Autoxidation of borane 308
Azo initiators 4, 85, 99, 112, 113, 281
Blooming 275
Borane containing polymers 304
Borane functionalized olefin polymers
synthesis
borane monomers 305
direct copolymerization 306
post copolymerization 307
Bound antioxidants, see Reactive
antioxidants
Brittle-ductile temperature 156, 157
Brittle-ductile transition 189
Brominated maleic anhydride 116
Cage effect 7, 88, 323

Catalysts
metallocene 84, 104, 303, 306
Ti or Cr-based 257
Zeigler-Natta 13, 84, 104,303,306
Ceiling temperature(s) 18-19, 27, 28, 73
Chain breaking antioxidants, see
Antioxidant mechanisms
Chain breaking mechanism, see Antioxidant
mechanisms
Charge transfer complexes
effect of addition of electron donating
solvent 46
effect of addition of second electron
donating monomer 45-6
equilibrium constants of formation 66
grafting 37-40
microstructure of graft 68-71
reactivity of free maleic anhydride 67,
72
reactivity of free styrene 67, 72, 75
relative importance 74, 78
specific interactions 74, 76
stability 35-36
see also NMR
Compatibilization 133, 153, 192
see also Technological compatibilization
Compatibilization in-situ 134, 136, 148, 149,
151, 158, 163, 175, 186, 192,381
Compatibilization of polyamide blends 141,
157
Compatibilization of PP and polyamide 119
Compatibilization using borane-based
copolymers
PP/PC blends 325
PP/PCL blends 325
PP/PMA blends 323
Compatibilizer(s) 133, 134, 136, 149, 150,
156, 163, 303, 305, 323
reactive 156
Controlled degradation of PP 13, 85, 92-8
Controlled-rheology PP 13, 92
Copolymers 189, 303, 305, 332
396
INDEX
Copolymers, contd.
block or graft 117, 122, 133, 136, 141, 148
formation of alternating 16
from maleic anhydride/styrene-modified
PP system 72-3
in-situ formation 151-2, 163
random 226
of ricinoloxazoline maleinate with styrene
77
steric effect 16
see also Maleic anhydride
Copolymerization of boranes with olefins,
see Borane functionalized olefin polymers
synthesis
Correlation between blend properties and
properties and characteristics of
plastics and elastomers
correlation with blend components 3779
critical entanglement spacing 376
critical surface tension 374
crystallinity 374
dynamic shear modulus 314
tensile strength of the hard phase 374
see also Thermoplastic elastomer
vulcanizates
Coupling agents 202, 249, 252
Crosslinking 13, 14
Crosslinking coagents 100-1
Crosslinking of EPDM 121
Crosslinking of polyolefins
crosslinking catalysts 214-15
by irradiation 198-9
by peroxides 199-201
by silane technology 201-4,
thermal crosslinking 211-14
see also IR spectroscopy; Moisture
crosslinking
Crosslinking of PP 98-101, 109
Crystallization of silane grafted polyolefins
227
Curing systems for dynamic vulcanization
Lewis acid catalysed methylol-phenol
360,365
peroxide based 352
m-phenylenebismaleimide 365
self-curing 364, 365
sulfur based 355
see also Thermoplastic elastomer
vulcanizates
Depropagation reactions 18, 19
Diblock copolymers, see Graft and block
copolymers from borane functional
polymers
Diels-Alder adducts 106, 111
Die swell 14,388
DSC
microstructure of grafts on PP 69
of modified EP copolymer 313
oxazoline modified polystyrene blends
171
for polyamide blends 141, 150
of PP-polycaprolactone copolymer 315,
317
for PP with peroxides 96, 103
of silane grafting 224
of silane modified polyolefins 222
Dynamic vulcanization
preparation of elastomer plastic blends
351-3
properties of blends 353
see also Polyolefin bazed thermoplastic
vulcanizates
Elastomer (thermo)plastic blends, 349,
351-3
see also Dynamic vulcanization;
Thermoplastic elastomers
Electron beam grafting
adhesion 342
applications 340-4
controlled release of drugs 344
effect of monomer 336
effect of polymer 335
effect of radiation dose 334
effect of solvent 336-7
effect of surface area 338
effect of temperature 337
fuel cells 344
ion exchange 343
membrane reactors 344
polymer physical form 340
principles 332-4
separations 343
supports for catalyst and reagents 342
textiles 342
Electron donating monomers, see Charge
transfer complexes
ESR detection of radicals 85, 86, 103
Ethyl radicals
formation via p-scission 12
hydrogen abstraction 11
Evans-Polanyi relation 10
Flory-Rehner equation 355
Free radical grafting
mechanistic view 2-16
grafting vs. polymerization 3
see also Melt free radical grafting
Free radicals, see radicals
see also Initiators
FTIR, see IR
Glass fibre reinforced PP, 104
Glass ionomer cement 342
397
INDEX
grafting on PP
effect of nature and concentration of
peroxide 54
effect of temperature 54
grafting in a mixture with styrene 50
effect of glycidyl methacrylate initial
concentration 60
effect of peroxide concentration
59-60
effect of presence of styrene 56
effect of specific throughput 63-5
effect of screw speed and feed rate 62
in epoxidized rubber 285
grafting in twin screw extruder
56-65, 116
grafting yield 49, 53, 61, 74, 75
kinetics 52
local residence time 63
residence time 58, 61-2
screw length 57-9
styrene-assisted grafting 50, 113
see also Charge transfer complexes
Graft and block copolymers from borane
functional polymers
autoxidation of alkyl-9-BBN 308
chain extension via diblock copolymers
318-23
free radical reactions 309-14
ring opening reactions 314-18
Grafting
plasma induced 331
radiation induced, see Electron beam
grafting
Grafting in polymer melts
bifunctional polymerizable antioxidants
294
co-grafting 295-7
monofunctional non-polymerizable
antioxidants 293
monofunctional polymerizable
antioxidants 292
monofunctional polymerizable
antioxidants with coagent 294- 7
by reactive processing 290-3
Grafting reaction(s)
on PP in aqueous suspension 111
on PP in the solid state 109, 117
on PP in solution 111, 117
on PP in the melt 112, 117
steric effect 16
temperature effect 19
Graft length 4, 19, 28, 73
Grafting of radicals 13
decomposition 4-7
grafting efficiency 7-10, 43-4
halfiife 5-7
hydrogen abstracting capacity 10-13

Green strength 388
Hindered amine light stabilizers, see
Antioxidants
Hindered phenols, see Antioxidants
Homopolymer(ization) 2, 4, 7, 22, 106, 108,
289, 292, 295
Homopropagation of radicals 16
Hydroboration reaction 307, 318, 321
Hydrogel ion exchanger 343
Hydrogen abstraction
from alkanes 11
by radicals 11, 13, 88
Hydrolysis of alkoxysilanes, see Moisture
crosslinking
Hydroperoxides 267
Hydroquinones as crosslinking agents 119
see also peroxides
Immiscible polymers 151, 153, 163
Immobile interface 154
Initiator, see Peroxides
Initiator efficiency 93-4
C-C initiators 97
Inorganic peroxides 85
Interfacial adhesion 155, 157
Interfacial reactions, see Oxazoline
modified polystyrene (OPS) blends
Ionic crosslinking 105
Ionizing radiation 4
see also, Electron beam grafting
IR spectroscopy
of dibutylthiodilaurate 215
of hydrolysis of silane grafted PE 209
of 2-isopropenyl-2-oxazoline 164, 166
of maleic anhydride/styrene- modified PP
72
of modified polyethers 167

of oxazoline grafted PP 165
of polyamide blends 141-2, 143, 144
of reactive oxazoline-modified
polystyrene blends 167-8, 169
Irradiation crosslinking of PE 198
Irradiation crosslinking of PVC 254
Itaconic acid as reactive monomer 105, 109
Linear low density polyethylene
films 14
Low density polyethylene
films 14
Macroporous membrane 340
Macroradicals
branching and crosslinking 13-14
chain scission 13
grafting 14-16
intramolecular/intermolecular transfer 73
398
Macroradicals, contd.
reaction with oxygen 86
reaction with vinyl silanes 205
Maleic anhydride
activation of the double bond 34-40, 46,
66,75
grafting on EPOM, 24
grafting on EPR 26, 28
grafting on HOPE 24, 28
grafting on LOPE 28
grafting on n-icosane 27, 28
grafting on PP
p-scission 34
effect of absence of peroxide 41- 3
effect of mechanical mixing 41
effect of nature and concentration of
peroxides 43-5
effect of temperature 40-1
grafting of charge transfer complexes
37-40
grafting yield 22, 24, 32-4
IR studies 25
mechanism 106-8
molecular weight changes 29
NMR studies 26-7, 28, 36-7
reaction with nitrile rubber 381
in twin screw extruder 47-9
see also Poly(maleic anhydride)
Mechanical adhesion 155, 156, 157
Mechanochemical initiation 290
Melt elasticity 92
Melt fracture 387
Melt free radical grafting
grafting versus homopolymerization
18-20
heterogeneity effect 20
mechanism and graft microstructure
25-9
mechanisms 65
peroxide decomposition 17-20
processing effects 23 - 5
temperature effects 17
use of batch internal mixers 23
viscosity effects 20
Melt strength 14, 105
Metallocene catalysts, see Catalysts
Methyl radicals
formation via p-scission 12
reactivity 11
Mixed plastics waste 119
Model studies with low molecular weight
alkanes 88-91
Moisture crosslinking
effect of crosslinking conditions 229
effect of polyolefin structure 226-8
of silane grafted PE 207 -11
Moisture crosslinkable PP 255
Moisture crosslinkable PVC 254-5
INDEX
Molecular weight changes 13

Monohydroboration reaction 305
Monomer solubility 21, 33, 41, 43, 114
see also Charge transfer complexes;
Poly(maleic anhydride)
Monosil process 203, 217-18, 225
Nitrile rubber-nylon thermoplastic
elastomer vulcanizates see,
vu1caniza tes
NMR
liB 307
of crosslinked PP 101
to determine monomer grafting on PP
165
of irradiated PP 85
of modified EP copolymer 312
of polyamide blends 143
of PP diblock copolymer 319-20
of PP-polycaprolactone copolymer
315-16
spectral changes of maleic anhydride and
styrene grafts on PP 69-72
OPS, see Oxazoline modified polystyrene
Organic peroxides, see Peroxides
Oxazoline modified polystyrene, 164, 165
Oxazoline modified polystyrene (OPS)
blends
interfacial reactions
characterization 167-71
comparison of reactivity 175
effect of blending sequence 186
extent of reaction 174-5
kinetics 171-4
morphology 176-9
tensile properties 179-80
impact properties 180
preparation by copolymerizationl64-5
preparation by reactive melt grafting
165, 168
preparation by solution modification
167
solubility characteristics 169
Peroxidation of PP 102-4
Peroxide induced PP degradation 96
Peroxides
activation energies 6, 8-9
chain scission 12, 89, 241
classification 87, 91
crosslinking of silane grafted PE 223, 240,
241,245
as coupling agents 121
decomposition and rate 17-20, 88
decomposition products 89, 90, 91, 101,
246
INDEX
effect of concentration on silane grafting

223
H-abstraction 89, 90, 91
halflife 6-7, 17, 86- 7, 200, 223
induced decomposition 6-7, 86
lifetime 52, 61
physical form 88, 91
reactivity 91
solubility 34, 115, 118
Peroxyborane 308-309
Phase inversion 151
Phase separated systems 133
Phenolic antioxidants 98, 115
Phosphite(s), see Antioxidants
Plasma induced grafting, see Grafting
Polyamide chain scission 139, 148, 157
Polyamide-ABS blends 155-6
Polyamide-maleic anhydride containing
polymer blends
chemistry of coupling 143-4
coupling versus crosslinking 147
effect of chemistry on morphology 14850
effect of chemistry on rheology 148
evidence of coupling reaction 141-2
length of polyamide graft 145
morphology 150-3
polymer analogous reactions 139-40
reactions of anhydride with amides 137-9
reactions of anhydride with amines 137
rheology 153-4
Polyamide poly(phenylene oxide) blends
156
Polyethylene
crosslinking 78, 268
free radical reactivity 25
radical stability 14
see also Crosslinking of polyolefins
Poly(maleic anhydride) 27, 28, 33, 107, 113,
135
Polymer bound antioxidants 225
Polymer bound light stabilizers 116
Polymer oxidation 267
Polyolefin based thermoplastic vu1canizates
butyl rubber based 362-4
diene rubber based 360-2
EPDM-based 353-0
Polypropylene, PP
chain scission 78, 85, 86, 91, 97, 103, 113,
121, 268
effect of peroxides on molecular weight 43
mechanisms of degradation 93-6
melt strength 14
physical state 40
radical reactivity 25
radical stability 14
shear and elongational viscosity 92, 99
steric effect 25
399
impact modification of blends 121

Polypropylene-polyamide blends 119
see also Controlled degradation,
crosslinking grafting reactions
PP modification by organic peroxides
controlled degradation of PP 92
mechanism 93
modelling 93
processing 96
crosslinking
crosslinking coagents 100
mechanism 98
silane crosslin king 10 1
grafting with reactive monomers
monomers 105
mechanism 106-8
reaction systems of monomer grafting
109-17
peroxidation of PP
mechanism 102
use of peroxides 103
reactive blending of PP
mechanism 118
PP/elastomer blends 120
PP/thermoplast blends 118
Preventive mechanism, see Antioxidant
mechanisms
Radiation crosslinking 98
Radiation induced grafting, see Grafting
Radicals
carbon-centered and oxygen-centered 10
decay 85
grafting mechanism scheme 3
reactivity 10, 12-13, 15, 99
stability 5-6, 85
thermochemically induced 4
see also Initiators
Reactive antioxidants, 274, 276-80, 285
chemical grafting post manufacture 282
in polymer melts, reactive processing
289-98
reaction with functional(ized) polymers
283-7
radiation induced surface grafting 287
copolymerization 280-2
Reactive blending of PP, see PP
modification by organic peroxides
Reactive compatibilization, see
Compatibilization in-situ
Reactive extrusion and processing 2, 92,
105,113,117,204,216,226,289,298
Reactivity ratios 15
Rubber toughened polyamides 154-5
Rubber toughened polymers
effect of rubber particle size 187
Scorch retardant additives 208, 235, 243
400
Scorching and scorch 200, 207
SEM and TEM
in moisture crosslinking 228
of oxazoline modified polystyrene blend
173
of polyamide-maleic anhydride functional
polymers 148, 150
of PPjPCL blend 325-6
of thermoplastic vulcanizate 363, 364
Set test 209
Silane copolymerization processes
high pressure polymerization 230-3
product differentiation
ambient cure 237-8
storage stability 233
processing stability 234-6
reactor copolymer(ization) 232, 234, 240
Silane crosslinked polyolefins
applications
adhesion 249
foams 250
moulding 249
others 250
pipes 247
wire and cable insulation 245
structure and properties 239-41
practical requirements
moisture crosslinking 243
polymer to product 242
recycling 244
storage and catalyst addition 242
Silane crosslinking process
crosslinking conditions 229
polyolefin structure 226-9
see also, Moisture crosslinking
Silane grafting processes
effect of polyolefin and silane type 220
grafting initiators 223
reaction temperature and time 224
the stabilization package 225
see also Sioplas process
Silane homopolymerization 205
Silane modified polyolefins
graft copolymerization 204
random copolymerization 206
see also Crosslinking of polyolefins
Sioplas process 203, 216-17
Strain hardening 14
INDEX
Succinic anhydride 137

Super tough materials 134
Super tough nylons 150, 163
Super tough PA, see Super tough nylons
Technological compatibilization
blends 379-83, 391
of nitrile rubber-polyolefin
resistance to hot oil and brittle point
383
overall assessment 384
Thermal crosslinking of silane modified PE
211
Thermoplastic elastomer vulcanizates 120,
351, 353
end use applications 390
nitrile rubber-nylon compositions
effect of curatives 364
effect of elastomers 365
effect of fillers 369
effect of plasticizer 367
effect of rubber-nylon proportion 365
overall assessment 369
other thermoplastic vulcanizates 369
processing fabrication technology 387 -90
see also Polyolefin bazed thermoplastic
vulcanizates; Thermoplastic
vulcanizates based on dissimilar
plastics
Thermoplastic vulcanizates based on
dissimilar plastics
blends of thermoplastic vulcanizates 385
prepared components 384
Thrommsdorff- N orrish effect 108, 109
Toughening mechanism 155
Triallyl(iso )cyanurate as comonomer 111
Uv absorbers, see Antioxidants
Vector effect 38
Vinyl acetate as reactive monomer 111, 113
Vinyl oxazoline monomer 164
Vulcanization in cables 201
Wire and cable insulation, see Silane
crosslinked polyolefins
Zeigler-Natta catalyst, see Catalysts

Reactive Modifiers For Polymers

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BLACKIE ACADEMIC & PROFESSIONAL

London Weinheim . New York Tokyo Melbourne Madras

Published by B1ackie Academic & Professional, an imprint of

1997 Chapman & Hall

@) Printed on acid-free text paper, manufactured in accordance with

Free-radical grafting of monomers onto polymers by

G.-H. HU, J.-J. FLAT and M. LAMBLA

Modification of polypropylene by organic peroxides

A.H. HOGT, J. MEIJER and J. JELENIC

Blends of polyamides and maleic-anhydridecontaining polymers: interfacial chemistry

M. VAN DUIN and R.J.M. BORGGREVE

Modification of polymer melts by oxazolines

N.C. LIU and W.E. BAKER

Moisture cross-linkable silane-modified polyolefins

Reactive antioxidants for polymers

Synthesis of polyolefin graft and block

Electron beam radiation graft modification of

Thermoplastic elastomers based on elastomerl

A.Y. CORAN and R.P. PATEL

Polymer Processing and Performance Group,

Department of Chemistry, Queen's University,

DSM Research, PO Box 18,6160 MD,

Department of Materials Science and Engineering,

University of Akron, Institute of Polymer

Laboratoire d'Extrusion Reactive, ECPM Departement Polymeres Institut Charles Sadron,

Akzo Nobel Central Research, Zutphenseweg 10, 7418

Laboratoire d'Extrusion Reactive, ECPM Departement Polymeres Institut Charles Sadron,

Akzo Nobel Central Research, Zutphenseweg 10,7418

Laboratoire d'Extrusion Reactive, ECPM Departement Polymeres Institut Charles Sadron,

Polymeric Materials Research Institute, Shanghai Jiao

*Presently at CERDATO Elf Atochem, 27470 Serguigny, France.

Akzo Nobel Central Research, Zutphenseweg 10, 7418

Polymer Research Centre, 25 Garii Street, R-1900

Advanced Elastomer Systems, 388 South Main Street,

Materials Research, Department of Polymer

DSM Research, PO Box 18,6160 MD, Geleen, The

Chemical modification of polymers by reactive modifiers is no longer an

microstructure of the graft and the nature and importance of competing

Free-radical grafting of monomers onto polymers

In recent years, increasing activities have been directed towards chemical

S. Al-Malaika (ed.), Reactive Modifiers for Polymers

REACTIVE MODIFIERS FOR POLYMERS

Overall reaction scheme

A free-radical grafting system usually contains three types of reactants:

FREE-RADICAL GRAFTING OF MONOMERS ONTO POLYMERS

Figure 1.1 Overall scheme of free-radical grafting onto a polymer backbone.

backbone (kH) a macroradical is then formed. As will be discussed later in

REACTIVE MODIFIERS FOR POLYMERS

Initiator decomposition: halflife, initiator grafting efficiency and

Free-radical initiators are sources of free radicals necessary for initiating a

FREE-RADICAL GRAFfING OF MONOMERS ONTO POLYMERS

rene. When azo-bis-isobutryonitrile (AIBN) was used as initiator no grafting

(a) Halflife. The halflife of a peroxide, t1/2 is a measure of its rate of

REACTIVE MODIFIERS FOR POLYMERS

functions stabilise peroxides. These factors are manifested in the activation

Thus the temperature dependence of t 1/2 can be written as

FREE-RADICAL GRAFTING OF MONOMERS ONTO POLYMERS

t-butyl a-cumyl peroxide

118; 120c ; 124d

116; 115 c ; 117d

128; 128 c ; 131 d