Article

pubs.acs.org/Macromolecules

Synthesis and Characterization of Maleic Anhydride Grafted

Polypropylene with a Well-Dened Molecular Structure
Min Zhang, Ralph H. Colby, Scott T. Milner, and T. C. Mike Chung*,

Department of Materials Science and Engineering and Department of Chemical Engineering, The Pennsylvania State University,
University Park, Pennsylvania 16802, United States

Tianzi Huang and Willem deGroot

The Dow Chemical Company, 2301 Brazosport Blvd., Freeport, Texas 77541, United States
S Supporting Information
*

ABSTRACT: Despite the commercial importance of maleic

anhydride grafted polypropylene (PP-g-MAH), it has long been
a scientic challenge to prepare this polymer with a wellcontrolled molecular structure. This paper discusses a new
chemical route that can form PP-g-MAH with desirable MAH
content, a single MAH incorporated unit, white color, high
molecular weight, and narrow molecular weight and composition distributions. The chemistry involves a unique PP-co-p-BT
copolymer as the reactive intermediate that can be eectively
prepared by metallocene-mediated copolymerization of propylene and p-(3-butenyl)toluene (p-BT), with narrow molecular
weight and composition distributions, high molecular weight,
and a broad range of p-BT contents. The incorporated p-BT
comonomer units provide the reactive sites for the subsequent
free radical MAH graft reaction under a suspension condition at a low reaction temperature. The resulting PP-g-MAH polymers
were carefully examined by a combination of NMR and GPC measurements, which shows almost no change in polymer
molecular weight and distribution and a single MAH incorporation (no oligomerization). The incorporated MAH units increase
with the increase of initiator concentration, p-BT content, and reaction time. Evidently, the combination of high reactivity of CH3 moiety, a favorable mixing condition between the reactive sites and chemical reagents in the swollen amorphous phases, and
low reaction temperature results in MAH grafting reaction selectively taking place at the -CH3 moieties without side reactions
(i.e., chain degradation and MAH oligomerization). In addition, this suspension reaction process presents an economic method
to prepare PP-g-MAH with high polymer content and easy product purication.

INTRODUCTION
Isotactic polypropylene (PP) represents a quarter of
commercial polymers produced in the world and is one of
the fastest growing thermoplastics due to its unique
combination of properties, including high melting point, high
tensile strength, stiness, chemical resistance, excellent
processability and recyclability, and low cost.1 Despite its
commercial success, the functionalization of PP has long been a
scientically challenging and industrially important area.25
The constant interest is driven by the strong desire to improve
PPs poor interactive properties and broaden its applications to
higher value products, especially in polymer blends and
composites those in which adhesion and compatibility with
other materials are paramount. Despite signicant research
eorts in the past decades by both direct and postpolymerization approaches, limited success has been yielded.
By far, maleic anhydride modied polypropylene (PP-gMAH)6 is the most important commercial functionalized PP
2013 American Chemical Society

polymer due to its unique combination of the low cost of

maleic anhydride (MAH) reagent, high activity of the resulting
succinic anhydride moiety, and good processability of the PP-gMAH polymer. Despite its low molecular weight (most of them
<20 kg/mol), deep color (with impurities), and ill-dened
molecular structures, PP-g-MAH is the most popular choice of
material for improving the compatibility, adhesion, and
printability of polypropylene. They can be found in many
important commercial products, such as glass ber reinforced
PP,7 anticorrosive coating for metal pipes and containers,8
metalplastic laminates,9 multilayer sheets of paper for
chemical and food packaging,10 and polymer blends such as
PP/polyamide and PP/polyester1114 as well as polymer/clay
nanocomposites.1519
Received: March 31, 2013
Revised: May 5, 2013
Published: May 20, 2013
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Scheme 1. Reaction Mechanism of a Free Radical Mediated MAH Grafting Reaction on PP

handling of borane reagents (highly air sensitive).44 Another

reactive PP copolymer studied included poly(propylene-co-pmethylstyrene) (PP-co-p-MS) copolymers45 prepared by the
heterogeneous ZieglerNatta catalyst, which has low p-MS
content (<0.8 mol %) and broad molecular weight and
composition distributions. The subsequent free radical graft
reaction46 of PP-co-p-MS copolymerscarried out under a
suspension reaction condition using dicumyl peroxide initiator
at 125 Cshows good selectivity on the p-MS units with
minimal reduction of PP molecular weight. Unfortunately, the
preparation of the PP-co-p-MS copolymer was failed by isospecic metallocene catalysts due to the chain transfer reaction
in the presence of styrenic monomers.45,46 Therefore, this PPco-p-MS method only aords the PP-g-MAH copolymers with
low MAH content and broad molecular weight and
composition distributions. In fact, due to the broad
composition distribution in the PP copolymers, the incorporated MAH moieties at p-MS units are mostly located in
relatively low molecular weight polymer chains, making for a
nonideal molecular structure for interfacial agents. It is still
elusive to prepare the well-dened PP-g-MAH polymers with
economic process.
In this paper, we will discuss three closely related issues in
the formation of the well-dened PP-g-MAH polymer. First is
the redesign and synthesis of the reactive PP copolymer that
contains active benzylic proton (-CH3) moieties in the exible
side chains. This copolymer can be conveniently prepared by a
metallocene catalyst to form copolymers with various
comonomer content, high molecular weight, and narrow
molecular weight and composition distributions. Second is a
systematic free radical MAH grafting study to identify the most
suitable reaction condition for selective free radical grafting an
MAH single unit onto the -CH3 moieties without side
reactions. In other words, the resulting PP-g-MAH polymers
should have nearly the same molecular weight and composition
distributions as the starting PP copolymer and MAH content
that is proportional to the incorporated -CH3 units in the PP
copolymer, while exhibiting a white color (without purication). Third is a comprehensive polymer structure characterization to conrm the resulting well-dened PP-g-MAH
polymers.

As illustrated in Scheme 1, PP-g-MAH is normally prepared

via a free radical grafting reaction of maleic anhydride with a
preformed isotactic PP homopolymer in the presence of an
organic peroxide initiator in homogeneous (solution2024 or
melt2535) reaction conditions at elevated temperatures. It is
generally believed that the grafting reaction starts with
hydrogen abstraction by the alkoxyl radical upon the thermal
decomposition of the peroxide initiator. Most of the formed
tertiary macroradicals (I) in the PP chain involve a facile
intramolecular -scission reaction and degrade the polymer
chain into two shorter PP chains:2535 one with an unsaturated
chain end (II) and the other having a terminal macroradical
(III) that subsequently reacts with maleic anhydride monomers. As expected, the incorporated MAH content is reversely
proportional to PP molecular weight. Many experimental
results also suggest that the incorporated MAH monomer units
are a mixture of single and multiple succinic anhydride moieties
due to the oligomerization of maleic anhydride. In addition,
other side reactions, such as direct oligomerization of MAH
monomers by the alkoxyl radical to form the ungrafted
impurities (IV), also take place during this free radical grafting
reaction, especially under high reaction temperatures. Much
work has been done in optimizing the reaction conditions and
extruder parameters to promote the desired reactions while
suppressing the undesired ones.2036
The nal product is usually a complicated (deep color)
mixture. Unfortunately, the performance of PP-g-MAH as an
interfacial agent is highly dependent on its molecular weight
and MAH content as well as the ability to remove impurities. It
is very important to develop a new method that can prepare a
high PP-g-MAH polymer with a well-controlled molecular
structure.
In the past decade, we have been investigating a new
approach by using PP copolymers containing some reactive
sites that can oer selective MAH modication reactions. The
objective was to minimize side reactions (PP chain degradation,
MAH oligomerization, etc.) and to obtain a white PP-g-MAH
polymer with high molecular weight, desirable MAH content,
and a single MAH incorporated structure. The rst method
involved the borane-containing PP copolymer.37 The incorporated borane groups in the side chains or chain end are
spontaneously oxidized by oxygen to form the polymeric
radicals3842 that are associated with in situ formed stable
borinate radicals.43 With the presence of MAH monomers, the
polymeric radical in situ reacts with MAH at ambient
temperature to produce PP-g-MAH without altering the PP
main chain structure. However, the major concerns around this
chemistry are the lack of commercial availability, cost, and

EXPERIMENTAL DETAILS

Materials and Instrumentation. All O2- and moisture-sensitive

manipulations were carried out inside an argon-lled Vacuum
Atmospheres drybox. The metallocene catalyst rac-Me2Si[2-Me-4Ph(Ind)]2ZrCl2 was prepared using the published procedures.47
Polymerization-grade propylene (from Matheson Gas) was used as
received. Toluene (Wiley Organics) was distilled over sodium
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Scheme 2. New Reaction Mechanism To Prepare PP-g-MAH Polymer and Derivative

benzophenone under argon. Allylmagnesium bromide (1.0 M solution

in diethyl ether), TiCl3AA, AlEt2Cl (10 wt % in toluene), calcium
hydride, diethyl ether (anhydrous), 4-methylbenzyl chloride, chlorobenzene (anhydrous), (trimethylsilyl)methylamine, benzyl peroxide
(BPO), AlEt2Cl (10 wt % in toluene), and methylaluminoxane (MAO,
10 wt % in toluene) were purchased from Sigma-Aldrich and were
used as received. Maleic anhydride (MAH) was purchased from
Sigma-Aldrich and was puried by sublimation before use. 3Butenylbenzene (BB) was purchased from Sigma-Aldrich and was
distilled with calcium hydride before use.
All high-temperature 1H NMR spectra were recorded on a Bruker
AM-300 instrument in 1,1,2,2-tetrachloroethane-d2 at 110 C. The
melting temperatures of the polymers were measured by dierential
scanning calorimetry (DSC) using a PerkinElmer DSC-7 instrument
controller with a heating rate of 10 C/min. The MAH content was
calculated from FTIR by the following equation: MAH wt % = K
(A1780/d), where A1780 is the absorbance of carbonyl group at 1780
cm1 and d is the thickness (mm) of the lm; K constant (0.25) is
determined by a calibration curve of the known MAH content of PP-gMAH polymers.48 The polymer molecular weights were determined by
intrinsic viscosity of polymer measured in decahydronaphthalene
(Decalin) dilute solution at 135 C with a Cannon-Ubbelohde
viscometer. The viscosity molecular weight was calculated by the
MarkHouwink equation: [] = KMv where K = 1.05 104 dL/g
and = 0.80.49 The polymer molecular weights were also analyzed on
a PL-220 series high-temperature gel permeation chromatography
(GPC) unit equipped with triple detectors, including a Precision
Detectors 2-angle laser light scattering detector Model 2040, a
Viscotek model 210R viscometer, a dierential refractive index
detector, and four PLgel Mixed-A (20 m) columns (Polymer
Laboratory Inc.). The oven temperature was at 150 C, and the
temperatures of autosamplers hot and warm zones were at 135 and
130 C, respectively. The solvent 1,2,4-trichlorobenzene (TCB)
containing 200 ppm tris(2,4-di-tert-butylphenyl)phosphite (Irgafos
168) was nitrogen purged. The ow rate was 1.0 mL/min, and the
injection volume was 200 L. A 2 mg/mL sample concentration was
prepared by dissolving the sample in N2 purged and preheated TCB
(containing 200 ppm Irgafos 168) for 2.5 h at 160 C with gentle
agitation.
Synthesis of p-(3-Butenyl)toluene. To a dry 500 mL threenecked round-bottom ask equipped with an addition funnel,
condenser, and magnetic stir bar, 200 mL (0.2 mols) of
allylmagnesium bromide solution was transferred. A 20 mL (0.14
mol) aliquot of 4-methylbenzyl chloride diluted with 50 mL of diethyl
ether was added dropwise to allylmagnesium bromide at ice bath

temperature. After complete addition of 4-methylbenzyl chloride, the

mixture was warmed to room temperature and reuxed for 12 h. Then,
200 mL of distilled water was slowly added to the mixture. The
aqueous layer was separated and washed three times with diethyl ether.
The organic phases were combined and dried with anhydrous sodium
sulfate. After evaporation of the solvent the residue was puried on a
silica column with hexane as eluent to give the crude product a pale
yellow oil. The crude product was further dried with calcium hydride
and distilled under vacuum before use. Yield: 20.1 g, 94%. 1H NMR
spectrum: 7.11 (m, PhH), 5.87 (m, 1 H, CHCH2), 5.04 (m, 2
H, CHCH2), 2.70 (t, 2 H, PhCH2), 2.39 (m, 2 H, CH2CH
CH2), 2.34 (s, 3 H, PhCH3).
Slurry Copolymerization of Propylene and p-(3-Butenyl)toluene with Metallocene Catalyst. In a typical copolymerization
reaction, 50 mL of toluene and 4.2 mL of MAO (Al/Zr = 3000) were
charged into a Parr 450 mL stainless autoclave equipped with a
mechanical stirrer in a drybox. After removal from the box, the reactor
was injected with a certain amount of p-(3-butenyl)toluene and then
charged with 2.72 atm of propylene to saturate the toluene solution at
ambient temperature. About 2 106 mol of rac-Me2Si[2-Me-4Ph(Ind)]2ZrCl2 in 2 mL of toluene solution was then injected into the
reactor with 130 psi of propylene under rapid stirring to initiate the
copolymerization. Additional propylene was fed continuously into the
reactor to maintain a constant pressure (8.84 atm) during the entire
course of the polymerization. After a 15 min reaction time elapse at 45
C, the reaction solution was quenched by methanol (10 mL), and the
product was ltered, washed with a large amount of acidied methanol
solution, and then dried under vacuum at 60 C for 24 h. Similar
synthetic procedures were used to prepare propylene/3-butenylbenzene copolymers, except changing the comonomer to 3-butenylbenzene.
Bulk Copolymerization of Liquid Propylene with p-(3Butenyl)toluene with Metallocene Catalyst. In a typical
copolymerization reaction, 50 mL of toluene and 14 mL of MAO
(Al/Zr = 10 000) were charged into a Parr 450 mL stainless autoclave
equipped with a mechanical stirrer in a drybox. After removal from the
box, the reactor was injected with 3 mL of p-(3-butenyl)toluene and
then charged with 60 mL of liquid propylene at ambient temperature.
The reactor was heated to 45 C within 3 min. Then 2 106 mol of
rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2 in 2 mL of toluene solution was
then injected into the reactor by the use of 19.04 atm of argon gas
under rapid stirring to initiate the copolymerization. The reaction was
stopped by the addition of methanol (10 mL) and cooled; the pressure
was released, and the product was taken out, washed with a large
amount of acidied methanol solution, and dried in vacuum at 60 C
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Figure 1. 1H NMR spectra of (a) PP-co-p-BT copolymer containing 0.8 mol % of p-BT units (run B-3) and (b) a PP-co-BB copolymer containing 2
mol % BB units (run C-1 in Table 1).
mL two-necked ask equipped with a magnetic stirrer and a condenser
along with a water knockout trap. Subsequently, 1.0 mL of
(trimethylsilyl)methylamine was added to the ask. The mixture was
heated to 110 C under nitrogen for 8 h before precipitating the
reaction mixture into 200 mL of acetone. The nal product was
isolated by ltration, washed with acetone three times, and nally dried
under vacuum at 60 C for 24 h.

for 24 h. Similar procedures were used to prepare propylene/3butenylbenzene copolymers.

ZieglerNatta Mediated Propylene Copolymerizations.
Similar copolymerization procedures were used to prepare both
propylene/p-(3-butenyl)toluene and propylene/3-butenylbenzene copolymers, except the catalyst system of metallocene/MAO, which was
changed to TiCl3AA (0.10g) and AlEt2Cl (5 mL, 10 wt % toluene).
The reaction temperature was kept at 60 C for 15 min with 75 mL of
toluene as the total volume. The pressure of propylene gas was
maintained at 4.08 or 8.84 atm.
Maleic Anhydride Grafting Reaction of Poly(propylene-co-p(3-butenyl)toluene). In a typical reaction, 2 g of the propylene/p-(3butenyl)toluene copolymer (powder form) was suspended in 40 mL of
chlorobenzene at 25 C under nitrogen in a 100 mL ask equipped
with a magnetic stirrer. Then, 2.5 g of maleic anhydride and 0.02 or
0.04 g of BPO were added. The reactor was heated to a high
temperature (75 or 85 C), and the reaction was stirred for another
period of time (3 or 9 h) at that temperature before precipitating the
reaction mixture into 200 mL of acetone. The resulting PP-g-MAH
was isolated by ltration, washed with acetone four times, and dried
under vacuum at 60 C for 24 h.
Reaction between PP-g-MAH Polymer and (Trimethylsilyl)methylamine. Maleic anhydride modied polymer (1.0 g) was
suspended in 20 mL of chlorobenzene at 25 C under nitrogen in a 50

RESULTS AND DISCUSSION

Poly(propylene-co-p-(3-butenyl)toluene) and Poly(propylene-co-3-butenylbenzene) Copolymers. Scheme
2 illustrates the new reaction scheme. Compared to the
previous reaction using p-methylstyrene (p-MS) comonomer,
this chemistry is centered on a new p-(3-butenyl)toluene (pBT) comonomer (I) that contains -olen moiety (instead of
styrene). The similar -olen moieties in both propylene and pBT monomers oer a favorable metallocene-mediated copolymerization to form PP-co-p-BT copolymers50 (II) with a broad
range of p-BT contents and narrow molecular weight and
composition distributions. It is logical to predict that the
incorporated bulky p-BT comonomer units (located in the
exible side chains) shall be excluded from the PP crystalline
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Table 1. Comparison of the Experimental Results in the Propylene Polymerization with and without p-BT and BB Comonomers
polymerization conditions
run

catalysta

propyleneb
(atm/M)

control-A
A-1
A-2
A-3
A-4
A-5
A-6
control-B-1
control-B-2
control-B-3
B-1
B-2
B-3
B-4
B-5
B-6
B-7
C-1
C-2
C-3
C-4

A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
B
B
A
B
B
B

4.08/1.64
4.08/1.64
4.08/1.64
8.84/3.68
8.84/3.68
14.96/6.48
14.96/6.48
4.08/2.29
8.84/5.26
14.96/9.58
4.08/2.29
4.08/2.29
8.84/5.26
8.84/5.26
8.84/5.26
14.96/9.58
14.96/9.58
4.08/1.64
4.08/2.29
8.84/5.26
14.96/9.58

comonomerc
(mL)
p-BT/1
p-BT/2
p-BT/1
p-BT/2
p-BT/2
p-BT/3

p-BT/1
p-BT/2
p-BT/0.5
p-BT/1
p-BT/2
p-BT/2
p-BT/3
BB/2
BB/1
BB/1
BB/2

polymer products

temp
(C)

time
(min)

polymer yield
(g)

60
60
60
60
60
60
60
45
45
45
45
45
45
45
45
45
45
60
45
45
45

15
15
15
15
15
5
5
15
15
5
15
15
15
15
15
5
5
15
15
15
5

10.5
6.9
5.0
8.3
6.2
7.3
5.6
9.3
13.3
12.1
4.3
3.4
8.4
5.8
3.9
8.1
5.3
4.4
3.8
5.1
7.8

comonomerd
(mol %)
0.7
1.3
0.5
0.8
0.3
0.4

2.3
4.2
0.8
1.4
2.5
1.0
1.4
1.0
2.0
1.2
0.7

Mve
(kg/mol)

Tm
(C)

H
(J/g)

881
433
401
517
482
581
532
202
253
682
178
157
217
182
164
608
540
374
180
191
477

162.9
155.3
150.1
156.2
153.8
156.9
156.4
156.8
156.7
156.9
140.3
132.7
148.8
144.3
139.1
144.9
143.2
152.4
142.3
145.6
149.0

78.9
61.7
49.9
73.2
57.1
77.8
74.7
110.2
106.3
88.3
50.3
40.8
91.3
70.9
47.1
77.8
54.9
53.8
58.3
73.8
78.1

Catalyst A: 0.1 g of TiCl3AA, 5 mL of Et2AlCl, and 75 mL of toluene. Catalyst B: 2 mol of rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2 catalyst, 50 mL of
toluene; 4.2 mL of MAO (Al/Zr = 3000). bPropylene pressure and concentration51 used in all reactions except runs A-5, A-6, control-B-3, B-6, B-7,
and C-4 using liquid propylene. cComonomer p-BT: p-(3-butenyl)toluene; comonomer BB: 3-butenylbenzene. dComonomer content (mol %) in
the copolymers determined by 1H NMR under 110 C in 1,1,2,2-tetrachloroethane-d2. eEstimated by intrinsic viscosity of polymer/decalin dilute
solution at 135 C with K = 1.05 104 dL/g and = 0.8.
a

phases and will position themselves into the amorphous

domains.
In the subsequent free radical MAH grafting reaction to
prepare PP-g-MAH polymer (III), this polymer morphology,
in conjunction with a suspension reaction condition, directs the
grafting reaction selectively at the reactive -CH3 moieties in
the swollen amorphous domains under low reaction temperatures to avoid the side reactions. For comparative studies to
understand the free radical grafting reaction, the corresponding
control copolymerization reactions using 3-butenylbenzene
(BB) comonomer were also carried out to obtain the PP-coBB copolymers that contain no reactive -CH3 moieties.
Figure 1 compares the 1H NMR spectra between a PP-co-pBT copolymer (run B-3 in Table 1) and a PP-co-BB copolymer
(run C-2 in Table 1), both containing 0.8 and 2 mol %
comonomer units (with and without -CH3 group, respectively). They are prepared by the same rac-Me2Si[2-Me-4Ph(Ind)]2ZrCl2/MAO catalyst under similar copolymerization
conditions. Both spectra show three major chemical shifts at
0.95, 1.35, and 1.65 ppm, corresponding to the methine,
methylene, and methyl groups in the PP chain. In Figure 1a,
there are three additional chemical shifts around 2.35, 2.65, and
7.1 ppm, corresponding to -CH3, CH2--CH3, and aromatic
protons, respectively, in the PP-co-p-BT copolymer. In Figure
1b, there are only two additional chemical shifts around 2.65
and 7.1 ppm, corresponding to the CH2- and aromatic
protons, respectively, in the PP-co-BB copolymer. The
integrated intensity ratio of the chemical shifts between 0.9
and 1.7 ppm and the chemical shift at 7.1 ppm, and the number
of protons both chemical shifts represent, determines the
concentration of p-BT and BB units in the copolymers.

Tables 1 summarizes two comparative propylene/p-BT

copolymerization sets (A and B) using a heterogeneous
TiCl3AA/Et2AlCl ZieglerNatta catalyst and a homogeneous
rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO metallocene catalyst
to prepare the reactive PP-co-p-BT copolymers, respectively.
Four corresponding control reactions in set C using the 3butenylbenzene (BB) comonomer were also carried out to
obtain the PP-co-BB copolymers, without reactive -CH3
moieties. The resulting polymers were analyzed by 1H NMR,
dierential scanning calorimetry (DSC), and intrinsic viscosity
() to determine polymer composition, melting temperature,
and average molecular weight (Mv). For several comparative
sets, the high-temperature gel permeation chromatography with
a series of detectors, including deferential reection index, light
scattering, and intrinsic viscosity (GPC-triple detectors), was
applied to obtain detailed information about the change of
polymer molecular weight and molecular weight distribution
before and after MAH grafting reactions (discussed later).
In general, two p-BT and BB comonomers with the same olen moiety exhibit similar copolymerization reactivity (run A2 vs C-1, run B-1 vs C-2, run B-4 vs C-3, and run B-6 vs C-4),
showing similar polymer yield, comonomer incorporation, and
copolymer molecular weight and crystallinity, in both the
ZieglerNatta and metallocene catalyst systems. In other
words, the resulting PP-co-p-BT and PP-co-BB copolymers are
very similar, except having the reactive benzylic protons (CH3) in PP-co-p-BT copolymers. Comparing runs in set A, the
heterogeneous ZieglerNatta catalyst oers good catalyst
activities and high molecular weight copolymers. The
comonomer incorporation is proportional to the comonomer
concentration, while the molecular weight and polymer yield
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systematically decreased. There are no issues around preparing

a high molecular weight PP-co-p-BT copolymer with >1 mol %
comonomer content and high crystallinity (run A-2). However,
as will be discussed later, the major concern in this PP-co-p-BT
copolymer is the broad molecular weight and composition
distributions. On the other hand, the metallocene catalyst oers
a much better copolymerization capability to prepare the
copolymers with narrow molecular weight and composition
distributions. In the comparative set B, the increase of the p-BT
comonomer feed results in the systematical increase of
comonomer content (up to 4 mol % in run B-2). The
copolymerization results are very dierent from those using the
p-methylstyrene (p-MS) comonomer feed, showing almost no
catalyst activity. Evidently, the -olen moiety in p-BT
comonomer (vs styrenic moiety in p-MS) provides eective
comonomer incorporation in the metallocene-mediated
propylene copolymerization. Even a small amount of
comonomer incorporation (1 mol %) has a signicant eect
to the melting temperature (Tm) and heat of fusion (H) of
polypropylene, indicating the homogeneous distribution of
bulky comonomers in the resulting PP-co-p-BT copolymers.
The increase of the p-BT comonomer feeding also results in the
systematical reduction of catalyst activity and polymer
molecular weight. The incorporation of bulky p-BT comonomer slows down the polymerization rate and increases of the
chain transfer reaction. Both can be compensated by
introducing high propylene concentration (runs B-6 and B-7
using liquid propylene feed).47 Similar results were observed in
the PP-co-BB copolymer (run C-4).
Reactivity Ratios. The optimal way to investigate a
copolymerization reaction is to measure the reactivity ratio of
the comonomers. To obtain meaningful results, a series of
experiments were carried out by varying monomer feed ratio ( f
= [propylene]/[p-BT] = [M1]/[M2]) and comparing the
resulting copolymer composition (F = d[M1]/d[M2]) at a low
monomer conversion (<5%) in order to maintain a constant
comonomer mole ratio ([M1]/[M2]). In the Supporting
Information, Tables S1 and S2 summarize two experimental
sets of propylene/p-BT copolymerization using a heterogeneous TiCl3AA/Et2AlCl ZieglerNatta catalyst and a homogeneous rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO metallocene
catalyst, respectively. The reactivity ratios between propylene
(r1 = k11/k12) and p-BT (r2 = k22/k21) were estimated using the
MayoLewis equation. As shown in Figure 2, both plots of f(1
F)/F vs f 2/F give straight lines with slope for r1 and intercept
for r2. The linear slope in Figure 2a shows r1 = 1.535 and r2 =
0.425, with r1 r2 = 0.65 (not far from unity), indicating a
relatively good random copolymerization reaction with a
slightly higher propylene reactivity in the rac-Me2Si[2-Me-4Ph(Ind)]2ZrCl2/MAO mediated propylene/p-BT homogeneous copolymerization reactions. In other words, the propylene/
p-BT copolymers shown in runs B (Table 1) are mostly
random copolymers. As will be discussed later, they also exhibit
narrow molecular weight distribution. On the other hand, the
similar linear propylene/p-BT copolymerization plot in Figure
2b results in r1 = 23.638 and r2 = 0.75, with r1 r2 = 17.73 (far
from unity), indicating the strong tendency of propylene
consecutive insertion while using a heterogeneous Ziegler
Natta (TiCl3AA/Et2AlCl) catalyst system. The crossover
reactions from the propagating propylene site to p-BT
comonomer are small. Overall, the results suggest the
propylene/p-BT copolymers shown in runs A (Table 1) having
inhomogeneous copolymer structure and a broad composition

Figure 2. MayoLewis plots for copolymerization between propylene

and p-BT comonomer by using (a) rac-Me 2 Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO and (b) TiCl3AA/Et2AlCl catalysts.

distributions. They are also exhibit broad molecular weight

distributions (discussed later).
PP-g-MAH Polymers. The availability of a wide range of
well-dened PP-co-p-BT copolymers, prepared by a homogeneous (single-site) metallocene catalyst, oers us with an
excellent opportunity to systematically study the free radical
MAH grafting reaction and examine their resulting PP-g-MAH
molecular structures. The objective is to develop an eective
chemical route to prepare desirable white PP-g-MAH polymers
with a single MAH grafting enchainment, controlled MAH
concentration, high polymer molecular weight, and narrow
molecular weight and composition distributions (which have
never been reported before). Table 2 summarizes the
experimental results of MAH modication reactions involving
three PP-co-p-BT copolymers with 0.8, 1.0, and 1.3 mol % p-BT
contents (runs B-3, B-6, and A-2 in Table 1) and two control
polymers, including a PP homopolymer (control-B-2) and a
PP-co-BB copolymer (run C-3), using benzyl peroxide (BPO)
initiator under a temperature range between 75 and 95 C. The
MAH contents and locations in the resulting PP-g-MAH
polymers were determined by FTIR and 1H NMR measurements. The polymer molecular weights were determined by
intrinsic viscosity measurement (Mv). The melting point (Tm)
and heat of fusion (H) of the polymer were determined by
dierential scanning calorimetry (DSC). As will be discussed
later, some of the PP-g-MAH polymers were further
interconverted into the corresponding PP-g-MAHCH2
Si(CH3)3 polymers (compound IV in Scheme 2), allowing
detailed molecular structure characterization by a combination
of 1H NMR and GPC triple detector measurements.
Infrared spectroscopy is the most commonly used method in
determining MAH content in the polymer.49 Figure 3 compares
FTIR spectra of the starting PP-co-p-BT (run B-6) and two
corresponding PP-g-MAH copolymers (runs B-6-MAH-1 and
B-6-MAH-3). After the MAH graft-from reaction, two new
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Table 2. Summary of PP-g-MAH Polymers Prepared by Free Radical Mediated Grafting Reactions with Various PP Polymers
PP-g-MAH polymers
runa
control-B-2 (PP)
control-B-2-MAH-1
control-B-2-MAH-2
A-2 (PP-co-p-BT)
A-2-MAH-1
A-2-MAH-2
A-2-MAH-3
B-3 (PP-co-p-BT)
B-3-MAH-1
B-3-MAH-2
B-3-MAH-3
B-3-MAH-4
B-3-MAH-5
B-3-MAH-6
B-3-MAH-7
B-6 (PP-co-p-BT)
B-6-MAH-1
B-6-MAH-2
B-6-MAH-3
C-3 (PP-co-BB)
C-3-MAH-1
C-3-MAH-2

[comonomer]
(mol %)

1.3
1.3
1.3
1.3
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
1.0
1.0
1.0
1.0
1.2
1.2
1.2

initiator
(wt %)

temp/time
(C/h)

MAHb
(wt %)

MAHc
(wt %)

MAHc
(mol %)

2.0
2.0

75/9
85/3

n.d.d
n.d.d

n.d.d
n.d.d

n.d.d
n.d.d

2.0
2.0
2.0

75/3
75/9
85/3

0.5
1.4
1.5

0.37
1.0
1.1

0.16
0.42
0.48

1.0
2.0
2.0
1.0
2.0
1.0
2.0

75/3
75/3
75/9
85/3
85/3
95/3
95/3

0.1
0.3
0.8
0.6
1.0
0.5
0.9

0.07
0.24
0.55
0.40
0.76
0.33
0.67

0.03
0.10
0.24
0.17
0.32
0.14
0.28

2.0
2.0
2.0

75/3
75/9
85/3

0.4
1.0
1.2

0.29
0.76
0.90

0.12
0.32
0.38

2.0
2.0

75/9
85/3

0.2
0.3

0.17
0.21

0.07
0.09

Mv
(kg/mol)

Tm
(C)

H
(J/g)

253
241
235
401
377
353
342
217
209
202
191
198
179
112
73
608
581
575
541
191
165
152

156.7
156.4
156.2
150.1
149.6
149.3
148.9
148.8
148.6
148.2
148.0
148.1
147.7
147.5
146.9
144.9
144.7
144.2
144.0
145.6
145.2
145.0

106.3
100.7
98.1
49.9
42.8
38.3
32.9
91.3
85.2
80.3
76.8
74.3
70.2
63.1
55.2
77.8
70.3
61.8
58.3
73.8
65.2
60.7

Reaction conditions: polymer ne powders 1.0 g, MAH 2.0 g, chlorobenzene 20.0 g, BPO as initiator. bEstimated by FTIR spectra. cEstimated by
H NMR spectra. dNot detectable.

showed much higher MAH incorporation than the corresponding PP-co-BB copolymers and PP homopolymers, under the
same reaction conditions (Table 2). In two PP homopolymer
runs (control-B-2-MAH-1 and control-B-2-MAH-2), the
resulting PP-g-MAH polymers showed no detectable MAH
content as well as little change in the PP molecular weight. In
addition to the lack of reactive sites, high PP crystallinity, and
thus less matrix swelling at 75 and 85 C, may contribute to its
chemical ineciency. However, under the same suspension and
relatively low reaction temperature conditions, all PP-co-p-BT
copolymers show a systematic increase of MAH content with
the increase of the initiator concentration, temperature, and
time. In the B-6 set, using the starting PP-co-p-BT copolymer
with 1 mol % p-BT content, we can obtain PP-g-MAH with >1
wt % MAH content without a major change in polymer
molecular weight and distribution (discussed later). Evidently,
most of the graft reactions were taken place in the p-BT side
chains located in the swollen amorphous phase under this
suspension reaction condition. Interestingly, only very low
MAH contents were observed in the comparative PP-co-BB
copolymer runs (C-3-MAH-1 and C-3-MAH-2). This copolymer, with only CH2- moieties (without -CH3 moiety),
clearly shows very ineective in free radical grafting reactivity
under this suspension reaction condition.
Polymer viscosity (in melt or solution) is commonly used to
monitor polymer molecular weight during the MAH grafting
reaction. As summarized in Table 2, the intrinsic viscosities of
all polymers were measured in decalin dilute solution at 135 C,
and the viscosity molecular weight (Mv) was calculated by the
MarkHouwink equation: [] = KMv where K = 1.05 104
dL/g and = 0.80.48 Comparing all PP-g-MAH polymers in the
B-3 set, the polymer molecular weight (Mv) seems to be quite
sensitive to the reaction temperature and less dependent on the

Figure 3. FTIR spectra of (a) starting PP-co-p-BT (run B-6) and two
corresponding PP-g-MAH copolymers, including (b) run B-6-MAH-1
and (c) run B-6-MAH-3.

absorption peaks were observed at 1860 and 1780 cm1,

corresponding to the symmetric and asymmetric stretching of
the two CO groups in the resulting succinic anhydride group
(compound III in Scheme 2). The incorporated MAH content
in PP-g-MAH was calculated by the following equation: MAH
(wt %) = K(A1780/d), where A1780 is the absorbance of the
carbonyl group at 1780 cm1, d is the thickness (mm) of the
lm, and K is a constant (0.25) that is determined by a
calibration curve of several commercial PP-g-MAH polymers
with known MAH contents. Overall, PP-co-p-BT copolymers
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Figure 4. DSC plots of (left) heating and (right) cooling cycles for (a) starting PP-p-BT (run B-6) and three corresponding PP-g-MAH copolymers,
including (b) run B-6-MAH-1, (c) run B-6-MAH-2, and (d) run B-6-MAH-3.

GPC-triple detectors techniques in conjunction with the

imidization of succinic anhydride groups with (trimethylsily)methylamine to form the corresponding PP-g-MAHCH2
Si(CH3)3 polymer (compound IV in Scheme 2). For 1H NMR
measurements, the new silane-capped MAH moieties reveal the
true MAH grafting structure, especially answering single or
multiple MAH enchainment. On the other hand, the silanecapped MAH moieties in PP-g-MAH polymers prevent
polymer chain interactions during GPC measurements, which
provide fair side-by-side comparison of polymer molecular
weights and distributions before and after MAH grafting
reaction.
Figure 5 compares 1H NMR spectra of two corresponding
PP-g-MAH and PP-g-MAHCH2Si(CH3)3 polymers and the
starting PP-co-p-BT copolymer. In Figure 5b, in addition to
three major chemical shifts at 0.95, 1.35, and 1.65 ppm,
corresponding to the methine, methylene, and methyl groups in
the PP chain, and three smaller chemical shifts around 2.35,
2.65, and 7.1 ppm, corresponding to -CH3, CH2--CH3,
and aromatic protons in p-BT comonomer units, there is an
additional new chemical shift at 2.78 ppm, corresponding to
-CH2-MAH. It is dicult to directly observe the resonance
of methylene and methane protons of the graft MAH units,
possibly due to the dipolar broadening of resonance near the
graft points that have restricted mobility. Overall, the intensity
of this new -CH2-MAH chemical shift systematically
increases while the peak intensity for -CH3 group proportionally decreases. On the other hand, the peak intensity for
CH2--CH3 maintains almost constant throughout the MAH
modication steps. The combination strongly suggests that the
selective MAH grafting reaction at -CH3 active sites and
internal CH2-- sites with similar benzyl protons but lower
accessibility are not eective. The MAH grafting eciency at
the active -CH3 sites can be directly estimated by the peak
intensity ratio between CH2--CH3 and -CH2-MAH. The
detailed MAH contents in the resulting PP-g-MAH polymers
are summarized in Table 2, which are slightly lower than the
results obtained from FTIR studies. In general, the MAH
incorporation increases with the initiator concentration,
reaction time, and temperature. Up to 40% of -CH3 active
sites in the PP-co-p-BT copolymer were grafted with MAH
groups without signicant changes in the PP molecular weight

BPO initiator concentration and reaction time. The most

suitable reaction temperature for this free radical induced MAH
grafting reaction on PP-co-p-BT copolymers is near 85 C, in
which the MAH grafting reaction is eective and the polymer
maintains similar molecular weight. In addition to the
heterogeneous reaction condition to minimize exposure of PP
backbone, the lower activation energy for H-extraction from
benzylic protons in the -CH3 moiety (vs that of tertiary
protons in PP backbone) shall also contribute to the selectivity.
Figure 4 compares DSC curves of the same reaction set (runs
B-6). The resulting melting temperature (Tm) and heat of
fusion (H) data are summarized in Table 2. They are
obtained in the second heatingcooling cycle at 10 C/min,
which removes any thermal history of each sample and provides
reproducible results for side-by-side comparison. All DSC
curves show similar melting and crystallization temperatures
with a relatively narrow peak and a at baseline, indicating a
uniform crystalline structure in semicrystalline morphologies
and narrow composition distribution along all copolymer
chains. As discussed in Table 1, both Tm and H values are
strongly dependent on the density of the comonomer (i.e.,
branch density) in the PP-co-p-BT copolymer; the higher the
density, the lower the Tm and H. Even a small amount of
comonomer incorporation (1 mol %) has a signicant eect on
the crystallization of PP. On the other hand, the subsequent
modication of p-BT comonomer units in forming PP-g-MAH
polymers (Table 2), the change of melting temperature, and
heat of fusion are very small. Both Tm and crystallinity seem to
be only governed by branch density and are independent of
comonomer type, consistent with Florys prediction for
semicrystalline copolymers. Under the equilibrium condition,
each polymer chain runs from one side of lamellae to the other,
and the consecutive propylene units govern the thickness of
lamellae. The comonomer units (side chains) are restricted in
the amorphous regions. It is interesting to note that the
commercial PP-g-MAH polymers usually show a lower and
broader melting peak, indicating inhomogeneous polymer
structures that are associated with polymer chain degradation
during the MAH modication.
Structure Characterization of PP-g-MAH Polymers. To
understand the detailed molecular structure of PP-g-MAH
polymers, we have applied a combination of 1H NMR and
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Figure 5. 1H NMR spectra of (a) the starting PP-co-p-BT copolymer with 1.0 mol % p-BT units (run B-6 in Table 1), (b) the resulting PP-g-MAH
containing 0.76 wt % MAH (B-6-MAH-2 in Table 2), and (c) the associated silane modied PP-g-MAH-Si(CH3)3 polymer.

MAHCH2Si(CH3)3, respectively. It is interesting to note

the peak intensity ratio (2:2:9) between three types of protons
in the resulting CH2MAHCH2Si(CH3)3 moiety, which
strongly indicates a clean immidization reaction and conrms a
important fact: each grafting point only contains one MAH

(discussed later) under this low-temperature reaction condition.

Figure 5c shows 1H NMR spectrum of the corresponding
PP-g-MAHCH2Si(CH3)3 polymer. There are two new
chemical shifts at 2.95 and 0.32 ppm, corresponding to
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Figure 6. Absolute GPC (LS) curves for (left) starting PP-co-p-BT (run B-6) and three corresponding PP-g-MAH copolymers (runs B-6-MAH-1, B6-MAH-2, and B-6-MAH-3) and (right) starting PP-co-p-BT (run A-2) and three corresponding PP-g-MAH copolymers (runs A-2-MAH-1, A-2MAH-2, and A-2-MAH-3).

2.1); the molecular weight dierence before and after the MAH
modication is extremely minimal. We also note a slight retreat
in the B-6-MAH-3 sample, implying the up limit for the
selective free radical MAH grafting reaction condition (85 C
for 3 h) without signicant side reactions. As shown in set B-3
(Table 2), a reduction of polymer molecular weight becomes
more apparent for PP-g-MAH polymers (runs B-3-MAH-6 and
B-3-MAH-7) that were operated at a slightly higher reaction
temperature (95 C). Similarly well-controlled MAH grafting
reactions were also observed in set A-2, with the exception of a
broad molecular weight distribution (PDI > 4.8) with a low
molecular weight shoulder shown in all polymers, which are
indicative of the starting PP-co-p-BT copolymer being prepared
by the heterogeneous ZieglerNatta catalyst. It is important to
note that these polymers in set A-2 also exhibit a broad
composition distribution. Most of the reactive p-BT groups and
the subsequent incorporated MAH moieties are located in low
molecular weight polymers that have highly undesirable
molecular structures serving as the interfacial agents.

unit. In other words, there was no oligomerization of MAH

monomers during this low-temperature free radical MAH
grafting reaction of PP-co-p-BT copolymer to form white PP-gMAH product, which is quite dierent from the brown
commercial PP-g-MAH polymers that also exhibit low polymer
molecular weight.
Figure 6 compares absolute GPC (LS) curves of two reaction
sets A-2 and B-6 (Table 2), using light scattering (LS) detector
to determine the absolute polymer molecular weight. Figure 6
(left) compares the starting PP-co-p-BT copolymer (with 1 mol
% p-BT reactive comonomer units) prepared by the
homogeneous metallocene catalyst and three corresponding
PP-g-MAH polymers (with 0.29, 0.76, and 0.90 wt % MAH
contents determined by 1H NMR). Figure 6 (right) compares
the starting PP-co-p-BT copolymer (with 1.3 mol % p-BT
reactive comonomer units) prepared by the heterogeneous
ZieglerNatta catalyst and three corresponding PP-g-MAH
polymers (with 0.37, 1.0, and 1.1 wt % MAH contents
determined by 1H NMR). The calculated polymer molecular
weight information is summarized in Table 3. As discussed,
before GPC measurements, the MAH groups in all PP-g-MAH
polymers were also converted to MAHCH2Si(CH3)3 groups
to prevent polymer chain interactions.
All polymers in set B-6, including the starting PP-co-p-BT
copolymer prepared by the homogeneous metallocene catalyst
and three corresponding PP-g-MAH polymers with varying
degrees of MAH grafting reactions, show very high molecular
weights with narrow molecular weight distributions (PDI

CONCLUSION
This paper addresses a long-standing scientic challenge and
industrially important issue in the free radical maleic anhydride
grafting reaction of polypropylene to prepare a desirable PP-gMAH molecular structure with high molecular weight, narrow
molecular weight and composition distributions, single MAH
grafting unit, and a controlled amount of MAH content. This
new chemical strategy is started with the design of poly(propylene-co-p-(3-butenyl)toluene) copolymer that can be
eectively prepared by metallocene-mediated propylene copolymerization to form a broad composition range of high
molecular weight PP-co-p-BT copolymers with narrow
molecular weight and composition distribution. The bulky pBT comonomer units containing the reactive -CH3 moieties
are largely located in the amorphous domains with good side
chain exibility that facilitates the selective MAH grafting
reaction at -CH3 moieties in suspension reaction conditions.
Despite the proton concentrations of secondary CH2 and
tertiary CH in the PP backbone, which are much higher than
that of the fewer -CH3 in the PP-co-p-BT copolymer, we
observed a remarkable selectivity of the free radical MAH

Table 3. Summary of Absolute GPC (LS) Results for Two

Comparative Sets Shown in Figure 6
sample

Mn (g/mol)

Mw (g/mol)

Mz (g/mol)

B-6
B-6-MAH-1
B-6-MAH-2
B-6-MAH-3
A-2
A-2-MAH-1
A-2-MAH-2
A-2-MAH-3

262 900
255 300
245 100
226 000
60 100
64 900
57 100
59 700

559 400
531 400
526 700
466 200
369 200
357 900
336 300
291 400

946 300
885 800
878 500
773 700
1 030 300
1 005 800
916 900
738 000

Mw/Mn Mz/Mw
2.12
2.08
2.14
2.06
6.14
5.52
5.89
4.88

1.69
1.67
1.67
1.66
2.79
2.81
2.73
2.53
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grafting reaction on -CH3 moieties. It appears that the

combination of reactivity sequence of -CH3 > CH2-
CH (backbone) and CH2 (backbone), intact PP semicrystalline
structure under suspension reaction condition, and low reaction
temperature (<85 C) allows this free radical MAH grafting
reaction to avoid nearly all undesirable side reactions, including
PP backbone degradation and MAH oligomerization. The
resulting PP-g-MAH polymers essentially keep their similar
molecular weight as the starting PP-co-p-BT copolymer, and the
content of the single MAH unit is controlled by p-BT
comonomer concentration, the free radical initiator, and
reaction time. Overall, this well-controlled MAH grafting
reaction is very dierent from those in the commercial MAH
grafting reaction of PP homopolymers, in which the MAH
content is reversely proportional to the polymer molecular
weight (Scheme 1). In addition, the suspension reaction allows
for the use of a high concentration of the PP-co-p-BT reactant
and simple ltration and washing of the resulting PP-g-MAH
product. Overall, it also provides an economic reaction process.
Lastly, these new PP-g-MAH polymers shall eectively increase
the needed PP interactive properties in many applications,
including PP blends and composites, which are currently under
investigation.

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ASSOCIATED CONTENT

* Supporting Information
S

Propylene/p-BT copolymerization reactions with low monomer conversions using rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/

MAO and TiCl3AA/AlEt2Cl catalysts. This material is available
free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*E-mail: chung@ems.psu.edu (T.C.M.C.).

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors at Penn State University thank the National
Science Foundation for the nancial support. The authors also
thank Dow Chemical Company for the kind assistance in the
high-temperature GPC triple detector measurements.

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