EUROPEAN

POLYMER
European Polymer Journal 41 (2005) 1979–1984
JOURNAL
www.elsevier.com/locate/europolj

A novel technique for preparing of maleic anhydride

grafted polyolefins
Wulin Qiu *, Takashi Endo, Takahiro Hirotsu
National Institute of Advanced Industrial Science and Technology (AIST), 2217-14 Hayashi-cho, Takamatsu 761-0395, Japan

Received 31 January 2005; received in revised form 19 March 2005; accepted 30 March 2005
Available online 10 May 2005

Abstract

A novel mechanochemical method of preparation of maleic anhydride grafted polypropylene (MAPP) was devel-
oped. The preparation was performed by ball milling of polypropylene (PP) powder, maleic anhydride (MA), and per-
oxide initiator in balls-containing jars with a planetary ball mill for a certain time. Compared with the conventional
melt-mixing method, MAPP obtained through ball-milling technique reveals higher graft degree, particularly alleviated
degradation of PP, or even increased molecular mass of the resulting MAPP. Maleic anhydride grafted polyethylene
(MAPE) was obtained via this technique, and the optimization of the technique is in progress. The novel technique
offers new opportunities in modification of polyolefins, which has also the advantages of solventless, lower process tem-
perature, energy efficient, low cost, and simple running process. Furthermore, it is very easy to obtain purified products.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Ball milling; Polypropylene; Polyethylene; Maleic anhydride; Grafting

1. Introduction [1–7]. The grafting of polyolefins has been successfully

Chemical modification of polyolefins is an important
method, to expand the applications of polyolefins and
generate value-added materials with improved mechani-
cal, thermal, and chemical properties. The modification
of polyolefins through free-radical grafting maleic anhy-
dride (MA) in the presence of an initiator has received
much attention over the past decades. MAPP or MAPE
has been widely used to improve the interfacial interac-
tion between the components in polymer blends and
polymer composites to maximize the physical properties
*
Corresponding author. Present address: Department of
Chemistry, The University of Tennessee, Knoxville, TN
37996-1600, USA. Tel.: +1 865 9742087; fax: +1 865 9740652.
E-mail address: qiuwulin@yahoo.com (W. Qiu).
achieved using solution [8–13], melts [1,5,8,14–19], and
even solid-state rout [8,18,20,21]. Surface grafting reac-
tions [8,22] induced by glow discharge, ultraviolet
(UV) irradiation, high-energy radiation such as c-ray
as well as photografting were also reported and concen-
trated mostly on modification of film, fiber, powder, and
other final product.
In the solution process, polyolefin is dissolved in an
appropriate solvent at elevated temperature, and MA
is added along with an initiator. The purified MAPP
or MAPE can be obtained by precipitation with large
quantity of a non-solvent. The process is extremely
expensive and relatively complex, and difficult to avoid
byproduct. The large quantity of solvents recycling also
made it impractical for large-scale production. In a melt
process, polymer and MA together with an initiator
are mixed in the molten state at elevated temperatures.

0014-3057/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2005.03.016
1980 W. Qiu et al. / European Polymer Journal 41 (2005) 1979–1984
The reaction is conducted in an extruder or internal
mixer without (or with small amount of) solvent in a
short process time. The melt process is the most wide-
spread industrial method. However, to remove the
remaining MA and initiator is still a problem. The result-
ing product is a mixture containing the residual reactants
and low-molecular products. Moreover, PP suffers severe
degradation at the processing temperature beyond
200 °C. In the solid-phase process reported, PP powder
was mixed with MA and a high concentration of initia-
tor assisted by an interfacial wetting agent (usually sol-
vent of PP). The reaction is performed usually in a
stainless steel reactor or low-shear mixer under a tem-
perature of 100–150 °C. MA was grafted on the surface
of the polymer powders. The homogeneity of the grafted
product depends on the size of polymer powder, and sol-
vents or other co-monomer are needed to obtain MAPP
with high degree of grafting. Besides the methods de-
scribed above, few special and seldom used methods
were also mentioned [17,20], such as suspension process
using water or toluene, high temperature thermal graft-
ing process (at 325 °C), vapor phase grafting process (in
modification of PP fiber), irradiation process (etch poly-
olefin film prior to printing), etc.
We have prepared polymer composites through the
ball-milling technique, and an enhancement in inter-
facial chemical reaction as well as mechanical properties
of the composites has been obtained [23–25]. Ball-
milling process gives a fine powder as well as a very high
efficient of mixing (thus high accessibility) of the compo-
nents in solid state at low temperature. The local high
temperature resulted from milling may cause the perox-
ide decompose and yields free radicals, which makes the
grafting reaction possible. In this work, the ball-milling
technique was used to prepare MAPP and MAPE
through the free radical grafting.
2. Experimental
2.1. Materials
Isotactic PP powder [melt flow index (MFI), 1.0; den-
sity, 0.90–0.91 g cm 3] and higher density polyethylene
(HDPE) powder (MFI, 1.0; density, 0.958 g cm 3) were
commercial products of Japan Polychem Corporation.
Maleic anhydride (MA) and benzoyl peroxide [BPO;
molecular weight, 242.23; melting point (mp), 105 °C],
were reagent grade, purchased from Aldrich.
2.2. Preparation of MAPP or MAPE
The ball-milling process was performed in a Plane-
tary Ball Mill (Pulverisette 5, Fritsch, Germany)
equipped with four jars, each of them is 500 cm3 in vol-
ume and is loaded with 25 balls (the diameter: 1.5 cm).
Fifty grams PP (or PE) powder with varied amounts
of MA and BPO were added in each jar, milled for 8 h
at a rotational speed of 300 rpm, with a cyclic mode of
50 min milling followed by a 10 min pause step. The
temperature of the powder mixture was measured with
a DE-3004 K-type thermometer at the beginning of
the pause steps during the process and immediately after
the completion of the process.
For comparing with the melt-mixing method, some
typical MAPP (or MAPE) samples were prepared and
purified as described elsewhere [26], under a mixing con-
dition of 190 °C, 75 rpm, and 15 min, with the same rec-
ipes and loading masses of corresponding samples.
2.3. Purification
The milled mixture was moved into a beaker, a large
quantity of water/acetone (95/5, vol/vol, acetone was
used to get a good wetting of water to PP) was added
and the mixture was stirred for 3 h, then filtered. After
this process was performed two times, the product was
dried at 60 °C overnight, and then was thermal treated
at 120 °C in vacuo for 24 h.
2.4. Characterization
Thin films were prepared from the resulting product
by compression–moulding and FT-IR spectra were
recorded on a Perkin–Elmer 2000 spectrometer at a res-
olution of 2 cm 1 with the coaddition of 200 scans in the
spectral range of 4000–400 cm 1. The grafted MA onto
PP, graft degree (Gd), was determined by chemical titra-
tion [26], and expressed as the weight percentage of MA
(wt.%) in the product.
The MFI was measured by a Takara X416 Melt In-
dexer, Takara Thermistor Instruments Co. Ltd., Japan.
Measurement was performed at 230 °C and a load of
2.16 kg by using the resulting powder.
The morphology of powders was examined using a
Hitachi S-2 460N electron microscope at 25 kV. The
powders were sputter-coated with gold–palladium alloy
before viewing.
3. Results and discussion
Generally the grafting reaction involves initiation to
form macroradicals by abstraction of hydrogen atoms
from the polymer chain by the initiator radicals, and
addition of the unsaturated monomer to the macrorad-
icals. The grafting of MA onto PP was carried out nor-
mally at a high temperature in order to generate free
radicals from the thermal decomposition of the initiator.
The decomposition rate (activation energy and half-life
time) of peroxides depends on temperature. In the pro-
cess of preparing MAPP through ball milling, the tem-
 W. Qiu et al. / European Polymer Journal 41 (2005) 1979–1984
perature inside the jars is about 75–85 °C, which is much
lower than those through other methods. The melting
point of MA is 52 °C, while BPO is 105 °C, therefore
the PP (or PE) powder and BPO powder are wetted by
MA in the ball-milling process.
Fig. 1 shows clearly that ball-milling induced MA
grafting on the backbone of PP chains. The new absorp-
tions appeared at 1863 cm 1 (asymmetric C@O stretch-
ing) and 1786 cm 1 (symmetric C@O stretching) in the
spectra of the resultant samples are the characteristics
of maleic anhydride grafted polypropylene. The absorp-
tion bands around 1786 cm 1 were mathematically ana-
lyzed by an iterative curves fitting, each absorption band
was approximated by a Lorentzian function [17,27], and
the deconvoluted Lorentzians are considered as the ac-
tual absorption bands. Three characteristic bands in
the anhydride region at 1793, 1787, and 1775 cm 1 were
deconvoluted, which are corresponding to the signal
end-grafting (1793 cm 1) and oligomeric end-grafting
(1787 cm 1) [6,17,27], as well as bridging type
(1775 cm 1) [6], respectively. Compared with poly(ma-
leic anhydride), which shows absorption at 1784 cm 1
[17], the higher wavenumber shifts of MAPP obtained
(1787 cm 1) indicating that the average length of grafted
oligomeric moieties is shorter. The results above indicate
that the MAPP obtained is a mixture with main struc-
tures of an end-grafting type as well as a bridging type,
and analogous structures were obtained through melt-
ing-mixing method [26].
Fig. 2 shows that the Gd increases to a maximum with
the increase of initial MA concentration, then decreases.
Similar results were also obtained from melt-mixing
method [26]. The higher initial MA concentration in-
creases the probability that MA monomers react with
Fig. 1. FT-IR spectra of resultant specimens: (a) PP parents,
(b) MAPP obtained by melt-mixing method, and (c) MAPP
obtained by novel ball-milling method (PP/MA/BPO = 100/2/1,
by mass).
1981
Fig. 2. Effect of MA content on graft degree (s, d) and yield
(h, j) of the resultant MAPP (d, j: MAPP obtained via
melt-mixing, BPO = 1 phr).
PP macroradicals to graft, but also cause phase separa-
tion into two distinct phases—MA and PP phases,
which are disadvantageous to the grafting beyond a crit-
ical concentration of MA. The Gd increases fast within
the MA concentration of 1 phr (part of reagent per hun-
dred parts of PP), beyond which gets slowly, and shows
a maximum at about 3.0 phr. The increases of the Gd in
the initial MA concentration range of 0.25–1.0 phr and
1.0–3.0 phr, as well as the decrease in the range of 3.0–
7.0 phr are close to linear, with different slopes. The
yields varied very little at low initial MA concentrations,
but decreased with the increasing of MA concentration.
Fig. 2 shows that ball-milling technique yields MAPP
with satisfactory Gd by comparing to the melt-mixing
method, with the same recipe.
Fig. 3 shows that the Gd and yield increases with the
increasing of initial BPO concentration, until reaches a
plateau. With the increasing amounts of BPO, more
PP radicals are formed, leading to a higher Gd. However,
after the Gd reaches a maximum, a further increase in
BPO does not improve the extent of grafting. Instead
Fig. 3. Effect of BPO content on graft degree (s, d) and yield
(h, j) of the resultant MAPP (d, j: MAPP obtained via melt-
mixing, MA = 2 phr).
1982 W. Qiu et al. / European Polymer Journal 41 (2005) 1979–1984
of generating more free radicals, higher BPO concentra-
tion may cause the crosslinking of polymer molecules
due to radical growth and recombination reactions.
Fig. 3 shows also that under the same BPO concentra-
tions, the ball-milling method yields MAPP with higher
Gd and higher yield, compared with those obtained from
melt-mixing method.
Because the grafting of MA onto PP is a radical reac-
tion, the PP macroradicals absolutely cause scission and/
or crosslinking, and then result in a variation of its
molecular mass. When peroxide is used as an initiator,
crosslinking or chain scission occurs simultaneously
with the graft reaction. The dominant side reaction for
PE is crosslinking, while for PP is chain scission
Fig. 4. MFI of the specimens after purification and thermal
treated: (1) parents PP, (2) ball-milled PP, (3) ball-milled PP/
MA (100/2), (4) ball-milled PP/BPO (100/1), (5) MAPP
obtained via ball-milling (PP/MA/BPO = 100/2/1), and (6)
MAPP obtained via melt-mixing (PP/MA/BPO = 100/2/1).
Fig. 5. FT-IR spectra of resultant specimens: (a) HDPE
parents, (b) MAPE obtained by melt-mixing method, and
(c) MAPE obtained by ball-milling method (PE/MA/BPO =
100/2/1, by mass).
[1,13,28]. MFI of polymer reflects the molecular mass,
and a polymer with a higher molecular mass reveals a
smaller MFI value. It can also be observed from Fig. 4
that ball-milling causes a marked degradation of neat
PP, and the degradation is enhanced by BPO whereas
suppressed greatly by MA. The suppression by MA
maybe caused by the energy absorption of MA to melt
as well as the cushion effect of the melted MA, alleviat-
ing the mechanical effects of ball milling to the PP pow-
der. It is noted that MAPP obtained by ball-milling
method reveals large molecular mass compared with
that obtained through the conventional melt-mixing
method.
Fig. 5 shows clearly that MAPE was obtained
through ball-milling technique, too. The new absorp-
tions appeared at 1864 cm 1 (asymmetric C@O stretch-
ing) and 1786 cm 1 (symmetric C@O stretching) in the
spectra of the resulting samples indicate successfully
Fig. 6. Morphologies of (a) PP parents, (b) and (c) MAPP
obtained (PP/MA/BPO = 100/2/1, milled 8 h).
 W. Qiu et al. / European Polymer Journal 41 (2005) 1979–1984
grafting of MA groups onto PE chains. Similarly to
MAPP, that both the ball-milling method and melt-mix-
ing method yields MAPE the similar main structures.
However, unlike MAPP, the MFI of MAPE decreased
obviously compared with its HDPE parents. In some
samples, the MFI of MAPE is too small to be measured,
no matter through melt-mixing or ball-milling
technology.
As shown in Fig. 6(a), PP used is nearly spherical
powders with diameter of 0.1–0.5 mm, and these pow-
ders are composed of globular particles with diameters
between 0.1 and 0.15 mm. Ball-milling treatment chan-
ged the powder to flake morphology, and some particles
get smaller while some get much larger, as shown in
Figs. 6(b) and (c). HDPE used are irregular powders,
their major axis is about 0.07–1.2 mm (Fig. 7(a)). Ball-
milling makes the powders get much smaller and homo-
geneous (Fig. 7(b)). It is proposed from Figs. 6 and 7
that the reacted MA is more homogeneous in MAPE
than in MAPP, since MA could not react with PP (or
HDPE) inside the powders because it just reacted on
the surface of the powders. The distribution of reacted
MA in MAPP (or MAPE), the changes of molecular
Fig. 7. Morphologies of (a) HDPE parents, (b) MAPE
obtained (HDPE/MA/BPO = 100/2/1, milled 8 h).
1983
weight and its distribution, the effect of powder size on
the graft degree, as well as the detailed grafting mecha-
nism is under investigated.
4. Conclusions
A novel solid-state ball-milling technology of prepa-
ration of MAPP or MAPE was developed. The method
reveals advantages of solventless, lower process temper-
ature, energy efficient, low cost, and easily running pro-
cess, yields the resulting MAPP or MAPE with high
purity, particularly alleviated degradation of polymer,
and higher graft degree compared with the conventional
melt-mixing method. The technology is expected to have
potential applications in modification of polymers with
other reactive moieties (such as methacrylic monomers,
vinyl silanes, etc.) as well as in preparation of polymer
blends.
References
[1] Moad G. The synthesis of polyolefin graft copolymers by
reactive extrusion. Prog Polym Sci 1999;24:81–142.
[2] Boucher E, Folkers JP, Hervet H, Leger L, Creton C.
Effects of the formation of copolymer on the interfacial
adhesion between semicrystalline polymers. Macromole-
cules 1996;29:774–82.
[3] Kudva RA, Keskkula H, Paul DR. Morphology and
mechanical properties of compatibilized nylon 6/polyeth-
ylene blends. Polymer 1999;40:6003–21.
[4] Terzis AF, Theodorou DN, Stroeks A. Entanglement
network of the polypropylene/polyamide interface. 2.
Network generation. Macromolecules 2000;33:1397–410.
[5] Kelar K, Jurkowski B. Preparation of functionalised low-
density polyethylene by reactive extrusion and its blend
with polyamide 6. Polymer 2000;41:1055–62.
[6] Zhang FR, Endo T, Kitagawa R, Kabeya H, Hirotsu T.
Synthesis and characterization of a novel blend of poly-
propylene with chlorella. J Mater Chem 2000;10:2666–72.
[7] Qiu WL, Zhang FR, Endo T, Hirotsu T. Preparation and
characteristics of composites of high-crystalline cellulose
with polypropylene: effects of maleated polypropylene and
cellulose content. J Appl Polym Sci 2003;87:337–45.
[8] Russell KE. Free radical graft polymerization and co-
polymerization at higher temperatures. Prog Polym Sci
2002;27:1007–38.
[9] Jung WC, Park KY, Kim JY, Suh KD. Evaluation of
isocyanate functional groups as a reactive group in the
reactive compatibilizer. J Appl Polym Sci 2003;88:2622–9.
[10] Wu CJ, Chen CY, Woo G, Kuo JF. A kinetic study on
grafting of maleic anhydride onto a thermoplastic elasto-
mer. J Polym Sci Polym Chem 1993;31:3405–15.
[11] Priola A, Bongiovanni R, Gozzelino G. Solvent influence
on the radical grafting of maleic anhydride on low density
polyethylene. Eur Polym J 1994;9:1047–50.
[12] Rosenmöller HW, Wenzel CB, de Groot HJM, Lugten-
burg J, van Duin M. 13C NMR study of the grafting of
1984 W. Qiu et al. / European Polymer Journal 41 (2005) 1979–1984
maleic anhydride onto polyethene, polypropene, and
ethene-propene copolymers. Macromolecules 1996;29:
1151–7.
[13] Machado AV, Covas JA, van Duin M. Effect of polyolefin
structure on maleic anhydride grafting. Polymer 2001;42:
3649–55.
[14] Samay G, Nagy T, White JL. Grafting maleic anhydride
and comonomers onto polyethylene. J Appl Polym Sci
1995;56:1423–33.
[15] Gayload NG, Mehta R, Kumar V, Tazi M. Maleation of
linear low-density polyethylene by reactive processing.
J Appl Polym Sci 1992;44:1941–9.
[16] Ho RM, Su AC, Wu CH, Chen SI. Functionalization of
polypropylene via melt mixing. Polymer 1993;34:3264–9.
[17] De Roover B, Sclavons M, Carlier V, Devaux J, Legras R,
Momtaz A. Molecular characterization of maleic anhy-
dride-functionalized polypropylene. J Polym Sci Polym
Chem 1995;33:829–42.
[18] De Roover B, Devaux J, Legras R. Maleic anhydride
homopolymerization during melt functionalization of iso-
tactic polypropylene. J Polym Sci Polym Chem 1996;34:
1195–202.
[19] Shi DA, Yang JH, Yao ZH, Wang Y, Huang HL, Jing W,
et al. Functionalization of isotactic polypropylene with
maleic anhydride by reactive extrusion: mechanism of melt
grafting. Polymer 2001;42:5549–57.
[20] Rengarajan R, Vicic M, Lee S. Solid phase graft copoly-
merization. I. Effect of initiator and catalyst. J Appl Polym
Sci 1990;39:1783–91.
[21] Lazár M, Hrčková L, Fiedlerová A, Borsig E, Rätzsch M,
Hesse A. Functionalization of isotactic poly(propylene)
with maleic anhydride in the solid phase. Die Angew
Makromol Chem 1996;243:57–67.
[22] Gao J, Lei JX, Su ZJ, Zhang BS, Wang J. Photografting of
maleic anhydride on low density polyethylene powder in
the vapor phase. Polym J 2001;33:147–9.
[23] Zhang FR, Qiu WL, Yang LQ, Endo T, Hirotsu T.
Mechanochemical preparation and properties of a
cellulose–polyethylene composite. J Mater Chem 2002;12:
24–6.
[24] Qiu WL, Zhang FR, Endo T, Hirotsu T. Milling-induced
esterification between cellulose and maleated polypropyl-
ene. J Appl Polym Sci 2004;91:1703–9.
[25] Qiu WL, Endo T, Hirotsu T. Interfacial interactions of a
novel mechanochemical composite of cellulose with
maleated polypropylene. J Appl Polym Sci 2004;94:
1326–35.
[26] Qiu WL, Endo T, Hirotsu T. Interfacial interaction,
morphology and tensile properties of a composite of highly
crystalline cellulose and maleated polypropylene. J Appl
Polym Sci, submitted for publication.
[27] Sclavons M, Carlier V, Roover BDe, Franquinet P,
Devaux J, Legras R. The anhydride content of some
commercial PP-g-MA: FTIR and titration. J Appl Polym
Sci 1996;62:1205–10.
[28] Al-Malaika S, editor. Reactive modifiers for poly-
mers. London: Blackie Academic and Professional; 1997.
p. 13–4.