Maleic anhydride grafting of polypropylene:

peroxide and solvent effects

L. E. Krause-Sammartino1, J. C. Lucas1, M. M. Reboredo2 and M. I. Aranguren*2
The grafting of polyolefins with maleic anhydride (MA) has been incorporated into industrial
practice to generate copolymers that can act as coupling agents between the non-polar
polyolefins and different polar fillers and reinforcements. In the present study, two different
peroxides were used to initiate the MA grafting onto polypropylene (PP), namely dicumyl peroxide
(DCP) and 1,3-bis (terbutylisopropyl peroxi)benzene (DIBP). The use of DIBP allowed similar
grafting yields to DCP to be obtained, but with less chain scission of the polyolefin. Moreover, the
utilisation of a coagent, toluene (Tol), leads to a reduction in the chain scission of PP. A
monotonous decrease in the melt flow index (MFI) of the polymer was observed with increasing
molar ratio of Tol/MA, in the range of ratios considered (0–2.5). In addition, the free radical
grafting of MA onto PP remained high and optimum grafting was obtained for a molar ratio Tol/MA
of y0.5. It was observed that the addition of toluene was effective, independent of the reaction
process utilised, namely batch mixing or extrusion.
Keywords: Maleic anhydride grafted polypropylene, Chain scission, Peroxide, Solvent effect

Introduction occurring during PP grafting is chain scission.19,21 This

leads to a final product with much lower viscosity, a fact
Grafting polyolefins with acrylic acid or maleic anhy- that must be considered and carefully controlled to
dride is a technique used for the preparation of obtain the desired product. There have been reports in
copolymers that can act efficiently as coupling agents the literature that studied the use of coagents to improve
in plastic composites containing metals, inorganic fillers, grafting efficiency, while reducing secondary reactions.
fibres or any other polar filler or reinforcement.1–6 They For example, aromatic compounds containing benzylic
can also be used in the compatibilisation of polar and hydrogens have been previously used to modify the
non-polar immiscible blends.7–11 efficiency of the grafting reaction.22 In these cases, the
The preparation of maleic anhydride grafted poly- molecules were added to the mixture in large concentra-
propylene (MA-g-PP) is particularly interesting, given tions and consequently, this effect was studied as a
the wide commercial use of PP.12–18 Usually, dialkydic solvent effect. This resulted in the improved efficiency of
peroxides are commonly used to initiate this reaction, the grafting reaction and the reduction in the occurrence
because of their stability and halflife. Too short a halflife of secondary reactions in the polyolefin. However, it
will lead to a high radical production in short periods of would also be interesting to investigate this effect at
time, increasing the probability of secondary reactions lower concentrations of these coagents to facilitate the
such as chain scission of the PP. Long halflife may lead elimination step.
to incomplete thermal decomposition of the peroxide Interesting studies have been published on the melt
during mixing, reducing the efficiency of the graft grafting of PP in the presence of more than one
reaction, with the potential risk of the presence of monomer, such as styrene (St) and MA.23,24 The
peroxides in the melt as it is leaving the extruder.19 formation of a chain transfer complex between the
Dicumyl peroxide (DCP) and 1,3-bis(terbutylisopropyl two monomers is reported, which activates MA to
peroxi)benzene (DIBP) were selected for the present increase the yield and reduce PP degradation. Similar
study. DIBP is easy to handle and has low volatility, results were also reported using a-methylstyrene in
therefore it is usually preferred in reactive extrusion.20 molar ratios around one with respect to the MA
Unfortunately, the grafting copolymerisation is monomer.
accompanied by secondary reactions also initiated by In the present study, small quantities of toluene have
the action of the peroxide. The main secondary reaction been incorporated in PP in the molten state to analyse
the resulting MA grafting of PP and the occurrence of
1
the solvent effect.
INTI-Plásticos, Center of Research and Development for the Plastic
Industry, National Institute of Technology, Buenos Aires, Argentina The results of the MA modification of PP obtained
2
INTEMA-Facultad de Ingenierı́a; Universidad Nacional de Mar del Plata, from batch mixing as well as extrusion processes are also
Mar del Plata, Argentina included in the present work to illustrate and compare
*Corresponding author, email [email protected] the solvent effect of toluene in both cases.

ß 2006 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 3 January 2006; accepted 5 May 2006
DOI 10.1179/174328906X103132 Plastics, Rubber and Composites 2006 VOL 35 NO 3 117
Krause-Sammartino et al. Maleic anhydride grafting of polypropylene

Experimental Composite preparation

Polypropylene and short glass fibres were mixed in the
Materials extruder using a screw speed of 30 rev min21, and a
Two PP homopolymers with different MFI and density temperature profile of 175, 200, 200 and 210uC (head).
of 0.908 g cm23, both from Petroquı́mica Cuyo Required specimens were obtained by injection mould-
(Argentina) were selected as the raw materials (Table 1). ing of the previous mixture, using an ENGEL injection
DCP (Perkadox BC, Akzo Nobel Quı́mica SA, machine (ES 75 ST, Austria).
Argentina) and DIBP (Perkadox 14, Akzo Nobel
Quı́mica SA, Argentina) were utilised as alternative Characterisation techniques
peroxides during MA grafting onto PP. The two FTIR
peroxides have different halflives (9.2 and 13 min, for
Polymeric thin films obtained by compression were
DCP and DIBP at 150uC)20 and were selected to
analysed by Fourier transformed infrared spectroscopy
compare their efficiency in grafting and degradation
(FTIR, Nicolet 5SXC) in the transmission mode. The
reactions.
absorption spectra were obtained as the average of 120
The grafting molecule was maleic anhydride (MA, scans at a resolution of 2 cm21. The spectra were
technical grade, Maleic SA, Argentina). Irganox 1010 normalised using the 1100 cm21 peak as reference.
(Ciba, Argentina) was used as antioxidant in all the
preparations (0.2 wt-%) to inhibit oxidation, and Titration
toluene (analytical reagent, Sintorgan SA, Argentina)
Samples were dissolved in water saturated xylene and
was utilised as coagent to reduce chain scission.
refluxed for 1 h under constant stirring. A KOH
Finally, glass fibres were incorporated into PP, with
solution (0.05 N in methanol) was added to the hot
and without addition of the synthesised coupling agents,
solution from a burette in the presence of Thymol Blue
for the preparation of composites to illustrate the until the mixture turned blue. Immediately, a 1 mL
efficiency of the grafting process to produce useful excess of the alkali solution was added to ensure the
coupling agents. The selected fibres were Vetrotex P337 complete hydrolysis of the anhydride. The excess KOH
(Isotex) of 14 mm diameter, which were cut to a length of was further titrated using a solution of HCl (0.05 N in
5 mm. isopropanol) up to yellow colour. The wt-% of grafted
MA was calculated as15
Copolymer preparation methods
%MAH(g MA=g sample)~
Two different techniques were utilised in the preparation
of grafted polypropylenes. First, an intensive mixer ½(VKOH NKOH {VHCl NHCl ){
(Brabender W30) with a 30 cm3 chamber capacity was
(VKOH NKOH {VHCl NHCl )blank
98=(20|sample weight)
utilised to investigate the behaviour of different for-
mulations. This laboratory scale method requires small where V indicates the volume used of the given solution
amounts of raw materials. It was used to identify the (mL) and N is the normal concentration (mol L21). The
best formulations to achieve the required final material subindexes indicate the solution being considered and
characteristics. Grafting reactions were carried out in the sample weight is given in grams.
the mixing chamber at 190uC and at a rotating speed of
60 rev min21. The dried raw materials, PP, MA and Melt flow index
oxidation inhibitor were added to the chamber and The MFI of each sample (2.16 kg) was measured using
mixed for 1 min. Then, the peroxide was incorporated an indexer (Galli Hnos., Argentina) at 190 or 230uC
and mixing was continued for a further 7 min. following the standard ASTM D-1238.
The second preparation method was performed on a
pilot plant scale. The equipment used was a single screw Composite characterisation
extruder (Killion, STD KL 100 24:1, USA) with an L/D Composites were tested according to ASTM D-638
of 24 and a diameter of 25 mm. The screw speed was tensile test and ASTM D-790 flexural test using an
15 rev min21 with a temperature profile of 190, 195, 200 INSTRON 1125 universal testing machine. Impact tests
and 200uC (head). A water bath was used to cool the were performed on unnotched Izod specimens according
extruded material and a Cisca (Argentina) pelletiser mill to ASTM D-256 using a pendulum model CS 137
completed the line. (Custom Scientific Instruments, Inc.).
In all cases, to eliminate the MA that might The surfaces of the samples were fractured under
remain unreacted in the mixture, the samples were liquid nitrogen and coated with gold, and were observed
vacuum dried at 120uC for 48–72 h, so that maleic by scanning electron microscopy (SEM) to analyse the
anhydride was volatilised and separated from the quality of the interfacial adhesion. A Philips SEM 505
grafted polymers.14,15 was used.

Table 1 Melt flow indexes of two PPs used in present Results and discussion
study measured under two different conditions
Batch mixing process
MFI, g 10 min21 Measuring conditions, uC; kg
Varying MA and peroxide concentrations
PP 1 3 (catalogue) 230; 2.16 Initially, MA was added to molten PP in the absence
1.09 190; 2.16 of peroxides to investigate the effect on PP molecular
PP 2 0.70 230; 2.16 weight. Table 2 shows the concentrations of the anhy-
0.34 190; 2.16
dride added in the initial mixtures and the resulting MFI

118 Plastics, Rubber and Composites 2006 VOL 35 NO 3

 Krause-Sammartino et al. Maleic anhydride grafting of polypropylene

1 Wt-% composition of grafted MA and MFI (0.1 g min21,

at 190uC and 2.16 kg of pressure) of copolymer mea-
sured at different MA concentrations in initial reaction 2 Transmission FTIR spectra of MA-g-PP, anhydride
mixture absorption region

measured in each case. Evidently, the addition of MA in Similar results were also reported by Li et al.23 on the
the absence of peroxide does not significantly modify the melt grafting of PP in the presence of St and MA
original PP. However, some degradation takes place monomers and using DCP to initiate radical formation.
during mixing, since all samples show a higher MFI than On the other hand, the decrease in MFI with increasing
the original polypropylene (PP1). The observed change MA can be simply explained by an increase in the
is explained as the result of heating and mixing of the PP concentration of MA in the mixture, which leads to a
during the process. higher probability of macroradicals meeting the MA
On the other hand, the addition of increasing amounts molecules. This higher probability would favour the
of peroxide leads to the scission of the PP chains, as grafting reaction instead of chain scission.
already discussed in the ‘Introduction’.24 This effect is Transmission infrared spectroscopy was also used to
illustrated for DCP in Table 3, which shows increasing characterise the grafted products. The results shown in
MFI values as the concentration of peroxide increases. Fig. 2 are in agreement with the quantitative determina-
A large reduction in the PP molecular weight (higher tions obtained by titration, confirming that there is a
MFI) at high peroxide concentrations would make it maximum yield in the reaction at about 1.5–2.0 pph MA
more difficult to pelletise the modified polymer and in the reaction mixture, without improvements obtained
therefore precluding its further use as a coupling agent by further increase in the MA concentration. Taking
in the most common fabrication methods. into account these results, the rest of the studies were
After observation of these separate effects, different performed using a MA concentration of 1.5 pph in the
wt-% of MA were added to the reaction mixture in the reaction mixture.
presence of DIBP peroxide at a constant concentration
of 6780 ppm. The wt-% of MA moieties attached to PP Use of different peroxides
as a result of the reaction were measured by titration,
The efficiencies of the two peroxides were compared
while the chain scission effect on the product was
with respect to the MFI of the resultant product and the
assessed by measuring MFI of the product at 190uC and
percentage of MA grafted. All the mixtures were
2.16 kg. The combined results are shown in Fig. 1.
prepared with 1.5 pph MA in the initial mixture and
The addition of 1.5–2.0 pph (parts per hundred) MA
at a constant concentration of antioxidant (0.2 wt-%).
to the mixture results in a maximum grafting yield of
y0.67%. Further addition of MA to the mixture at
constant peroxide concentration does not improve Table 3 Melt flow index (measured at 230uC and 2.16 kg)
significantly the yield of the reaction. Other authors of PP1 after batch mixing in presence of
have also reported a maximum yield in that MA different concentrations of dicumyl peroxide, no
MA added
concentration range, indicating that using MA concen-
trations higher than 2 pph produces a phase separation DCP, ppm
of the system.14,25 Since the peroxides used are more
soluble in MA than in PP, fewer radicals are formed in 0 304 523 969 2031
MFI, g 10 min21 3 (catalogue) 7.14 13.83 25.96 68.84
the polymer and the efficiency of grafting is reduced.14,25

Table 2 Melt flow index of PP1 after batch mixing in presence of different concentrations of MA without peroxide and
MFI corresponding to unprocessed PP1 without MA and batch mixing for comparison

MA, pph MFI (190uC, 2.16 kg), g 10 min21 MFI (230uC, 2.16 kg), g 10 min21

0 (no mixing) 1.09¡0.02 3 (catalogue)

1 1.71¡0.19 5.12¡0.08
1.5 1.35¡0.25 5.03¡0.24
2 1.52¡0.01 4.91¡1.56
3 1.38¡0.07 4.96¡0.09
4 1.48¡0.34 5.41¡1.22

Plastics, Rubber and Composites 2006 VOL 35 NO 3 119

Krause-Sammartino et al. Maleic anhydride grafting of polypropylene

4 Wt-% of grafted MA in PP, prepared with MA concen-

3 Melt flow index of PP grafted in presence of 1.5 pph tration of 1.5 pph and two different peroxides: DCP
MA and two different peroxides: DCP and DIBP and DIBP

It is clear from Fig. 3 that an increase in the

macroradicals react with the grafting monomer before
concentration of peroxides in the reaction mixture
undergoing chain scission.
favours chain scission, as has already been discussed.
In general, low MA grafting and severe PP degrada-
It is perhaps more interesting to note the large difference
tion occur because of the low reactivity of MA towards
in the effects of the two peroxides on the MFI of the
the PP macroradicals and its low solubility in the PP
polymer. At a fixed concentration of peroxide, DIBP
melt. The symmetry of the MA molecule and the
produces a much smaller effect on the molar mass of the
deficiency of electrons around the C5C group are the
PP, indicating that this peroxide is more effective in
reasons for its low reactivity. However, in the presence
favouring the reaction steps that lead to grafting instead
of scission.14,25 This may be related to the longer halflife of an electron donating monomer, MA is activated, its
of DIBP with respect to DCP. A peroxide such as DCP electric structure becomes asymmetrical and the C5O
may generate a larger number of short lived macro- group acquires a radical anion character, which
radicals, which do not necessarily react to form the enhances MA reactivity.23 Because of the increased
grafted copolymers and therefore, chain scission occurs reactivity of the MA monomer, there are more reactive
with higher frequency. species available to graft, which can react with the PP
On the other hand, Fig. 4 shows that the yield of the macroradicals, reducing PP degradation. Therefore, the
grafting reaction improves with the use of higher MFI of the modified PP is lower under these conditions.
amounts of peroxide, but the effect of the two peroxides Tan et al. have also presented interesting results on
is essentially the same at a given concentration. the St assisted grafting of fluorinated acrylic (FA)
Considering the two results, it was decided to continue monomers onto PP. Although the reactivity of FA
the studies using DIBP to achieve high grafting yields towards PP was said to be low, grafting yield was much
with less molar mass reduction of the PP. improved by addition of St. In that case, more stable
styril macroradicals were formed that could copoly-
MA grafting in presence of toluene merise readily with the grafting monomer. Therefore,
As discussed previously, a large proportion of chain grafting was favoured, while PP chain degradation was
scission may lead to a product with too low viscosity, reduced.26
which makes further processing more difficult. Some Related grafting methods have been presented by Hu
researchers have investigated the reaction of MA with et al.,27 in their case through the use of activated PP (an
xylene in the presence of peroxides during the modifica- alkenyl-benzyl isocyanate bearing PP), obtained by the
tion of polyolefins.22 They reported either reaction with attachment of an activating monomer to the polymer
MA or formation of chain transfer complexes. These backbone. Then the reaction with the grafting monomer
results were obtained when xylene or other aromatic (caprolactam) took place at a higher rate, which was
compounds (containing benzylic hydrogens) were added also beneficial for the yield in extrusion processing.
to the mixture as solvents that were in large excess with In the present study, toluene, a benzylic hydrogen
respect to the MA content.22 The observations indicated containing aromatic compound, was added to reduce
that the chain reaction took place through the mobile chain scission reactions. However, it was added in small
hydrogens of the polymer (polyethylene in that study) quantities, so that it acts as a coagent and not as a
and the benzylic hydrogens of the solvent (coagent). solvent. This approach is more interesting because of its
Under these conditions, scission reactions took place to easier elimination. Therefore, toluene was added to the
a much lower degree. Depending on the structure of the mixtures containing 8400 ppm DIBP and 1.5 wt-%MA.
aromatic compound, the proportion of MA molecules Figure 5 shows the reduction in MFI (directly related to
grafted to the polyolefin or forming addition products the reduction in chain scission) with increasing toluene
with the solvent can also vary. concentration.
Styrene assisted melt grafting of PP has also been It is clear from the results that toluene is reducing
reported in the literature23 and a similar effect may the possibility of chain scission reaction, as was dis-
occur in the toluene assisted grafting observed in the cussed above. The MFI decreases greatly as the ratio
present work. As stated by Li et al.,23 a high graft yield Tol/MA is increased (Fig. 5). The value corresponding
and reduced PP degradation can be obtained if the PP to the sample prepared without toluene addition was

120 Plastics, Rubber and Composites 2006 VOL 35 NO 3

 Krause-Sammartino et al. Maleic anhydride grafting of polypropylene

5 Melt flow index of PP grafted in presence of 1.5 pph

MA, 8400 ppm DIBP and increasing amounts of 6 Infrared anhydride absorption region of samples pre-
toluene, with linear regression coefficient 0.998 pared in presence of toluene as chain scission inhibitor:
spectra are normalised with respect to 1100 cm21 peak

interpolated from Fig. 3, showing a good correlation

between the results of the different series.
Small differences were also observed with respect to
the amount of MA effectively grafted onto the PP.
Figure 6 shows the region of IR absorption of the
anhydride group corresponding to the MA grafted
moieties. The first observation is that grafting efficiency
increases when toluene is added to the reaction mixture
at Tol/MA50.5 (molar). However, further increase in
the ratio Tol/MA (just .0.5) results in a reduction in the
percentage of grafted MA.
Toluene molecules can tolerate the attack of the
peroxide to form benzyl radicals, which are stabilised
through the resonance of the aromatic ring.28 Therefore,
under the reaction conditions, toluene competes with the 7 Melt flow index of samples prepared with different
formation of the macroradicals, reducing the occurrence amounts of DIBP, with and without addition of toluene
of polymer chain scission reactions. At the same time,
toluene can compete with MA for the reactive sites is relatively fast and easy to handle. Table 4 shows a
generated in the polymer chain, so that if the toluene comparison for the maleinisation of PP realised on
concentration is further increased, the grafting yield is the same polymer and with similar amounts of
reduced. A similar effect has been reported for St peroxide (DIBP) and MA. In the extrusion process, a
assisted grafting of MA onto PP. In that case, at high slightly higher MA% was utilised to compensate for
concentrations of St, this monomer reacts to stabilise the volatilisation. The use of extrusion gave a product with
PP macroradicals and reduce PP degradation. Because essentially the same MFI, but higher grafting efficiency.
of the increased stability, further MA grafting may Similarly, Sun et al. have also reported grafting trends in
become difficult, and therefore, the grafting efficiency batch mixing and extrusion processes in their work on
decreases after reaching an optimum at a molar ratio St/ the grafting of glycidylmethacrylate onto PP. In that
MA51.0 (molar). In the present case, the results indicate study, styrene was used in the assisted melt grafting of
that the optimum grafting efficiency occurs at Tol/ PP.29
MA50.5 (molar). Although the results were satisfactory with regard to
the MA grafting, the resulting material had very low
Reactive extrusion process viscosity, because of the molar mass reduction.
Comparison with batch process results Therefore, the use of an initial PP of higher molecular
After identifying the main effects of peroxide, MA weight (MFI 0.34 g 10 min21, measured at 190uC and
concentration and toluene addition on the grafting 2.16 kg) was considered as well as the addition of
process under study, the maleinisation of PP was also toluene as chain scission inhibitor during the maleinisa-
performed in a single screw extruder. This type of tion process. Figure 7 shows the beneficial effect of
equipment is more commonly utilised in commercial toluene addition to the extrusion process to reduce chain
practice, because it involves a continuous operation and scission of the polymer.

Table 4 Melt flow index and MA grafting results obtained by intensive batch mixing and reactive extrusion: raw PP had
MFI of 1.1 g 10 min21 measured at 190u and 2.16 kg

MA, pph DIBP, ppm Wt-% grafted MA MFI, g 10 min21

Batch mixer 1.50 7873 0.76 91.98

Extrusion 1.88 7400 1.08 94.68

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Krause-Sammartino et al. Maleic anhydride grafting of polypropylene

As observed in the batch mixer study, the addition of

toluene to the reaction mixture reduces the influence of
chain scission reactions, giving acceptable MA grafting
(0.6–1 wt-%) without degrading the polymer excessively.
Therefore, the material can be handled as usual, produc-
ing pellets. This step of the process is important to
facilitate its addition as coupling agent to different
formulations. In addition, a relatively high molar mass
of the coupling agent is a desired feature because the
grafted moieties can interact with the polar surface of
the filler, while simultaneously the long chains of the
modified polymer can interact with the polymer matrix
through entanglements or cocrystallisation.

Evaluation of produced MA-g-PP in composite a

formulations
To evaluate the utilisation of the obtained copolymers as
coupling agents, composite materials were manufac-
tured by incorporating 30% of short glass fibres. The
action of this type of grafted polyolefins is widely
known; the anhydride groups grafted to the polymer
interact with the polar Si–OH groups of the glass fibres,
through covalent bonds or strong electrostatic forces,
such as H-bonding. The non-polar part of the polymer
chain interacts with the matrix through entanglement
formation or through cocrystallisation in the case of
partially crystalline polymers, such as isotactic PP. Both
features are prerequisites to obtaining a good coupling
agent, since they will lead to improved mechanical
properties of the composite material.30 b
Therefore, a composite was prepared by mixing in the
batch mixer polypropylene PP1 (MFI: 3 g 10 min21, a no copolymer addition; b addition of 10 wt-%MA–PP
copolymer
measured at 230uC and 2.16 kg) as the matrix, short
8 Short glass fibre composites (30 wt-% fibres)
glass fibres at 30% by weight concentration and
10 wt-%MA–PP copolymer containing a MA grafted
concentration of 1.15 wt-%. there is no bonding between fibre and matrix; the fibre
The mechanical properties of the composites in surface is completely clean, and free of attached
tensile, flexural and impact tests were determined. An polymer. On the right-hand side of the micrograph,
important improvement (30–39%) in tensile and flexural there is a footprint of a fibre that was cleanly separated
strengths of the material was observed, with respect to from the matrix during the fracture because of low
that of the composite made without adding the coupling interfacial adhesion. On the other hand, when the
agent (Table 5). These results indicate improved inter- copolymer is added to the composite, the adhesion
facial adhesion. Analogously, the impact strength of the between matrix and fibre is improved. Figure 8b shows a
material increases by 86% with the addition of 10 wt-% fibre completely covered by the polymer, and there is
copolymer. Again, this indicates that strong interfacial no separation between the polymer and the fibre;
adhesion has improved the load transfer between the good wetting and strong adhesion are evident. These
matrix and the rigid glass fibres, with the consequent morphologies are in complete agreement with the
improvement in the mechanical behaviour of the mechanical results already presented.
composite. Therefore, MA grafted PP can be tailored to accept
Furthermore, the samples were freeze fractured and different copolymers according to the final properties
the resulting fracture surfaces were characterised by required. Of course, it is expected that a higher
SEM. The results can be observed in Fig. 8a and b. percentage of MA grafted to the modified PP would
Comparison of the two figures reveals the efficiency of generate a higher number of attachments of the chains
the MA–PP copolymer as coupling agent. In the com- to the fibre, leading to a stronger adhesion of the
posite prepared without the coupling agent (Fig. 8a), copolymer to the reinforcing fibres. On the other hand,

Table 5 Mechanical properties of short glass fibre composites with and without MA–PP copolymer addition

Without MA–PP With MA–PP

Tensile tests E, GPa 5.34¡0.29 5.18¡0.17

Strength, MPa 70¡2 92¡2
Deformation at break, % 1.9¡0.2 3.4¡0.4
Flexural tests Eb, GPa 4.91¡0.14 5.34¡0.21
Strength, MPa 87¡3 121¡3
Impact tests Impact resistance, J m21 97.5¡5.2 181.6¡14.3

122 Plastics, Rubber and Composites 2006 VOL 35 NO 3

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