Polymer Bulletin 48, 389-396 (2002)

Polymer Bulletin
 S p r i n g e r -Ver lag 2 0 0 2

Synthesis of graft copolymer of styrene and acrylonitrile

onto poly (butyl acrylate) by using polymeric peroxide
Xuezhen Shi1, Weizhuang Cheng1 ( ), Zhixiang Lu2, Qiangguo Du 2 ( ), Yuliang
Yang2
1
School of Materials, Tongji University, Shanghai 200092, People’s Republic of China
2
Department of Macromolecular Science, Fudan University, the Key Laboratory of Molecular
Engineering of Polymers, Shanghai 200433, People’s Republic of China
email: qgdu @ fudan.edu.cn, Tel.: +86-21-65643891, Fax: +86-21-65640293

Received: 6 March 2002 / Revised version: 8 May 2002 / Accepted: 13 May 2002

Summary
Two-stage seeded emulsion copolymerization of butyl acrylate with tert-butyl 3-
isopropenylcumylperoxide (D120) was performed at 70°C . Copolymer latex with
0.2m of particle size was obtained. Emulsion graft polymerization of styrene and
acrylonitrile onto the copolymer of butyl acrylate was initiated by peroxy bonds in the
D120 units of the backbone chains at 120°C . Graft copolymers with higher grafting
ratio were derived. It was found that the grafting ratio tends to increase with the
increasing D120 in feed of copolymerization with butyl acrylate. The graft
copolymers were blended with SAN resin, and a kind of AAS resin was obtained.
Both elongation at break and Izod impact strength of the AAS resin reached maximum
at grafting ratio of 0.25, which were comparable with the values of ABS resin for
general purpose. A method to improve the grafting efficiency on the saturated
polyacrylate elastomer rubber was developed.

Introduction
Graft copolymers are required widely in various application fields of polymer alloys
(blends), compatibility improvements, surface modifications, and so on. The processes
to prepare graft copolymers has been investigated intensively including radical graft
copolymerization, which can be performed by using special initiators, chain transfer
reaction [1], radiation polymerization [2,3], light polymerization[4], and mechanics
[5,6]. Recently studies on controlled radical copolymerization, especially the atom
transfer radical polymerization (ATRP), were developed for preparation of graft
copolymer [7-11], by which the graft copolymers of well-controlled molecular weight
and molecular weight distribution can be obtained. On the other hand, polymeric
peroxides have also been studied with regard to their potential initiating characteristics
in vinyl polymerization to prepare block and graft copolymers [12-14]. Graft
copolymers initiated by the thermal cleavage of pendant proxy bonds always result in
higher grafting efficiency [13].
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ABS resin is a widely used plastic; however, the polybutadiene in the resin is easy to
be oxidized. The use of saturated rubber instead of polybutadiene has been tried to
overcome the poor weatherability of ABS resin. Usually it is difficult to graft onto the
saturated rubber because of its chemical stability.
The purpose of this paper is to develop a process to improve the grafting efficiency on
the poly (butyl acrylate), which is saturated and mostly used as rubber backbone in
AAS resin. First, the copolymerization of butyl acrylate (BA) with tert-butyl 3-
isopropenylcumylperoxide (D120), a commercially available polymeric peroxide, was
performed in emulsion. Next, the graft of styrene (St) and acrylonitrile (AN) onto the
copolymer of BA/D120 initiated by the pendant peroxy bonds was studied. In
addition, the relationship between grafting ratio and mechanical properties of the AAS
resin thus obtained was studied as well.

Experimental

Materials
Styrene (St), butyl acrylate (BA), and acrylonitrile (AN) from Shanghai Gaoqiao
petrochemical Co. and ethylene glycol dimethacrylate (EGDM) from Tokyo Kasei
Kogyo Co were purified by distillation under reduced pressure before use. D120 was
kindly supplied by Kayaku AKZO Co (Japan). The oligomer and other impurities in
D120 were removed by precipitation in methanol, which was removed then by
distillation under reduced pressure. Potassium persulfate (KPS) and sodium dodecyl
sulfate (SDS) from reputable suppliers were used as received. Sodium dimethyl
dithiocarbamate was obtained from Shanghai Changjiang Chemical Co., and water
solution of 10wt% was prepared for use. SAN resin (24wt% of AN content, 2.2
g/10min of Melt Index) was purchased from Lanzhou Petrochemical Co., and dried in
oven at 60°C for 5h before use.

Preparation of copolymer of BA with D120

Two-stage seeded emulsion copolymerization was performed to prepare the
copolymer latex with 0.2 m of particle size. At first 100g of BA was added to 250g
of water containing 1.2g of SDS and 0.3g of KPS, the mixture was stirred under
nitrogen for 4h at 70°C . Latex with 0.085m of particle size was obtained and used as
seed. In the second stage monomer mixture consisting of 97.5g of BA, D120 and 1g of
EGDM was added dropwise to 100g of water containing 0.1 g of KPS and 2.5g (by
solid) of seed latex within 4h at 70°C with stirring and under nitrogen. At the same
time additional 0.2g of KPS and 1g of SDS were dissolved in 25g water and added in
batches. After addition was complete, stirring was continued for another 2h at 70°C .
The conversion, usually higher than 95% °C was calculated from total solid content.

Characterization of the copolymer latex

Particle size and particle size distribution of latex was measured on BECKMAN
COULTER LS230 Particle Size Analyzer.
Some latex of the copolymer was precipitated, filtered, washed extensively with
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water, and soaked in excessive methanol for 24 hr to remove residual monomer, then
dried in vacuum below 50°C . The solid product obtained was used for gel
determination, Raman analysis and DSC measurement.
0.5 g samples obtained above (accurately weighed) were added to the tubes containing
50ml toluene and kept swelling at room temperature for 96 h. After filtration with
metal mesh and drying under vacuum, the gel percentage was calculated. The degree
of swelling Q was calculated as follows:
Q= (W1/ρ1+ W2/ρ2)/ (W2/ρ2)
Where W1 and W2 are the weight of solvent and copolymer in the swollen gels
respectively, and ρ1 and ρ2 are the density of solvent and copolymers before swelling.
All the results are listed in Table 1.
Differential Scanning Calorimetry (DSC) analysis was performed on a Natzsch DSC-
200 instrument, with the heating rate of 10°C /min, while nitrogen gas purge was
used.
Raman Spectra were recorded with a LabRam-1B Micro-spectrometer, with excitation
line of 631.81nm and power of 6mw.

Synthesis of graft copolymer

A 200ml autoclave was charged with 100g of water, 22g of St, 8g of AN, 0.4g of
SDS, 0.4ml of aqueous solution of sodium dimethyl dithiocarbamate, and 20g of
copolymer latex (by solid) obtained above. Solution of sodium dimethyl
dithiocarbamate was used as a terminator to react with the residual KPS, which may
initiate homopolymerization or copolymerization of St and AN and decrease grafting
efficiency. After purged by nitrogen, the autoclave was sealed and stirred, then heated
to 120°C gradually within 2h and kept for another 4h. After coagulation, filtration,
washing and drying in vacuum, the powder product of graft copolymer was obtained.

Determination of grafting ratio

0.5g of dried powder product obtained above was immersed in 50ml of acetone for
48h at room temperature. The insoluble residue, composed of graft copolymer and
ungrafted poly (butyl acrylate), was separated from solution, which containing binary
copolymer of St and AN, on ultracentrifuge, and washed with acetone for three times.
The grafting ratio was calculated from IR spectrum, which was recorded on a Nicolet
Magna 550 FTIR spectrometer. Calibration curve for IR analysis was established by
using a series of quantitatively prepared blends of poly (butyl acrylate) and SAN
(copolymer of St and AN) in various compositions. The peak heights of absorption at
2237cm-1, 1735cm-1 and 701cm-1, assigned to monomer units of AN, butyl acrylate
and St in graft copolymer respectively, was measured.

Blending and mechanical properties testing

The graft copolymer obtained above was blended with SAN resin in a Brabender
mixer with a capacity of 60g at 220°C for 5min, with rotor speed of 45 rpm. In every
blend sample the content of poly (butyl acrylate) was kept as 20(wt) %. Standard bar
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was prepared by compression molding at 200°C . Tensile properties and notched Izod
impact strength were measured according to ASTM D638 and ASTM D256,
respectively. Five to ten bars were tested on each instrument and standard deviation of
less than 20% was found for each property.

Morphology observation

Morphology of undeformed molded test specimens was examined using a Hitachi H-

600 TEM. The sample was stained with Ruthenium solution for 10 days, and then cut
on a Riechet-Jung Ultramicrotome.

Results and discussion

Copolymer latex

Main features of the BA/D120 copolymer latex, such as conversion, gel percentage,
swelling degree in toluene and particle size, are summarized in Table1. Generally, in
the preparation of ABS resin the important aspects of the rubber substrate affecting
properties such as impact, flow, and surface gloss are the average rubber particle size
and particle size distribution. Larger than 0.2m of diameter is believed to be required
for satisfying high impact value. As shown in Table1, after two-stage seeded emulsion
polymerization, the particle sizes of the copolymer latex were about 0.2m in
diameter, which can meet the requirement for toughening purpose in SAN matrix. On
the other hand in the rubber-toughened resin cross linking of the rubber component is
also required to some extent to minimize deformation of the rubber particles. Table1
shows that EGDM, as a diene-type monomer, is effective in cross linking the rubbery
product, gel fraction of which was 80% or more.
The existence of D120 monomer units in the copolymer molecules was confirmed by
both Raman spectra and DSC curves. The content of D120 introduced to the
copolymer in the present research was so trifle that the feature absorption peaks of
D120 units on the normal IR spectra were too weak to be distinguished. Therefore, the
more sensitive Raman spectrometer was used. Figure 1 shows the Raman spectra of
copolymer D120 (3wt %) with BA and homopolymer of BA. In comparison to
homopolymer of BA, the copolymer has absorption at 1006cm-1 assigned to meta-
substituted benzene ring, which was introduced by incorporating D120. The result
indicates that the copolymerization of D120 with BA took place, which was also
confirmed by DSC measurements. As shown in Figure 2, an exothermic peak
corresponding to the characteristic decomposition of peroxy groups in D120 [15]
emerges around 190°C on the DSC curves of the product of copolymerization. The
area of the exothermic peak increases gradually with increasing of D120 in feed
whereas the product in the absence of D120 in feed shows no exothermic peak there.
Accordingly, the result shows that the units of D120 have been incorporated to
polymer chains, and the pendant O-O bonds of D120 units survived after
copolymerization at 70°C . The product is real copolymer of butyl acrylate with D120.
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Grafting ratio

The measurement result of grafting ratio, which is defined as the weight ratio of
grafted SAN to the backbone of the copolymer of butyl acrylate, is shown in Figure 3.
The grafting ratio tends to increase with the increasing D120 in feed of
copolymerization with butyl acrylate. The result means that the more D120 units
introduced to the backbone, the more graft sites created by decomposition of the
pendant peroxy bonds on the backbone during graft polymerization at 120°C .On the
other hand, graft copolymerization of St and AN onto the copolymer of BA with D120
may also take place via chain transfer, which resulted in a finite grafting ratio for zero
D120/BA% in feed.
394

It can be found that a certain amount of SAN was not grafted onto the backbone. It
may be attributed to the copolymerization of AN with St initiated by heat or by
fragmentary free radicals produced during decomposition of pendant peroxy bonds on
the backbone.
The copolymerization of butyl acrylate with D120 and the graft copolymerization of
AN and St onto the copolymer can be shown schematically as follows:

The yield tensile strengths, elongation at breaks, and notched Izod impact strengths of
blends of SAN with the product of graft copolymerization are shown in Figure 3. It
can be seen that both elongation at break and Izod impact strength reached maximum,
when D120/BA in feed was 0.8/100 yielding grafting ratio of 0.25. The result obtained
in this study agreed closely with the conclusion of M.Rink [16], who reported that in
the toughening of ABS resin, the impact strength increased as grafting ratio increased
 395

and leveled off or decreased around 25% of grafting ratio due to the more
presence of glassy subinclusion reducing the thermal stresses in the matrix
surrounding the dispersed particles. Figure 4 also shows that the optimum
mechanical properties of AAS obtained in this study are close to those of ABS
resin.

Morphology

Although the weight fraction of Poly (butyl acrylate) in all the AAS samples was kept
constant, photomicrograph obtained by TEM shows remarkable morphologic
variations as the grafting ratio varies (Figure 5).

For scarcely grafted sample with grafting ratio of 10%, the incompatibility of poly
(butyl acrylate) with matrix polymer induces the particle to coalesce, while for highly
grafted sample with grafting ratio of 49%, the existence of an outer shell of SAN
grafted on the rubber particles seems to prevent them from coalescing, so that rubber
particles well dispersed in the matrix. The sample with intermediate grafting ratio of
25% showed “intermediate” dispersion of rubber particles with some clustering which
is usually associated with improved impact strength in comparison to blends with
uniform graft rubber particle dispersion [17].The electron micrograph indicates that
many connected particles tends to line up in long rows likely due to the incomplete or
wart-like graft coverage of the rubber particle. The similar morphology was observed
by H.Keskkula [18].

Conclusions

The emulsion copolymerization of butyl acrylate with D120 was performed. Peroxy
bonds of D120 units survived after reaction of copolymerization at 70°C . The free
radicals produced during decomposition of the pendant peroxy bonds on the
copolymer at 120°C can initiate the graft polymerization of AN and St onto the
backbone of the copolymer. The grafting ratio tends to increase with increasing D120
in feed of copolymerization with butyl acrylate. Izod impact strength reached
maximum when D120/BA in feed was 0.8/100 yielding grafting ratio of 0.25. A new
396

method to raise grafting on the saturated polyacrylate rubber in the synthesis of AAS
resin was developed.

Acknowledgements. Special Funds for Major State Basic Research Projects (G199064800) are
greatly acknowledged.

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