Materials Letters 66 (2012) 219221

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Preparation, microstructure and properties of ABS resin with bimodal distribution of

rubber particles
Gongsheng Li a, c, Shulai Lu a, b,, Jianxun Pang b, Yanjun Bai c, Liu Zhang b, Xuhong Guo a
a
b
c

School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
Research Institute of Jilin Petrochemical Company, PetroChina Company Ltd., Jilin 132021, China
Synthetic Resin Factory of Jilin Petrochemical Company, PetroChina Company Ltd., Jilin 132021, China

a r t i c l e

i n f o

Article history:
Received 23 June 2011
Accepted 15 August 2011
Available online 22 August 2011
Keywords:
ABS resin
Polymers
Microstructure
Bi-seeded emulsion grafting
copolymerization
Toughness
Rigidity

a b s t r a c t
A novel ABS resin with bimodal distribution of rubber particles (BM-ABS) was prepared by bi-seeded emulsion
grafting copolymerization (Bi-SEGP) using two different size polybutadiene (PB) particles (320 nm and 575 nm)
as seeds. For property comparisons, a model ABS resin with unimodal distribution of rubber particles (UM-ABS)
was prepared by only using 320 nm PB particles as seeds. Microscopical morphology of BM-ABS and UM-ABS
was observed by transmission electron microscope (TEM). The results showed that BM-ABS possessed higher
properties than UM-ABS. Specically, keeping the same rubber content, BM-ABS had higher toughness than
UM-ABS and almost the same rigidity as UM-ABS; keeping the same toughness, BM-ABS had higher rigidity
and needed less rubber content than UM-ABS. The synergistic effect of the bigger and the smaller rubber particles
was the essential reason why BM-ABS displays improved properties than UM-ABS.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Acrylonitrile(AN)butadiene(BD)styrene(ST) (ABS) resin is a
rubber-toughened thermoplastic polymer. Its microstructure was the
so called sea-island two phases, i.e. dispersed rubbery polybutadiene
(PB) phase distributed over rigid poly(ST-co-AN) (SAN) continuous
phase [1,2]. It shows outstanding allround properties, such as excellent
impact strength, satisfactory tensile strength and easy processibility,
and thus has extensive applications in automotive parts, ofce machines, house appliances etc. [3].
ABS resin was prepared mainly by blending emulsion grafting copolymer (PB-g-SAN) with matrix STAN copolymer (m-SAN) [4]. PBg-SAN was prepared by seeded emulsion grafting copolymerization
(SEGP) of ST and AN using PB particles as seeds, and STAN copolymer grafting onto the surface of PB particles (g-SAN) to achieve the
necessary interaction with the m-SAN. Usually, PB particles were
300 nm 50 nm in mean diameter obtained by conventional emulsion polymerization.
Generally, the toughness (mainly characterized by impact
strength) and rigidity (mainly characterized by tensile strength) of
ABS could be adjusted by changing the proportion of PB and m-SAN

Corresponding author at: School of Chemical Engineering, East China University of

Science and Technology, Shanghai 200237, China. Tel.: +86 21 64253491; Research Institute of Jilin Petrochemical Company, PetroChina Company Ltd., Jilin 132021, China.
Tel.: +86 432 63995724/63972733.
E-mail address: shulailu@hotmail.com (S. Lu).
0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.08.037

to tailor the different end-use applications [5]. But ABS resin is such
a kind of material that its toughness and rigidity are contradicting
[6], they are just like the two ends of a seesaw, and one end goes up
as the other goes down. So it is a technical challenge to notably increase impact strength of ABS resin while maintaining tensile
strength for matching some higher quality applications such as the
large area faceplate.
For ABS resin, the properties were determined not only by polymer compositions, but by the size, the number and the size distribution of PB rubber particles. Usually, the bigger size rubber particles
were beneted to enhance toughness but with rigidity lost, and smaller size rubber particles were favorable to keep rigidity but with
lower toughness [7]. The combination use of bigger and smaller rubber particles was expected to solve the contradiction of toughness
and rigidity, and to obtain a novel ABS with higher properties than
that of alternatives.
In this work, bi-seeded PB-g-SAN (Bi-PB-g-SAN) was prepared by
bi-seeded emulsion grafting copolymerization (Bi-SEGP) using two
different size PB particles (320 nm and 575 nm) as seeds, and then
blending Bi-PB-g-SAN with m-SAN to obtain a novel ABS (BM-ABS)
with bimodal distribution of rubber particles (Bi-MDRP). For the
property comparisons, a model ABS (UM-ABS) with unimodal distribution of rubber particles (Uni-MDRP) was prepared by blending
normal mono-seeded grafting PB-g-SAN (Mo-PB-g-SAN, using
320 nm PB particles as seeds only) with the same m-SAN as BMABS. The mechanism of bi-seed rubbery phase to improve property
of ABS resin was analyzed in brief.

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G. Li et al. / Materials Letters 66 (2012) 219221

2. Experimental
2.1. Materials
PB latex with number-average particle size of 320 nm (PB-320,
57 wt.%) and m-SAN (bonding AN 25.5% in weight) were obtained
from ABS plant of Jilin Petrochemical Company (JPC). PB latex with
number-average particle size of 575 nm (PB-575, 37 wt.%) was supplied
by Daqing Petrochemical Company. Acrylonitrile (AN), butadiene (BD)
and styrene (ST) were all industrial products freshly supplied by JPC.
Disproportionated potassium rosinate solution (RK, 25 wt.%), cumine
hydroperoxide (CHP), sodium pyrophosphate (SPP), ferrous sulfate
(FES), and t-dodecyl mercaptan (TDDM) that were all industrial products purchased from market were used as received; double deionized
water (DDI) was used throughout.

2.2. Preparation of Bi-PB-g-SAN

Bi-PB-g-SAN was prepared by Bi-SEGP using two different size
PB particles (PB-320/PB-575 = 90/10 in weights in dry basis) as
seeds in a 10 L reactor. The detailed procedures were given as
follows.
Initial charge: (1) 13.5 g SPP and 0.12 g FES were dissolved in
3330 g DDI in the reactor, followed by adding 2842.1 g PB-320 and
486.5 g PB-575. (2) Adding 84.0 g AN, 216.0 g ST and 5.37 g TDDM.
(3) Turning on stirrer, and then purged with nitrogen to remove oxygen. (4) Raising temperature, when the reaction temperature arrived at 43 C, adding 1.65 g CHP, and keeping temperature at 45 C
for 1 h.
Addition 1: Mixing 6.50 g RK, 16.11 g TDDM, 255.0 g AN, 645.0 g ST,
6.60 g CHP and 300.0 g DDI to achieve an emulsion, and then feeding it
into the reactor continuously and lasting for 2 h. Keeping reaction temperature at 65 C during this step.
Addition 2: Dissolving 4.50 g SPP and 0.03 g FES in 82.5 g DDI, then
adding the SPP/FES solution and 2.55 g CHP into the reactor in one
batch in sequence. Keeping reaction temperature at 71 C for 30 min.
The resultant Bi-PB-g-SAN latex was coagulated using dilute sulfuric
acid at a certain temperature to get wet Bi-PB-g-SAN powder, then drying it by oven to obtain the expected Bi-PB-g-SAN with theoretical PB
proportion 60 wt.%.
Mo-PB-g-SAN also with the theoretical PB proportion 60% was prepared using the same recipe and preparation conditions as Bi-PB-gSAN except PB-575 being replaced by the same amount of PB-320 in
weights in dry basis.

Table 1
Property comparisons of BM-ABS with UM-ABS.
Sample No.

BM-ABS-1

BM-ABS-2

UM-ABS-1

UM-ABS-2

PB-320/PB-575, wt.%/wt.%
PB-g-SAN proportion, wt.%
PB proportion in ABS, wt.%
Izod impact strength, J/m2
Tensile strength, MPa
Flexural strength, MPa
Flexural modulus, MPa
Melting index, g/10 min

90/10
22.0
13.2
25.2
51.2
84.3
2847
21.8

90/10
20.0
12.0
20.6
55.4
87.8
2935
25.6

100/0
22.0
13.2
20.5
52.2
82.6
2839
22.5

100/0
25.0
15.0
25.3
46.8
78.2
2568
18.6

3. Results and discussion

3.1. Properties of BM-ABS
The properties of BM-ABS and UM-ABS were comparatively shown
in Table 1, wherein BM-ABS-1 possessed the same PB proportion as
UM-ABS-1 and the same level of Izod-IS as UM-ABS-2, and BM-ABS-2
possessed the same level of Izod-IS as UM-ABS-1.
By comparing the properties of BM-ABS-1 with UM-ABS-1 under the
same PB proportion (13.2 wt.%), it could be seen from Table 1 that the
Izod-IS of BM-ABS-1 was obviously higher than that of UM-ABS-1, the
increase ratio was more than 20%; the tensile strength and other properties change slightly. It could be concluded that with the same PB proportion, BM-ABS possessed higher toughness than UM-ABS, and kept
almost the same rigidity as UM-ABS.
From the comparison of UM-ABS-2 with BM-ABS-1 in Table 1, it
could be seen that to reach the same high level of Izod-IS as BM-ABS1 (25.2 J/m2), more rubbery phase content was needed in UM-ABS-2,
the PB proportion was 15 wt.% instead of 13.2 wt.%. Meanwhile, the tensile strength and all the other properties of UM-ABS-2 decreased remarkably. These results demonstrated further that Bi-SEGP could
improve Izod-IS of ABS without other properties loss.
The comparisons of UM-ABS-2 with UM-ABS-1 in Table 1 showed
that the cost for increasing toughness in UM-ABS-2 was so enormous
that all the other properties decreased evidently. This provided an obvious evidence to illustrate the contradiction of toughness and rigidity in
ABS resin.
Comparing the property of BM-ABS-2 with UM-ABS-1, it could been
seen from Table 1 that reaching the same value of Izod-IS as UM-ABS-1,
20.5 J/m 2, less PB content was needed in BM-ABS-2, it was only
12.0 wt.%. For BM-ABS-2 with reduced rubbery phase content, the rigidity characteristics were signicantly higher than those of UM-ABS-1.
Meanwhile, the melting index increased remarkably. These would be
benecial to matching the higher application demands for the rigidity
and processibility.

2.3. Preparation of BM-ABS

BM-ABS was prepared by melt blending Bi-PB-g-SAN with m-SAN
using a single screw extruder (DMG-40, Placo., Inc) with screw speed
of 80 rpm at 200 C. The UM-ABS was prepared by melt blending MoPB-g-SAN with the same m-SAN at the same condition.

2.4. Characterization
Samples for measuring the properties of nal ABS products were all
prepared by injection molding machine (IS80FPA-2A, Toshiba) at
200 C. Izod impact strength (Izod-IS) was tested using a notched Izod
Impact tester (Yasuda No. 158, ASTM D256). Tensile strength (ASTM
D638), exural strength and exural modulus (ASTM D790) tests
were performed using a universal test machine (AGS-5KN, Shimadzu).
Melting index was determined using a melting index apparatus (120FWP, Yasuda, ASTM D1238). Micromorphologies were observed by
Transmission Electron Microscopy (TEM, JEM-2000EX).

500nm
Fig. 1. TEM microphotograph of BM-ABS.

G. Li et al. / Materials Letters 66 (2012) 219221

221

ones, and the small ones could succeed and further disperse the impacting energy, the synergistic effect between the bigger and the smaller
rubber particles resulted in BM-ABS could defend against higher impacting energy than UM-ABS possessing only Uni-MDRP when they kept the
same rubber content. Briey, the synergistic effect of the two different
size rubber particles was the essential reason why BM-ABS displayed
better properties than UM-ABS.
4. Conclusions

500nm
Fig. 2. TEM microphotograph of UM-ABS.

BM-ABS prepared by Bi-SEGP possessed Bi-MDRP and thus possessed higher properties than UM-ABS. When keeping the same rubber
content, BM-ABS had higher Izod-IS than UM-ABS and almost the same
tensile strength as UM-ABS; with the same Izod-IS, BM-ABS had higher
tensile strength and needed less rubber content than UM-ABS. The synergistic effect of the two different size rubber particles was the essential
reason of BM-ABS possessing higher properties than UM-ABS.

3.2. Microscopical morphology of BM-ABS

Acknowledgments

The microphotographs of BM-ABS and UM-ABS were comparatively shown in Figs. 1 and 2, respectively.
It could be seen from Fig. 1 that there were small parts of bigger rubber particles distributed over the large part of smaller rubber particles,
namely BM-ABS was Bi-MDRP in micromorphology. This result corresponded well with the expectation of Bi-SEGP for preparing BM-ABS,
and the visible difference between bigger and smaller particles was derived from the different particle size of seeds. Fig. 2 showed that all the
rubber particles in UM-ABS were almost in the same size, i.e. UM-ABS
presented Uni-MDRP. It also corresponded to the preparation of UMABS by normal mono-SEGP, and the tiny difference of rubber particle
size in UM-ABS originated from the seed particle size distribution.

The authors are grateful for the nancial support by the key scientic and technological project of PetroChina (0704D01-01).

3.3. Mechanisms of bi-seed rubbery phase to improve property of ABS

By comparing the property and the micromorphology of BM-ABS
with those of UM-ABS, the mechanisms of bi-seeds to improve properties of ABS seemed perceptible: BM-ABS possessed Bi-MDRP, the bigger
rubber particles could absorb more impacting energy than the smaller

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