Filler–Polymer Interactions in Both Silica and Carbon Black-

Filled Styrene–Butadiene Rubber Compounds

SUNG-SEEN CHOI

Kumho Research and Development Center, 555, Sochon-dong, Kwangsan-gu, Kwangju 506-711, Korea

Received 21 August 2000; revised 29 November 2000; accepted 8 December 2000

ABSTRACT: Bound rubber in a filled rubber compound is formed by physical adsorption

and chemisorption between the rubber and the filler. Styrene– butadiene rubber (SBR)
is composed of four components of styrene, cis-1,4-, trans-1,4-, and 1,2-units. Filler–
polymer interactions in both silica and carbon black-filled SBR compounds were studied
by analyzing microstructures of the bound rubbers with pyrolysis-gas chromatography.
Differences in the filler–polymer interactions of the styrene, cis-1,4-, trans-1,4-, and
1,2-units were investigated. The filler–polymer interactions of the butadiene units were
found to be stronger than that of the styrene unit. The interactions of the cis-1,4- and
trans-1,4-units were stronger with carbon black than with silica, whereas the 1,2-unit
interacted more strongly with silica than with carbon black. © 2001 John Wiley & Sons,
Inc. J Polym Sci B: Polym Phys 39: 439 – 445, 2001
Keywords: filler–polymer interaction; bound rubber; styrene– butadiene rubber

INTRODUCTION Silica has been used as an important reinforc-

The filler–polymer interaction leads to the forma-
tion of bound rubber by physical adsorption,
chemisorption, and mechanical interaction. With
regard to the polymer, both the chemical struc-
ture of the molecules (e.g., polarity) and its micro-
structure (e.g., configuration and molecular
weight) influence the level of bound rubber con-
tent. Bound rubber, sometimes termed filler gel,
has been recognized as an important factor in the
mechanism of rubber reinforcement, and it is of-
ten considered to be a measure of surface activity.
Factors affecting the formation of bound rubber
have been studied by many researchers.1–5 Bound
rubber is a parameter that is simple to measure,
but the factors influencing the test results are
very complicated.
Correspondence to: S.-S. Choi (E-mail: sschoi@swan.
kumho.co.kr)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 39, 439 – 445 (2001)
© 2001 John Wiley & Sons, Inc.
ing agent in a rubber compound together with
carbon black.6 –9 The precipitated silica has a
unique characteristic of having many hydroxyl
groups on its surface.6,10 Because intermolecular
hydrogen bonds between hydroxyl groups on the
surface of silica are very strong, it can aggregate
tightly.7,11 Its property can cause a poor disper-
sion of silica in a rubber compound. For silica-
filled rubber compounds with an accelerated sul-
fur-cure system, the curatives are adsorbed on
the silica surface so that they have slow cure
characteristics compared to carbon black-filled
compounds.
Styrene-butadiene rubber (SBR) is a copolymer
of styrene and butadiene. The butadiene unit has
three different microstructures including the cis-
1,4-, trans-1,4-, and 1,2-units as shown in Scheme
1. In the present article, filler–polymer interac-
tions in both silica and carbon black-filled SBR
compounds have been studied by chemical analy-
sis of the microstructures of the bound rubbers
using pyrolysis-gas chromatography (pyrolysis-

439
440 CHOI

coupling agent, cure activators, antidegradants,

Scheme 1
GC). The use of pyrolysis-GC for the characteriza-
tion and analysis of polymers has been used.12–14
The filler–polymer interactions of the styrene, cis-
1,4-, trans-1,4-, and 1,2-units were compared.
EXPERIMENTAL
Both the silica and carbon black-filled compounds
were made of SBR, silica, carbon black, silane
and curatives. The silane coupling agent of 8.0 wt
% of the silica content was added. The total filler
content was 80.0 phr. The content ratio of silica/
carbon black was varied from 10.0/70.0 to 70.0/
10.0 phr. The formulations are listed in Table I.
SBR 1500 was supplied from Korea Kumho Pe-
troleum Co. The relative abundances of the sty-
rene, cis-1,4-, trans-1,4-, and 1,2-units were mea-
sured with a Fourier transform infrared test and
calculated using the typical absorptions of the
different units and their respective molar absorp-
tion coefficients. Contents of the styrene, cis-1,4-,
trans-1,4-, and 1,2-units in the raw SBR 1500 are
23.5, 9.1, 52.6, and 14.8 wt %, respectively. Z 175
[pH ⫽ 6.9, Brunauer–Emmett–Teller (adsorption
isotherm) ⫽ 175 m2/g] and N 330 (dibutylphtha-
late absorption ⫽ 1.02 mL/g) were supplied from
Kofran Co. and Columbian Chemicals Korea, re-
spectively.
Mixing was performed in a Banbury-type
mixer at a rotor speed of 40 and 30 rpm for master
batch (MB) and final mixing (FM) stages, respec-
tively. The initial temperatures of the mixer were
110 and 80 °C for the MB and FM stages, respec-

Table I. Formulations (phr) for Both Silica and Carbon Black-Filled SBR Compounds

Compound No. 1 2 3 4 5 6 7

SBR 1500a 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Z 175b 10.0 20.0 30.0 40.0 50.0 60.0 70.0
Si 69c 0.8 1.6 2.4 3.2 4.0 4.8 5.6
N 330d 70.0 60.0 50.0 40.0 30.0 20.0 10.0
ZnO 4.0 4.0 4.0 4.0 4.0 4.0 4.0
Stearic acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0
HPPDe 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0
DPGf 0.5 0.5 0.5 0.5 0.5 0.5 0.5
TBBSg 1.6 1.6 1.6 1.6 1.6 1.6 1.6
Sulfur 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Mooney
viscosity
ML 1 ⫹ 4 at
100°C 135.0 141.7 141.3 141.7 145.4 158.8 174.6
Bound rubber
content
(wt %) 33.1 34.2 34.6 34.6 35.6 35.2 36.3
a
SBR 1500: styrene-butadiene rubber with 23.5% styrene content.
b
Z 175: silica.
c
Si 69: silane coupling agent, bis[3-(triethoxisilyl)-propyl]-tetrasulfide.
d
N 330: carbon black.
e
HPPD: N-phenyl-N⬘-(1,3-dimethylbutyl)-p-phenylenediamine.
f
DPG: diphenylguanidine.
g
TBBS: N-tert-butyl-2-benzothiazole sulfenamide.
 FILLER–POLYMER INTERACTIONS 441

tively. The MB compounds were dumped at 4.0

min. The MB compounds were prepared as fol-
lows: First, the rubber was loaded into the mixer
and premixed for 0.5 min. Second, the silica and
silane coupling agent were compounded into the
rubber for 1.5 min. Third, the carbon black, cure
activators, and antidegradants were mixed for 2.0
min, and the compounds were dumped. The FM
compounds were prepared by mixing the cura-
tives with the MB compounds for 1.5 min.
Contents of bound rubber were determined by
extraction of unbound materials such as ingredi-
ents and free rubbers with toluene for 7 d and
n-hexane for 1 d as well as drying for 2 d at room
temperature. Weights of the samples before and
after the extraction were measured, and the
bound rubber contents were calculated. Viscosi-
ties of the compounds were measured using a
Mooney viscometer MV 2000 from Alpha Technol-
ogies. Rubber composition of the bound rubber
was determined using pyrolysis-GC. Curie point
pyrolyzer JHP-22 and HP5890 gas chromato-
graphs were used. The temperature of the pyro-
lyzer was 590 °C. The sample (0.5 ⫾ 0.1 mg) was
pyrolyzed at 590 °C for 5 s. An HP-5 capillary
column (length 21 m) was also used. The analysis
conditions for pyrolysis-GC have been described
in detail elsewhere.15

RESULTS AND DISCUSSION Figure 1. Pyrograms of the bound rubbers of the FM

Bound rubber contents of the compounds do not
show a big difference with the filler content ratio.
The bound rubber content is, on the whole,
slightly increased by increasing the silica content
ratio. This is due to the silane coupling agent.
Carbon black is more compatible with the rubber
than silica because carbon black and the polymer
are nonpolar whereas silica is polar. If the silane
coupling agent is not added to the compound, the
bound-rubber content will decrease with an in-
crease of the silica content ratio. SBR compounds
filled with carbon black or silica of 60.0 phr with
and without the silane were prepared to investi-
gate the influence of the silane on the bound rub-
ber formation. For the compounds without the
silane, the bound-rubber contents were 25.1 and
23.8% for the carbon black-filled and silica-filled
compounds, respectively. For the compounds with
the silane of 8.0 wt % of the filler content, the
bound rubber contents were 27.0 and 28.4% for
the carbon black-filled and silica-filled com-
compounds 2 (a) and 6 (b).
pounds, respectively. Thus, the silica-filled com-
pound has a lower bound rubber content than the
carbon-black-filled compound when without the
silane, whereas the former has a higher bound-
rubber content than the latter when containing
the silane. The silane coupling agent has a sul-
fidic linkage between triethoxysilylpropyl groups.
The ethoxy group of the coupling agent reacts
with the silanol group of the silica to form a si-
loxane bond of silica'Si-O-Si(OC2H5)2-(CH2)3-
Sx-(CH2)3-Si(OC2H5)3. The sulfide group of the
coupling agent bonded to the silica is dissociated
and reacts with the rubber molecule to form a
crosslink between the silica and the rubber. The
chemical bonds between the silica and the rubber
enhance the bound rubber formation.
Pyrograms of the bound rubbers of the FM
compounds 2 and 6, respectively, are illustrated
in Figure 1(a, b). The major pyrolysis products are
442 CHOI

rene unit in SBR will be less than 0.2%. Relative

Figure 2. Variation of the peak intensity ratios of the
major pyrolysis products for the bound rubbers of the
MB compounds as a function of the silica content (■ ⫽
butadiene/styrene, F ⫽ C7 species/styrene, Œ ⫽ 4-vi-
nylcyclohexene/styrene).
peak intensity of the C7 species (3.71 min) is
3.7– 4.8%. Thus, most of the C7 species will be
1,4-cycloheptadiene (more than 90% of the C7
species).
To investigate the influence of the filler-content
ratio on the filler–polymer interactions in detail,
the peak intensity ratios between the major py-
rolysis products were plotted as a function of the
silica content ratio as shown in Figures 2–5. Fig-
ures 2 and 3 are the variations of the peak inten-
sity ratios for the bound rubbers of the MB com-
pounds, and Figures 4 and 5 are for the bound
rubbers of the FM compounds. Variations of the
peak intensity ratios of the butadiene/styrene, C7
species/styrene, and 4-vinylcyclohexene/styrene
with the silica content were investigated to com-
pare the differences in the filler–polymer interac-
tions of the butadiene and styrene units (Figs. 2
and 4). Variations of the peak intensity ratios of
the C7 species/butadiene and 4-vinylcyclohexene/
butadiene were also investigated to compare the
differences in the filler–polymer interactions of
the butadiene units such as the cis-1,4-, trans-
1,4-, and 1,2-components (Figs. 3 and 5).

butadiene (1.44 min), the C7 species such as 1,4-

cycloheptadiene and toluene (3.71 min), 4-vinyl-
cyclohexene (5.01 min), and styrene (6.34
min).16 –19 The styrene and toluene are produced
from styrene units of SBR, and the other products
are formed from the butadiene units. The buta-
diene units have three components of the cis-1,4-,
trans-1,4-, and 1,2-sequences as shown in Scheme
1. The butadiene and 4-vinylcyclohexene are
formed from all the butadiene components,
whereas 1,4-cycloheptadiene can be formed from
the butadiene units including the 1,2-sequence.16
Toluene is formed from the styrene unit,17,18 and
its retention time is nearly the same as the 1,4-
cycloheptadiene peak so that both peaks are over-
lapped. To measure the portion of toluene of the
C7 species, polystyrene was pyrolyzed at 590 °C
and the products were analyzed. Relative abun-
dance of the toluene peak obtained from polysty-
rene under this experimental condition is about Figure 3. Variation of the peak intensity ratios of the
1% of the styrene peak intensity. Because (the major pyrolysis products for the bound rubbers of the
pyrolysis products of SBR) relative abundance of MB compounds as a function of the silica content (■ ⫽
the styrene peak is below 20%, relative abun- C7 species/butadiene, and F ⫽ 4-vinylcyclohexene/
dance of the toluene peak produced from the sty- butadiene).
 FILLER–POLYMER INTERACTIONS 443

1.332, respectively. This implies that the filler–

Figure 4. Variation of the peak intensity ratios of the
major pyrolysis products for the bound rubbers of the
FM compounds as a function of the silica content (■ ⫽
butadiene/styrene, F ⫽ C7 species/styrene, and Œ ⫽
4-vinylcyclohexene/styrene).
polymer interaction of the butadiene units is
stronger than that of the styrene unit. The peak
intensity ratio of the butadiene/styrene decreases
by increasing the silica content ratio. This implies
that the filler–polymer interaction of the buta-
diene units weakens as the silica-content ratio
increases. This can be explained by the difference
in the filler–polymer interactions of the butadiene
units with carbon black/silica. The filler–polymer
interaction of carbon black with the butadiene
units is stronger than that of silica.19
The peak intensity ratio of the 4-vinylcyclohex-
ene/styrene decreases with an increase in the sil-
ica-content ratio. This also may be due to the
stronger filler–polymer interaction of carbon
black compared to silica. Other possible reasons
are the increased viscosity and the strong inter-
action of the 1,2-unit with silica. The formation of
the 4-vinylcyclohexene is favorable when the
butadiene unit length is long because the 4-vinyl-
cyclohexene is a butadiene dimer species. The
polymer chain is dissociated by the shear force
during the mixing.20 –23 The shear force is more

The variations of the peak intensity ratios with

the silica content ratio show specific trends. The
peak intensity ratios of the butadiene/styrene and
4-vinylcyclohexene/styrene decrease as the silica
content increases, whereas that of the C7 species/
styrene increases irrespective of the MB and FM
compounds (Figs. 2 and 4). The peak intensity
ratio of the 4-vinylcyclohexene/butadiene de-
creases as the silica content increases, whereas
that of the C7 species/butadiene increases irre-
spective of the MB and FM compounds (Figs. 3
and 5). The variations of peak intensity ratios are
fitted well to a linear equation. Results for the
curve fittings are summarized for the MB and FM
compounds, respectively Tables II and III). The
correlation coefficients are, on the whole, reason-
able.
The peak intensity ratios of the butadiene/sty-
rene for the bound rubbers are larger than that
for the compounded rubber. For the compound Figure 5. Variation of the peak intensity ratios of the
with the silica/carbon black ⫽ 70.0/10.0 phr, the major pyrolysis products for the bound rubbers of the
butadiene/styrene ratio of the FM compounded FM compounds as a function of the silica content (■ ⫽
rubber is 1.327, whereas those of the bound rub- C7 species/butadiene, and F ⫽ 4-vinylcyclohexene/
bers of the MB and FM compounds are 1.475 and butadiene).
444 CHOI

Table II. Curve-Fitting Equations Obtained from Figures 2 and 3 (MB Compounds)

Pyrolysis Products Equation Correlation Coefficient

Butadiene/styrene y ⫽ ⫺0.0011x ⫹ 1.531 ⫺0.522

C7 Species/styrene y ⫽ 0.0010x ⫹ 0.193 0.870
4-Vinylcyclohexene/styrene y ⫽ ⫺0.0022x ⫹ 0.397 ⫺0.988
C7 Species/butadiene y ⫽ 0.0008x ⫹ 0.125 0.941
4-Vinylcyclohexene/butadiene y ⫽ ⫺0.0013x ⫹ 0.260 ⫺0.979

applied to a high viscous compound than to a low
compound. The viscosity of the compound in-
creases by increasing the silica content as shown
in Table I. The rubber chain scission causes the
molecular weight distribution to shift to a lower
molecular weight.20,21 The strong filler–polymer
interaction of the 1,2-unit with silica is discussed
subsequently.
4-Vinylcyclohexene is formed from all the buta-
diene units, but the 1,4-cycloheptadiene can be
produced only from the butadiene sequence in-
cluding the 1,2-unit.16 Thus, the relative peak
intensity of the 4-vinylcyclohexene is decreased
by increasing the 1,2-unit in the bound rubber.
This is evidence of the strong interaction of the
1,2-unit with silica because the 4-vinylcyclohex-
ene/styrene decreases with an increase in the sil-
ica-content ratio. The peak intensity ratio of 4-vi-
nylcyclohexene/butadiene also decreases with an
increase in the silica-content ratio; this cannot be
explained by the difference in the filler–polymer
interactions of silica and carbon black because
both 4-vinylcyclohexene and butadiene are pro-
duced from all the butadiene units. This also may
be due to the increased viscosity of the compound
and the strong filler–polymer interaction of the
1,2-unit with silica. The strong interaction of the
1,2-unit with silica leads to a relatively high por-
tion of the 1,2-unit in the bound rubber so that the
4-vinylcyclohexene/butadiene ratio becomes
lower as the silica content increases.
The peak intensity ratios of the C7 species/
styrene and C7 species/butadiene increase with
an increase in the silica-content ratio. This is an
interesting fact because the total filler–polymer
interactions of the butadiene become weaker as
the silica content increases, and most of the C7
species (1,4-cycloheptadiene) is formed from the
butadiene unit as discussed previously. The 1,4-
cycloheptadiene is formed from the 1,2-unit, not
from the cis-1,4- and trans-1,4-units.16 Thus, the
filler–polymer interaction of the 1,2-unit is stron-
ger with silica than with carbon black; on the
contrary, for the cis-1,4- and trans-1,4-units the
interactions with carbon black are more favor-
able.
CONCLUSIONS
Differences in the filler–polymer interaction of
the styrene, cis-1,4-, trans-1,4-, and 1,2-units with
silica/carbon black were studied by analysis of the
microstructures of the bound rubbers with the
pyrolysis-GC technique. The conclusions of the
present article may be summarized as follows: (1)
the total filler–polymer interactions of the buta-
diene units with silica/carbon black were stronger
than that of the styrene unit; (2) the interactions
of the cis-1,4- and trans-1,4-units were stronger
with carbon black than with silica; and (3) the

Table III. Curve-Fitting Equations Obtained from Figures 4 and 5 (FM Compounds)

Pyrolysis Products Equation Correlation Coefficient

Butadiene/styrene y ⫽ ⫺0.0029x ⫹ 1.565 ⫺0.938

C7 Species/styrene y ⫽ 0.0011x ⫹ 0.171 0.922
4-Vinylcyclohexene/styrene y ⫽ ⫺0.0020x ⫹ 0.396 ⫺0.988
C7 Species/butadiene y ⫽ 0.0011x ⫹ 0.106 0.921
4-Vinylcyclohexene/butadiene y ⫽ ⫺0.0009x ⫹ 0.255 ⫺0.989

1,2-unit interacted more strongly with silica than
with carbon black.
REFERENCES AND NOTES
1. Stickney, P. B.; Falb, R. D. Rubber Chem Technol
1964, 37, 1299.
2. Kraus, G. Adv Polym Sci 1971, 8, 155.
3. Blow, C. M. Polymer 1973, 14, 309.
4. Dannberg, E. M. Rubber Chem Technol 1986, 59,
512.
5. Wolff, S.; Wang, M.-J.; Tan, E.-H. Rubber Chem
Technol 1993, 66, 163.
6. Byers, J. T. Rubber World 1998, 219(2), 38.
7. Wolff, S.; Wang, M.-J. Rubber Chem Technol 1992,
65, 329.
8. Boonstra, B. B.; Cochrane, H.; Dannenberg, E. M.
Rubber Chem Technol 1975, 48, 558.
9. Voet, A.; Morawski, J. C.; Donnet, J. B. Rubber
Chem Technol 1977, 50, 342.
FILLER–POLYMER INTERACTIONS 445
10. Ou, Y.-C.; Yu, Z.-Z.; Vidal, A.; Donnet, J. B. Rubber
Chem Technol 1994, 67, 834.
11. Li, Y.; Wang, M. J.; Zhang, T.; Zhang, F.; Fu, X.
Rubber Chem Technol 1994, 67, 693.
12. Lehrle, R. S.; Robb, J. C. Nature 1959, 183, 1671.
13. Phair, M.; Wampler, T. ACS Proc Rubber Div 150th
Meeting, American Chemical Society: Washington,
DC, 1996; Paper No. 69.
14. Ohtani, H.; Ueda, S.; Tsukahara, Y.; Watanabe, C.;
Tsuge, S. J. Anal Appl Pyrolysis 1993, 25, 1.
15. Choi, S.-S. J Anal Appl Pyrolysis 1999, 52, 105.
16. Choi, S.-S. J Anal Appl Pyrolysis 2000, in press.
17. Hacaloglu, J.; Ersen, T.; Ertugrul, N.; Fares, M. M.;
Suzer, S. Eur Polym J 1997, 33, 199.
18. Hacaloglu, J.; Ersen, T. Rapid Commun Mass Spec-
trom 1998, 12, 1793.
19. Choi, S.-S. J Anal Appl Pyrolysis 2000, 55, 161.
20. Imoto, M. Rubber Chem Technol 1952, 25, 234.
21. Bristow, G. M. Rubber Chem Technol 1962, 35, 896.
22. Ahagon, A. Rubber Chem Technol 1996, 69, 742.
23. Choi, S.-S. Kor Polym J 2000, 8, 73.