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-

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

439
440 CHOI

coupling agent, cure activators, antidegradants,

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-,
Scheme 1 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
GC). The use of pyrolysis-GC for the characteriza- [pH ⫽ 6.9, Brunauer–Emmett–Teller (adsorption
tion and analysis of polymers has been used.12–14 isotherm) ⫽ 175 m2/g] and N 330 (dibutylphtha-
The filler–polymer interactions of the styrene, cis- late absorption ⫽ 1.02 mL/g) were supplied from
1,4-, trans-1,4-, and 1,2-units were compared. Kofran Co. and Columbian Chemicals Korea, re-
spectively.
Mixing was performed in a Banbury-type
EXPERIMENTAL mixer at a rotor speed of 40 and 30 rpm for master
batch (MB) and final mixing (FM) stages, respec-
Both the silica and carbon black-filled compounds tively. The initial temperatures of the mixer were
were made of SBR, silica, carbon black, silane 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

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

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

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
Figure 2. Variation of the peak intensity ratios of the differences in the filler–polymer interactions of
major pyrolysis products for the bound rubbers of the the butadiene units such as the cis-1,4-, trans-
MB compounds as a function of the silica content (■ ⫽ 1,4-, and 1,2-components (Figs. 3 and 5).
butadiene/styrene, F ⫽ C7 species/styrene, Œ ⫽ 4-vi-
nylcyclohexene/styrene).

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–

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
Figure 4. Variation of the peak intensity ratios of the polymer chain is dissociated by the shear force
major pyrolysis products for the bound rubbers of the during the mixing.20 –23 The shear force is more
FM compounds as a function of the silica content (■ ⫽
butadiene/styrene, F ⫽ C7 species/styrene, and Œ ⫽
4-vinylcyclohexene/styrene).

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 The peak intensity ratios of the C7 species/
compound. The viscosity of the compound in- styrene and C7 species/butadiene increase with
creases by increasing the silica content as shown an increase in the silica-content ratio. This is an
in Table I. The rubber chain scission causes the interesting fact because the total filler–polymer
molecular weight distribution to shift to a lower interactions of the butadiene become weaker as
molecular weight.20,21 The strong filler–polymer the silica content increases, and most of the C7
interaction of the 1,2-unit with silica is discussed species (1,4-cycloheptadiene) is formed from the
subsequently. butadiene unit as discussed previously. The 1,4-
4-Vinylcyclohexene is formed from all the buta- cycloheptadiene is formed from the 1,2-unit, not
diene units, but the 1,4-cycloheptadiene can be from the cis-1,4- and trans-1,4-units.16 Thus, the
produced only from the butadiene sequence in- filler–polymer interaction of the 1,2-unit is stron-
cluding the 1,2-unit.16 Thus, the relative peak ger with silica than with carbon black; on the
intensity of the 4-vinylcyclohexene is decreased contrary, for the cis-1,4- and trans-1,4-units the
by increasing the 1,2-unit in the bound rubber. interactions with carbon black are more favor-
This is evidence of the strong interaction of the able.
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 CONCLUSIONS
increase in the silica-content ratio; this cannot be
explained by the difference in the filler–polymer Differences in the filler–polymer interaction of
interactions of silica and carbon black because the styrene, cis-1,4-, trans-1,4-, and 1,2-units with
both 4-vinylcyclohexene and butadiene are pro- silica/carbon black were studied by analysis of the
duced from all the butadiene units. This also may microstructures of the bound rubbers with the
be due to the increased viscosity of the compound pyrolysis-GC technique. The conclusions of the
and the strong filler–polymer interaction of the present article may be summarized as follows: (1)
1,2-unit with silica. The strong interaction of the the total filler–polymer interactions of the buta-
1,2-unit with silica leads to a relatively high por- diene units with silica/carbon black were stronger
tion of the 1,2-unit in the bound rubber so that the than that of the styrene unit; (2) the interactions
4-vinylcyclohexene/butadiene ratio becomes of the cis-1,4- and trans-1,4-units were stronger
lower as the silica content increases. 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
 FILLER–POLYMER INTERACTIONS 445

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