Int J Ind Chem

DOI 10.1007/s40090-017-0130-3

RESEARCH

Synthesis and utilization of epoxidized polybutadiene rubber

as an alternate compatibilizer in green-tire composites
Vivek K. Srivastava1 • Ganesh C. Basak1 • Madhuchhanda Maiti1 •

Raksh Vir Jasra1

Received: 31 August 2016 / Accepted: 24 August 2017

 The Author(s) 2017. This article is an open access publication

Abstract In the present study, epoxidized polybutadiene Keywords Epoxidized polybutadiene rubber 
rubber (EBR) was synthesized from commercial-grade cis- Compatibilizer  Surface energy  Physico-mechanical
polybutadiene rubber (BR) and was characterized by NMR, properties
FTIR, differential scanning calorimetry, thermogravimetric
analysis and surface energy by contact angle measurement.
To circumvent the drawback of the existing compatibilizers, Introduction
the EBR was successfully used as an alternate compatibi-
lizer for a silica-based ‘green-tire’ composite. The signifi- The development of ‘green tires’ with lower rolling resis-
cant rise of surface energy was observed after epoxidation of tance along with safety and fuel efficiency is the focus of
BR, which represents the enhancement of the polar character the current tire research and developments. In fact, the
of the rubber chains and eventually leads to improved ‘green-tire’ concept was introduced in early 90s and has
compatibility between silica fillers and rubber chains. Out of emerged as a paradigm shift towards the improvements of
various epoxidation levels, EBR with 30 mol% epoxidation tire’s wet grip (safety) and rolling resistance (fuel effi-
showed the best compatibilizing effect. The optimum load- ciency) simultaneously [1–3]. Moreover, the impulsion and
ing of EBR was found to be 12% with respect to total silica the advantages associated with ‘green-tire’ concept initi-
content. Apart from using EBR alone as a compatibilizer, ated the investigation and utilization of various types of
combination of EBR with commercial silane-coupling novel fillers like nanosilica, nanoclay etc., to replace or to
agents, namely, bis(triethoxy-silylpropyl) tetrasulphide avoid the conventional carbon black [4, 5]. However, as
(TESPT) and 3-aminopropyltrimethoxy silane, was also compared to the carbon black, the use of other fillers such
investigated. The physico-mechanical and dynamic proper- as nanosilica in the rubber composites encounters few
ties of the compounds with a combination of TESPT:EBR major challenges such as [6–9];
(40:60–60:40) were comparable with those of the compound
• poor rubber–filler interaction due to difference of polar
prepared using TESPT compatibilizer. The results observed
characteristics and
with EBR-compatibilized samples revealed that EBR has a
• filler agglomeration due to higher filler–filler
potential to be an effective compatibilizer which eventually
interaction.
could minimize the drawbacks associated while using
commercial silane as a compatibilizer at the industrial scale. As a result of above-mentioned limitations, the rubber
composites prepared using nanofillers lead to poor pro-
cessability, inferior mechanical strength and unaccept-
able dynamic properties. However, such challenges can be
& Vivek K. Srivastava resolved up to greater extent using compatibilizers or
[email protected] coupling agents which reduces the difference in polar
1 characters of fillers and rubbers and leads to improved
Vadodara Manufacturing Division, Reliance Research and
Development Center, Reliance Industries Ltd., Vadodara, rubber–filler interactions [10, 11]. Typically, on industrial
Gujarat 391346, India scale, the modification of silica surface is done by

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introduction of coupling agents or compatibilizers like • epoxidation of tire-grade high cis-polybutadiene rubber
silanes, which reduce the filler–filler interaction and also (5, 10, 30, and 50 mol% epoxidation) to prepare the
enhance the rubber–filler interaction through chemical epoxidized polybutadiene rubber (EBR);
linkages between the silica surface and rubber chains • evaluation of compatibilizing efficacy of thus synthe-
[12, 13]. However, from industrial production viewpoint, sized EBR in silica-filled SBR/BR blend at various
the use of silanes as compatibilizer has shown the fol- epoxidation levels and loadings;
lowing major disadvantages: • comparative study of EBR as a compatibilizer with
commercially used silanes like bis(triethoxy-silyl-
• the coupling reaction produces alcohols as by-products
propyl) tetrasulphide (TESPT) and 3-amino propyl
which may cause chronic defects in the final product
trimethoxy silane (APS).
[14];
• the higher material costs of the coupling agents; and
• the higher production costs due to the difficult
processing behavior. Experimental
On the other hand, in the absence of silanes, the com-
Materials and methods
patibility between fillers and rubbers can be enhanced by
increasing the polar characteristics in the rubber chains
BR (Cisamer 01, ML1?4@ 100 C = 45; Mw = 3.5 9 105,
which ultimately reduces the risks associated with their
cis content 96%) was obtained from Reliance Industries
utilizations [15]. In the case of polyolefins, in general,
Ltd., India. SBR (1502, Mooney viscosity ML1?4@
functionalization such as epoxidation, carboxylation, oxi-
100 C = 48) was obtained from Japan Synthetic Rubber,
dation, sulfonation, maleination etc., are known [16–18].
Japan. Sulfur, stearic acid (98% purity), zinc oxide (ZnO),
However, among the various functionalizations, the
N-Cyclohexyl-2-benzothiazole sulphenamide (CBS) (98%
epoxidation of unsaturated –C=C– bond at mild reaction
purity), diphenyl guanidine (DPG), microcrystalline wax,
condition is a wonderful synthetic tool for introduction of
precipitated silica, and bis(triethoxy-silylpropyl) tetrasul-
versatile functionality to the rubber chain. The epoxidation
phide (TESPT) were purchased from Labort Fine Chem.
of rubber chain is an excellent synthetic tool to increase the
Pvt. Ltd., India. N-(1, 3-dimethyl butyl)-N-phenyl-p-
polar character by introduction of oxirane/epoxy ring to the
phenylenediamine (6PPD) was obtained from John Baker
rubber chain. The epoxidation of the rubber and polymer
Inc., USA. 3-amino propyl trimethoxy silane (APS) was
chains can be carried out by both methods: solution and
procured from Sigma-Aldrich Inc., USA. Naphthenic oil
melt-mixing [19, 20]. The epoxidation is carried out to
and di-tertiary-butyl-para cresol (DTBPC) were obtained
serve dual purpose, to improve the functionality, and also
from indigenous sources. meta-Chloroperbenzoic acid
to enhance the polar character of the non-polar rubber and
(MCPBA, 70%) was procured from Sigma-Aldrich, India.
polymer chains. Moreover, a controlled epoxidized rubber
would possess both the polar group epoxy ring and non-
Synthesis of epoxidized polybutadiene rubber (EBR)
polar hydrocarbon chain to interact with polar silica surface
and a non-polar rubber chain, respectively. Advanta-
A variety of different magnitude of epoxidation (5, 10, 30,
geously, the epoxidized BR can also be co-cured with the
and 50 mol%) of BR were conducted using modified pro-
main rubber matrix smoothly.
tocol (Scheme 1) [27].
The silica and silane-based styrene–butadiene rubber/
Typically for 10 mol% epoxidation, in a three-neck
polybutadiene rubber (SBR/BR) composites are currently
round-bottom flask equipped with magnetic stirrer, 16.2 g
being used in passenger car radial tire-tread [21]. In the
of BR (0.3 mol of C=C) was first dissolved in 1000 ml of
present study, the commercial-grade high cis-polybutadi-
toluene. A solution of 7.38 g of MCPBA (0.03 mol) in
ene rubber (BR) was epoxidized to synthesize epoxy-BR
300 ml of toluene was subsequently added drop-wise at
(EBR) at different epoxidation magnitude, and thus, pre-
room temperature into the rubber solution at such a rate
pared EBRs were used to replace and/or reduce the cou-
that the MCPBA solution was added in 1 h. The reaction
pling agent from SBR/BR composites. Although the use of
mixture was then further stirred for another 3 h. After 3 h,
epoxidized polydienes has been reported as compatibilizer
the stirring was stopped and epoxidized rubber was
for silica filler in a few patents [22–25], however, a com-
obtained by precipitation in methanol containing 0.5%
prehensive study has not been reported on the effect of
DTBPC as an antioxidant. The rubber was decanted and
epoxidation levels on compatibilization in the open litera-
then washed twice with methanol before subjecting to
ture [26]. Therefore, the present study focuses on the fol-
vacuum drying at room temperature for 5 h. The 10, 30,
lowing major aspects:

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Int J Ind Chem

Scheme 1 Epoxidation
reaction of polybutadiene
rubber

and 50 mol% epoxidized polybutadiene rubbers were UK) according to ASTM D2240-97. For determining the
designated as EBR10, EBR30 and EBR50 respectively. abrasion resistance of the composites, cylindrical test pie-
ces were molded. The tests were performed according to
Preparation of rubber composites DIN 5316 in DIN Abrader (Zwick Roell, Germany). Cut
and chip test was performed on Cut and Chip Tester (Alpha
A variety of rubber composites were prepared by melt- Technologies, USA). The conditions of testing were:
mixing method. Mixing was carried out in a Brabender sample speed 750 rpm, cut and chip cycle 60 rpm and
Plasticorder (PL2000, Germany), an internal mixer cycle time 10 min. Circular sample of 50 mm diameter
(volume 50 cm3) adopting a three-stage mixing proce- was used. Dynamic mechanical thermal analysis was done
dure at 60 rpm. Mixing temperature of first, second, and using DMA VA4000 (Metravib, France) in double sand-
third stages was 120, 140 and 80 C (unless otherwise wich shear mode. Strain sweep experiments were done
mentioned). Different composites were prepared in the range of 0.1–40% strain at 60 C. Sample dimen-
according to the formulations given in Table 1. The sion was of 10 mm in diameter and 2.0 ± 0.2 mm of
final curing of compound was done on compression thickness.
molding at 145 C and 10 MPa pressure at optimum The volume fraction of rubber in the swollen network,
cure time. Vr, was calculated by equilibrium swelling method and
crosslink density was subsequently calculated by the well-
Testing methods of different composites known Flory–Renner equation [28]. Rheology studies were
carried out using Hybrid Rheometer from -120 to 100 C
Dumbbell-shaped samples were cut from the molded sheets at 10 Hz frequency and 0.1% strain [29]. The bound rubber
according to ASTM D412-96 for tensile strength and content was determined as per method proposed by the
ASTM D624 for tear strength. The tensile strength, elon- reported literature [30]. The surface energy of the solid
gation at break, modulus and tear strength were determined polymers was determined by contact angle measurement.
on a Universal Testing Machine (Instron 3367, USA) with Fowkes [31] proposed that the surface energy of a pure
the crosshead speed of 500 mm/min. Hardness was mea- phase is a sum of the contribution from the dispersive cda
sured using 6 mm-thick sample in Durometer (Wallace, and polar cpa components, such that

Table 1 Formulation and designation of rubber composites

Ingredients Formulation in phra
Sample name A B C D E F G H I J K L M

SBR 70 70 70 70 70 70 70 70 70 70 70 70 70
BR 30 30 30 30 30 30 30 30 30 30 30 30 30
EBR (mol%) – – – 8.4 (10) 8.4 (30) 8.4 (50) 5.6 (30) 17.5 (30) 35 (30) 4.2 (30) 3.4 (30) 5.0 (30) 5.0 (30)
Precipitated silica 70 70 70 70 70 70 70 70 70 70 70 70 70
TESPT – 8.4 – – – – – – – 4.2 5.0 3.4 –
APS – – 8.4 – – – – – – – – – 3.4
Zinc oxide 5 5 5 5 5 5 5 5 5 5 5 5 5
Stearic acid 2 2 2 2 2 2 2 2 2 2 2 2 2
6PPD 2 2 2 2 2 2 2 2 2 2 2 2 2
Wax 1 1 1 1 1 1 1 1 1 1 1 1 1
Naphthenic oil 8 8 8 8 8 8 8 8 8 8 8 8 8
Sulfur 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3
CBS 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3
DPG 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
a
Parts per 100 parts of rubber

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 Int J Ind Chem

ca ¼ cda þ cpa : ð1Þ observed in which the Tg was increased from -103 C
(BR) to -99 C (EBR30). The change in Tg of the EBR is
A contact angle meter, Kernco (Model G II) was attributed to the fact that the presence of rigid polar bond in
adopted for contact angle measurement, using water and place of unsaturated group. Moreover, the single Tg value
formamide as testing liquids. Contact angle of water and also implies the uniform distribution of epoxy group along
formamide on BR is 93.01 and 74.52, respectively. with the BR main chain. The TGA and DTG studies have
Contact angle of water and formamide on EBR is 79.76 also been carried out to observe the effect of degradation
and 64.74, respectively. Now pattern in the presence of oxirane ring into the BR chain
2ðcds cdl Þ1=2 2ðcps cpl Þ1=2 (Fig. 4). A single pattern in the range of 300–480 C in
cos h ¼ 1 þ þ ; ð2Þ TGA curves and two distinct weight loss peaks in the DTG
cl cl
curves were observed. It is observed that the beginning of
where cds and cps are the dispersive and polar components of thermal degradation (Tonset) marginally delays on the
solid’s surface energy and cdl , cpl are the dispersive and introduction of oxirane ring in the BR chain. On the other
polar components of liquid’s surface energy. Using Eqs. 1 hand, the maximum degradation temperature (Tmax)
and 2, the surface energy of BR and EBR was calculated. increases by 2 from 448 to 450 C.
A change in the surface energy of the rubber chains
represents variance in the polar characters. To quantify the
Results and discussion extent of variance of polar character, the surface energy of
one of the synthesized epoxidized BR was compared with
Characterization of epoxidized polybutadiene corresponding virgin BR. The surface energy of BR and
rubber EBR5 was calculated to be 24.72 and 29.79 mJ/m2,
respectively. Hence, it was observed that typically, 5%
As mentioned earlier, introduction of oxirane group into epoxidized BR has shown about 20% rise in the surface
the rubber chain was aimed to increase the polar character energy in comparison to the virgin BR. Such increment of
of the polybutadiene rubber chain. The extent of epoxida- surface energy clearly indicates that the polar character has
tion was calculated by a methods as described in the lit- been significantly increased after epoxidation of the BR.
erature, e.g., 1H-NMR (Bruker—400 MHz AVANCE-III, Finally, the 1H-NMR, FTIR, DSC, TGA, and surface
Germany) and FTIR (Nicolet 6700, USA) spectroscopy and energy studies clearly signify that the presence of epoxy
addition of HCl in dioxane solution method [19, 20]. The ring leads to increments of polar character in the BR
extent of epoxidation was quantified by NMR spec- chains.
troscopy. A new singlet at 2.9 ppm (–CH of epoxy) in EBR
samples was observed in comparison to the NMR spectrum Effect of different magnitude of epoxidation level
of BR (Fig. 1). The epoxidation of polybutadiene rubber of EBR as a coupling agent
was further confirmed by ATR–FTIR method. After
epoxidation, in comparison to polybutadiene rubber, the The effect of different magnitude of epoxidation level of
appearance of new peaks at 809 and 1260 cm-1 (due to – EBR on the mechanical properties of SBR/BR–silica
C–O–C– stretching of epoxy group) was observed (Fig. 2). composites is shown in Table 2. The lower mechanical
It was also noticed that the peak height increases with the properties were observed in the SBR/BR–silica composite
extent of epoxidation. The typical 1H-NMR resonance without using compatibilizer (Sample A; Table 2) which
signals of BR and corresponding EBR30 samples are given may be due to higher filler–filler interaction and therefore,
below [19, 20, 27]. resulted poor dispersion of the silica filler in the rubber
BR: 1H NMR (400.13 MHz, CDCl3): in ppm 0. matrix. On the contrary, while using EBR10 and EBR30 as
911–1.444 (m, 0.12 H, –CH3), 2.093 (s, 2.04 H, –CH2), a compatibilizer, the tensile strength of the rubber com-
5.026–5.395 (m, 1.02 H, =CH). EBR: 1H NMR posite was increased by 16 and 39%, respectively (Sample
(400.13 MHz, CDCl3): in ppm 1.251–1.500 (m, 0.71 H, – D and Sample E; Table 2) in comparison to the rubber
CH3), 1.514–1.800 (m, 0.24 H, –CH3), 1.951–2.291 (m, composite without using compatibilizer (Sample A;
2.71 H, –CH2), 2.939–3.001 (m, 0.24 H, –C–O–C– Oxi- Table 2). However, lower values of the physico-mechani-
rane), 5.101–5.640 (m, 1.53 H, =CH). cal properties were observed while using higher magnitude
The samples were also characterized and compared by of epoxidized, EBR50 (Sample F; Table 2). This could be
thermal analysis such as DSC, TGA and DTG studies. The due to higher polarity at 50% epoxidation level, which
glass transition temperature (Tg) of a rubber changes makes epoxidized rubber incompatible with non-polar
expected to be increased on the introduction of oxirane SBR/BR blends. Although EBR50 with higher level of
ring. As shown in Fig. 3, similar kind of results was also epoxidation may react better with silica but due to

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Int J Ind Chem

Fig. 1 1H-NMR spectra of BR

and EBR30 samples

incompatibility with the SBR/BR blend matrix, the Sample B [ Sample E [ Sample C [ Sample D [ Sam-
improved effect of compatibilization was not realized in ple A [ Sample F (Table 2). The highest value of Vr was
the Sample F. Significantly higher improvement in the observed for the composite samples containing TESPT as a
tensile strength was observed in the rubber composites compatibilizer because of the presence of sulfur molecule
sample containing the conventional silane-coupling agents, in the TESPT (Scheme 2), which facilitated the
TESPT (95% increment, Sample B and Sample A; Table 2) crosslinking density of the silica–silane–rubber network.
and APS (51% increment, Sample C and Sample A; On the other hand, better Vr values were also observed
Table 2). Such improvements are due to better filler dis- while using EBR30 as a compatibilizer in the SBR/BR–
persion and filler–rubber interaction in the presence of silica composite (Sample E; Table 2) which further con-
conventional compatibilizers. The abrasion resistance and firms that the presence of polar epoxidized BR improves
hardness values of the composites follow the trend: Sample the crosslink density in the composite sample in compar-
B [ Sample A [ Sample E [ Sample D = Sample ison to sample A.
F [ Sample C (Table 2). The abrasion resistance and cut In general, it has been observed that the acidic silica
and chip are both closely related wear properties of the surface tries to make a strong hydrogen bond with basic
rubber composites. cure activators and consequently the crosslink density
The volume fraction of rubber in the swollen network reduces in the vulcanized rubber samples. To improve the
(Vr) for the studied rubber composites follows the trend: crosslink density of silica-filled rubber, the silane-coupling

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To support the proposed mechanism of Scheme 3, the

FTIR spectra of EBR30 and the composites sample made
from EBR30 and silica are compared (Fig. 5). It was
observed that the peak at 810 cm-1 due to oxirane ring of
EBR30 sample was disappeared in the composite sample of
EBR30 and silica.

Effect of variation of EBR concentration

on compatibilization

Out of the employed EBR samples, the EBR30 (30%

epoxidized BR) showed encouraging compatibilizer prop-
erties. Therefore, to investigate the optimum loading level,
further studies were carried out by variation of loading of
EBR30 as 8, 12, 25 and 50 weight % of total silica content
in the SBR/BR–silica composites. The highest tensile
strength was observed at 12% loading (Fig. 6) as compared
to higher (25 and 50%) as well as lower (8%) loading of
EBR30. Other properties like modulus at 300% elongation,
hardness, and tear strength also followed the similar trend
(Figs. 6, 7). It may be presumed that at lower loading, the
amount of epoxy groups may not be sufficient to interact
with the polar silica filler. On the other hand, at higher
EBR, loading increases the polarity difference between
polar-EBR and non-polar SBR/BR created incompatibility
and leads to inferior compatibilization effect.

Effect of EBR30 as partial substituent of silane

Though during our investigations, EBR samples showed

encouraging results as a potential compatibilizer for SBR/
BR–silica composites, however, the physico-mechanical
properties were not observed better than the composites
Fig. 2 FTIR spectra of BR and EBR30 samples samples containing the conventional silanes, especially for
TESPT. Similar observation was also reported earlier for
agents come into picture which basically prevents the other rubber composites samples [26]. Moreover, to
adsorption of the curatives on the silica surfaces by mod- observe the synergetic effects and also to minimize the
ifying the silica surface and makes crosslinks between disadvantages associated with the conventional silanes,
silica and rubber chain. The polarity of the polybutadiene another approach was undertaken by replacement of some
rubber is increased in the presence of polar epoxy group. part of conventional silanes by EBR samples SBR/BR–
This enhances the strong interaction between rubber and silica composites. A variety of SBR/BR–silica composites
silica in comparison to sample without silanes (Sample A). were prepared using different combination of TESPT and
This might be the reason behind the improvement of EBR30 samples. The ratio of TESPT:EBR30 was varied as
crosslink density of Sample L in the presence of polar 40:60 (Sample J), 50:50 (Sample K), and 60:40 (Sample L)
epoxidized BR. and the results obtained are reported in Table 3.
Finally, it can be concluded that among the employed As compared to the composite samples containing
EBR samples, EBR30 showed a better improvement in the exclusively EBR as a compatibilizer (Sample E; Table 2),
physico-mechanical properties while using as a compati- significant improvements (up to 31%) were observed for
bilizer in the SBR/BR–silica composites. the tensile strength of composite samples containing the
A proposed coupling reaction between silica surface and combination of EBR30:TESPT as compatibilizer (Sample
EBR is shown in Scheme 3. The surface silanol group of L; Table 3). However, the expected synergy was not
silica reacts with epoxy group of EBR, while the non-polar observed using a combination of TESPT and EBR in the
part of EBR is compatible with non-polar SBR/BR blend. composites as the mechanical and the wear properties were

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Int J Ind Chem

Fig. 3 DSC curves of BR and

EBR30 samples

only comparable but not better than those of TESPT con- investigate the rubber–filler interaction, the bound rubber
taining composite sample (Sample B; Tables 2, 3). Thus, it content values were also determined (Table 5). It was
can be concluded that 40–60% of silanes can be substituted observed again that sample containing only TESPT
by EBR which can minimize the drawbacks associated compatibilizer (Sample B) has shown the highest per-
while using only silane as a compatibilizer. centage of bound rubber values followed by the Sample
On the other hand, the Sample M (sample containing L, Sample K, and Sample M in comparison to the Sample
combination of EBR30:APS) showed mechanical proper- A (without any compatibilizer).
ties inferior to both the composite sample containing alone
APS (Sample C; Tables 2, 3) and EBR30 (Sample E; Payne effect
Table 2). The possible reason could be the non-availability
of polar oxirane ring of EBR30 to function as compatibi- To investigate further filler–filler interactions, the Payne
lizer because of the stoichiometric reaction between amino- effect studies were carried out. The Payne effect was cal-
group of APS and oxirane ring of EBR30 as represented in culated by the difference between the elastic modulus at
Scheme 4. Eventually, the remaining oxirane ring of 0.18 degree strain and at 2 degree strain
EBR30 was not adequate to provide a better compatibi- [DG0 = (G0 @0.18 - G0 @2.0)] in uncured and cured
lization effect into the SBR/BR–silica composite. samples at 1 Hz and 100 C (Figs. 8, 9). For the uncured
samples, as expected, it was observed that there is a
Rheology studies and bound rubber content maximum reduction in DG0 for Sample B due to the
presence of TESPT coupling agent in the rubber matrix.
The cure characteristics such as scorch time (t2), cure time Afterwards, the maximum reduction of DG0 was occurred
(t90), ML and delta torque of various important samples are for Sample L (Fig. 8). This might be a favorable interaction
given in Table 4. It was observed that except Sample M, all between epoxy groups and the hydroxy (–OH) group onto
the samples have shown a significant decrease of ML value the silica surface and, therefore, improve dispersion lead-
which indicates reduction of filler–filler interactions within ing to reduction of Payne effect was observed. However,
the rubber matrix. Moreover, it was also observed that for the all cured samples, there is an increase in DG0
sample containing only TESPT compatibilizer (Sample B) magnitude was observed (Fig. 9) owing to the probable re-
has shown the highest extent of ML reduction followed interaction of the filler particles by the low viscosity during
by the Sample K and Sample L in comparison to the crosslinking formation at higher temperature.
Sample A (without any compatibilizer). In addition,
improved crosslinking efficiency, which is reflected by SEM microscopy studies
highest values for both MH and delta torque for the
sample containing only TESPT compatibilizer (Sample B) To investigate the dispersion of silica filler particles in the
followed by Sample L and Sample K in comparison to rubber matrix, the SEM microscopy studies of various
Sample A (without any compatibilizer). Moreover, to samples were carried out. As shown in Fig. 10, the silica

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 Int J Ind Chem

Fig. 4 TGA and DTG

thermogram patterns of BR and
EBR30 samples

Table 2 Mechanical properties

Properties Sample A Sample B Sample C Sample D Sample E Sample F
of SBR/BR–silica composites
containing various coupling Tensile strength, MPa 5.40 10.55 8.13 6.29 7.51 4.75
agent
Hardness, shore A 64 66 58 62 63 62
Elongation at break, % 555 377 460 303 560 595
100% modulus, MPa 1.60 3.92 2.80 2.71 2.45 1.52
300% modulus, MPa 3.28 6.09 5.90 3.17 4.31 3.04
Vr 0.182 0.281 0.186 0.185 0.221 0.156
-4
Crosslink density 9 10 0.80 2.55 0.85 0.83 1.32 0.54
Sample A composite sample without any compatibilizer, Sample B composite sample using TESPT as a
coupling agent, Sample C composite sample using APS as a coupling agent, Sample D composite sample
using EBR10 as a coupling agent, Sample E composite sample using EBR30 as a coupling agent, and
Sample F composite sample using EBR50 as a coupling agent

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Int J Ind Chem

Scheme 2 Proposed coupling

reaction in the presence of
TESPT

Scheme 3 Proposed coupling reaction in the presence of EBR

filler particles were uniformly dispersed in Sample B,

Sample K, and Sample L, whereas an agglomeration of
silica particles was observed in Sample A (without any
compatibilizer). The observed SEM images clearly reflect
that the utilization of EBR along with TESPT improved the
silica filler dispersion by interaction between free –OH
groups of silica surface with oxirane ring of EBR30 rubber
chain to form strong interaction.

Dynamic mechanical properties

It has been reported that wet skidding resistance and rolling

resistance of tires are generally determined by the tan d
value at temperatures of -20 to 0 and 50 to 70 C,
respectively [32]. Higher tan d value at temperatures of
-20 to 0 C corresponds to improved wet skidding resis-
tance, whereas lower tan d value at temperatures of
50–70 C relates to low rolling resistance. Therefore, to
investigate the influence of employed compatibilizers EBR,
TESPT, and APS in BR/SBR rubber matrix, the tan d (loss
factor) of various samples were compared (Fig. 11). It was Fig. 5 FTIR spectra of EBR30 and composite of EBR30 and silica
observed that the tan d at lower temperature (-20 to 0 C) samples
was higher for Sample B followed by Sample L as com-
pared to those observed for the Sample A (without any higher temperatures (50–70 C) was lower for the Sample
compatibilizer). Therefore, both the Sample B and Sample B followed by Sample L as compared to those observed
L will show better wet skid resistance as compared to other for Sample A (without any compatibilizer). Therefore, it
Sample A, Sample K and Sample M. Moreover, the tan d at can be concluded that the Sample B and Sample L would

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 Int J Ind Chem

Magnitude of properes
8
phr TESPT silane as a compatibilizer) and Sample B
(only TESPT silane as a compatibilizer) have shown
6 comparable dynamic properties which further confirms
potential effectiveness of EBR30 as a compatibilizer in
4 green-tire composites.

Effect of EBR on viscoelastic properties

0
G E H I of the composites

Tensile strength, MPa Modulus at 300% elongaon, MPa The viscoelastic behaviors of various composite samples as
Fig. 6 Effect of variation of loading of EBR30 loading level on the
a function of strain percentage at 60 C were also inves-
tensile strength and modulus of the composite samples tigated for some of the samples (Fig. 12). The typical
features of the Payne effect, i.e., a decrease in the storage
modulus with increasing strain, can be seen for all the
70
studied composite samples. The Payne effect amplitude,
60 was calculated as a decrease in the magnitude of the non-
Magnitude of properes

50 linear effect was observed to follow the trend as Sample

40 E \ Sample L = Sample B \ Sample C \ Sample M.
30
The efficient silanization of EBR30 sample can be seen
from the observed lower values of the composite Sample E
20
and Sample L, which reflects a better rubber–filler inter-
10 action in the composite samples.
0 Interestingly, unlike the physico-mechanical properties,
G E H I
the dynamic mechanical properties of EBR-containing
Tear strength, N/mm Hardness, Shore A composite samples were comparable with the correspond-
ing composite sample containing the conventional silane
Fig. 7 Effect of variation of loading of EBR30 loading level on the
tear strength and hardness of the composite samples. Sample G like TESPT. Moreover, for the composite Sample M,
composite sample using EBR30 loading as 8% of silica content, ineffective silanization was observed which reduces rub-
Sample E composite sample using EBR30 loading as 12% of silica ber–filler interaction as explained in Scheme 4.
content, Sample H composite sample using EBR30 loading as 25% of In addition, the Payne effect amplitude v/s Vr was also
silica content, and Sample I composite sample using EBR30 loading
as 50% of silica content plotted (Fig. 13), where values followed a reverse trend in
comparison to the trend observed for Vr. The higher Vr
show better rolling resistance and wet skid resistance than values can be observed in Sample B and Sample L due to
other Sample A, Sample K, and Sample M. Important to additional crosslinking which caused by the presence of
mention here that the Sample L (60 phr EBR30 and 40 conventional silane TESPT in the composite sample.

Table 3 Physico-mechanical
Properties Sample B Sample C Sample J Sample K Sample L Sample M
properties of different SBR/BR–
silica composites sample Hardness, shore A 66 58 64 66 74 61
containing combination various
loading of TESPT and EBR30 Tensile strength, MPa 10.55 8.13 9.54 9.33 9.85 6.73
compatibilizers Elongation at break, % 277 460 340 309 386 425
100% modulus, MPa 3.92 2.80 2.81 3.24 2.94 2.38
300% modulus, MPa 6.09 5.90 8.56 8.95 7.73 4.95
Tear strength, N/mm 29 35 28 28 29 28
Abrasion loss, g/40 m 0.168 0.225 0.233 0.218 0.199 0.206
Cut and chip, g/10 min 2.83 3.28 2.46 2.82 2.83 3.21
Vr 0.311 0.209 0.231 0.265 0.243 0.183
Sample B composite sample using TESPT as a coupling agent, Sample C Composite sample using APS as a
coupling agent, Sample J composite sample using combination of EBR30: TESPT (40:60 ratio), Sample K
composite sample using combination of EBR30:TESPT (50:50 ratio), Sample L composite sample using
combination of EBR30:TESPT (60:40 ratio), and Sample M composite sample using combination of
EBR30:APS (60:40 ratio)

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Int J Ind Chem

Scheme 4 Proposed reaction

between the amino-group of
APS and oxirane ring of EBR30

Table 4 Cure characteristics of

Sample A Sample B Sample K Sample L Sample M
various samples
ML (dN - M) 4.9 3.3 4.2 4. 5 5.6
MH (dN - M) 25.77 31.48 28.89 30.08 21.59
ts2 (min) 4.07 4.04 4.07 3.76 1.11
t90 (min) 10.01 17.39 15.33 14.34 5.74
DTorque (MH - ML) (dN - M) 20.87 28.15 24.65 25.43 15.98

Table 5 Bound rubber content

Sample A Sample B Sample K Sample L Sample M

Bound rubber content (%) 46 79 69 74 51

Sample A composite sample without any compatibilizer, Sample B composite sample using TESPT as a
coupling agent, Sample K composite sample using combination of EBR30:TESPT (50:50 ratio), Sample L
composite sample using combination of EBR30:TESPT (60:40 ratio), and Sample M composite sample
using combination of EBR30:APS (60:40 ratio)

3 3.4

Sample A
2.8 Sample A
Sample B
Log G' (KPa)

Log G' (KPa)

3.2
Sample K Sample B
2.6 Sample K
Sample L
Sample M 3 Sample L
2.4
Sample M

2.2
2.8
0 0.5 1 1.5 2 2.5
0 0.5 1 1.5 2 2.5
Degree Strain Degree Strain
Fig. 8 Log storage modulus of uncured samples as a function of Fig. 9 Log storage modulus of cured samples as a function of degree
degree strain strain. Sample A composite sample without any compatibilizer;
Sample B composite sample using TESPT as a coupling agent;
Sample K composite sample using combination of EBR30:TESPT
Conclusions (50:50 ratio), Sample L composite sample using combination of
EBR30:TESPT (60:40 ratio), and Sample M composite sample using
combination of EBR30:APS (60:40 ratio)
In the present work, epoxidized polybutadiene rubber
(EBR) was synthesized, characterized and used as a com- increased till 30 mol% epoxidation (EBR30) and then
patibilizer in SBR/BR–silica composite blend. With decreased at higher epoxidation level (50 mol%). In addi-
increasing epoxidation level, the compatibilization effect tion, 12% loading was found as an optimum loading of

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 Int J Ind Chem

Fig. 10 SEM images of various

samples. Sample A composite
sample without any
compatibilizer; Sample B
composite sample using TESPT
as a coupling agent; Sample K
composite sample using
combination of EBR30:TESPT
(50:50 ratio), and Sample L
composite sample using
combination of EBR30:TESPT
(60:40 ratio)

1.0 3500000
Sample A G'0 L
Sample K E
Sample L
0.8
Sample B
3000000 M
Sample M B
C
G', Pa

0.6 2500000
Tanδ

0.4 2000000

G'α
1500000
0.2

1000000
-20 -10 0 10 20 30 40 50 60 70 80 0 10 20 30 40
Temperature (oC) Strain, %

Fig. 11 Temperature dependence of tan d values. Sample A com- Fig. 12 Plot of storage modulus versus percentage strain
posite sample without any compatibilizer; Sample B composite
sample using TESPT as a coupling agent; Sample K composite comparable with those of TESPT containing composite
sample using combination of EBR30:TESPT (50:50 ratio), Sample L
composite sample using combination of EBR30:TESPT (60:40 ratio), samples. On the other hand, the dynamic mechanical
and Sample M composite sample using combination of EBR30:APS properties obtained while using the composite sample
(60:40 ratio) containing combination of TESPT:EBR (40:60) were
comparable to the corresponding composite sample con-
taining TESPT as a compatibilizer. The rheological, bound
EBR30 in composite sample. It was observed that although rubber content, Payne effect, and SEM results indicated the
EBR can function as an effective compatibilizer, however, good compatibility between polar-EBR matrix and polar
all the physico-mechanical properties obtained with com- silica nanoparticles. The dynamic properties of the samples
mercial silane-coupling agent, TESPT was better than measured at low and high temperatures improved both
those of EBR-containing composite samples. The physico- good rolling as well as wet skid resistance. Finally, it can
mechanical properties of the composite sample containing be concluded that in the Green-tire composite, 40–60% of
combination of TESPT:EBR (40:60–60:40) were the expensive conventional silanes can be replaced by

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2000000 carbon black and silica fillers in elastomer blends. Macro-

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Kim (2006) Effect of compatibilizer and silane coupling agent on
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