FORM 2
THE PATENTS ACT, 1970
[39 OF 1970]
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
[See section 10 and rule 13]
“SILICA BASED FUNCTIONALIZED SBR COMPOSITES FOR HIGH PERFORMANCE GREEN
TIRE APPLICATIONS”
NAME AND ADDRESS OF THE APPLICANT:
RELIANCE INDUSTRIES LIMITED
3rd Floor, Maker Chamber-IV, 222, Nariman Point, Mumbai – 400 021, Maharashtra, India
NATIONALITY: IN
The following specification particularly describes the invention and the manner in which it is to be performed.

TECHNICAL FIELD
The present disclosure generally relates to the field of tyre technology and pertains to compositions employed for manufacturing tyre treads. More particularly, the present disclosure provides a composition comprising functionalized styrene butadiene polymer and silica filler, and processes for preparation thereof.
BACKGROUND OF THE DISCLOSURE
Automobile tyre companies are giving importance to the safety of travel, fuel economy, and environmental safety. The reduction of rolling resistance of tyres has become the preliminary objective for tyre industries, as it has close relation to the fuel consumption, hysteresis loss properties of tyre tread and carbon dioxide emission (greenhouse gases) of motor vehicles. Dispensability of filler is considered to affect hysteresis loss. The tyre tread is a major contributor to the tyre rolling resistance, its wet traction, and skid resistance.
Previous studies have shown that conventional tyres made of emulsion-based styrene butadiene rubber (ESBR) grade with carbon black show inferior properties compared to solution polymerized SBR (SSBR) grades. SSBR comprising silica filler and a silane coupling agent to improve dispersibility of silica filler shows lower rolling resistance, reduction in fuel consumption and thus, lower CO2 emission due to better SBR-silica compatibility than regular ESBR. Although solution polymerized SBR comprising silica fillers with a silane coupling agent has shown better results than ESBR comprising silica filler, compared to solution polymerization, emulsion polymerization is a mild and economical viable technique which tolerates large range of functionalized and non-functionalized monomers for styrene butadiene rubber synthesis. The major advantage of emulsion polymerization process is that it is less costly compared to SSBR process. Thus, there is a need to develop a composite tyre composition comprising emulsion based SBR comprising silica filler, the performance of which would be equivalent to or better than that of SSBR composite.
Further, in prior studies, silica filler is incorporated into SBR compositions with the help of a silane coupling agent. Studies have shown that when silica filler is added with the help of a silane coupling agent, there is a better dispersion of silica and there is less filler-filler interaction, both of which result in improved tyre performance. See, for example, a study published by Qingyuan Li et al. (“Mechanical Properties of Styrene-Butadiene Rubber Reinforced with Silica by in situ Tetraethoxysilane Hydrolysis over Acid Catalyst”, Elastomers

and Composites, Vol. 53, No. 2, pp. 57~66, June 2018), which shows that when silica filler was incorporated in the presence of a silane coupling agent such as bis [3-(triethoxysily) propyl] tetrasulfide, (3-glycidyloxypropyl) trimethoxysilane, and ethyltrimethoxysilane, mechanical properties of the tyre such as storage modulus, tensile stress, and hardness were improved compared to tyre composition comprising silica filler in the absence of a silane coupling agent. Various other studies also employ silane coupling agents for better dispersion of silica filler in tyre compositions.
However, incorporation of silane coupling agents have certain disadvantages. For example, during mixing of a silane coupling agent with silica filler at high temperature such as 165-170°C, the silane coupling agent starts donating sulfur and reacts with the rubber, resulting in scorching and deterioration of storage and dynamic modulus and subsequently final properties of the tyre composition. The silanization reaction between silica and the silane coupling agent also releases huge amounts of ethanol as a by-product during mixing, which is an environmental concern. Thus, there is a need to provide an emulsion-based styrene butadiene rubber composition comprising silica filler, wherein the composition does not comprise a silane coupling agent.
While there are documents that contemplate an emulsion-based styrene butadiene rubber (ESBR) composition comprising a silica filler, there are no teachings in the art that show how such ESBR compositions can be prepared without a silane coupling agent. Thus, as per the current understanding, one skilled in the art would manufacture a silica-containing ESBR with a silane coupling agent in view of earlier studies mentioned above that establish that the presence of a silane coupling agent is necessary for better dispersion of silica in the rubber composition, reduced filler-filler interaction, and consequently better tyre performance compared to a composition without a silane coupling agent. However, as discussed above, incorporation of a silane coupling agent has certain drawbacks. The present disclosure therefore aims to provide a tyre composition comprising a functionalized emulsion-based styrene butadiene rubber (FESBR) and about 60 to 100 PHR of silica filler, wherein the composition does not comprise a silane coupling agent, and at the same time, exhibits one or more properties equivalent to or better than that of SSBR composite.
SUMMARY OF THE DISCLOSURE
The present disclosure provides a composition comprising about 80-120 parts per hundred of rubber (PHR) of functionalized styrene butadiene polymer and about 60-100 PHR of silica,

wherein the functionalized styrene butadiene polymer comprises: a) about 45 to 90 PHR of a conjugated diene monomer; b) about 10 to 40 PHR of a vinyl substituted aromatic monomer; and c) about 1 to 20 PHR of a polar co-monomer selected from a group comprising acrylate, propoxylate, sulphonate, and a combination thereof. This composition is referred to herein as a FSBR silica composite composition. The FSBR silica composite of the present disclosure does not comprise a silane coupling agent.
The present disclosure also provides a process for preparing the FSBR silica composite composition, comprising: a) subjecting the conjugated diene monomer, the vinyl substituted aromatic monomer, and the polar co-monomer to an emulsion polymerization to obtain functionalized styrene butadiene polymer latex; b) coagulating the functionalized styrene butadiene polymer latex to obtain the functionalized styrene butadiene polymer rubber, and c) adding silica prior to or after said coagulating to obtain the composition.
The present disclosure also relates to a tyre tread comprising the composition of the present disclosure.
BRIEF DESCRIPTION OF THE ACCOMPANYING FIGURES
Figure 1 shows the results of a comparative bound rubber study between SSBR, ESBR (SBR 1502 (std)), and FSBR.
Figure 2 shows the results of a cross link density study of SSBR, ESBR (SBR 1502 (std)), and FSBR.
Figure 3 shows the results of a rheological study of SBR 1502 (std), Butyl Acrylate-based FSBR, and SSBR (NS116).
Figure 4 shows the results of modulus at 100% of SBR 1502 (std), Butyl Acrylate-based FSBR, and SSBR (NS116).
Figure 5 shows the results of tensile strength of SBR 1502 (std), Butyl Acrylate-based FSBR, and SSBR (NS116).
Figure 6 shows the results of tear strength of SBR 1502 (std), Butyl Acrylate-based FSBR, and SSBR (NS116).
Figure 7 shows the results of abrasion loss of SSBR, ESBR, and Butyl Acrylate-based FSBR.
Figure 8 shows the results of wet traction of SSBR, ESBR, and Butyl Acrylate-based FSBR.

Figure 9 shows the results of dry skid resistance of SSBR, ESBR, and Butyl Acrylate-based FSBR.
Figure 10 shows the results of rolling resistance of SSBR, ESBR, and Butyl Acrylate-based FSBR.
Figure 11 shows the results of a rheological study of SBR 1502 (std), propoxylate-based FSBR, and SSBR (NS116).
Figure 12 shows the results of physical properties study of SBR 1502 (std), propoxylate-based FSBR, and SSBR (NS116).
Figure 13 shows the results of tensile strength of SBR 1502 (std), propoxylate-based FSBR, and SSBR (NS116).
Figure 14 shows the results of dynamic properties study of SBR 1502 (std), propoxylate-based FSBR, and SSBR (NS116).
Figure 15 shows Mooney viscosity values of SBR 1502 (std), 2-Ethylhexyl Acrylate (EHA)-based FSBR, and SSBR before addition of silica filler.
Figure 16 shows the glass transition temperatures of SBR 1502 (std), 2-Ethylhexyl Acrylate (EHA)-based FSBR, and SSBR.
Figure 17 shows the results of a rheological study of SBR 1502 (std), 2-Ethylhexyl Acrylate (EHA)-based FSBR, and SSBR.
Figure 18 shows the results of physical properties study of SBR 1502 (std), 2-Ethylhexyl Acrylate (EHA)-based FSBR, and SSBR.
Figure 19 shows the results of dynamic properties study of SBR 1502 (std), 2-Ethylhexyl Acrylate (EHA)-based FSBR, and SSBR.
Figure 20 shows the results of a rheological study of SBR 1502-Silica composite and FSBR-silica composite prepared without a silane coupling agent.
Figure 21 shows the results of physical properties study of SBR 1502-Silica composite and FSBR-silica composite prepared without a silane coupling agent.
Figure 22 shows the results of % elongation at break of SBR 1502-Silica composite and FSBR-silica composite prepared without a silane coupling agent.

Figure 23 shows the results of tear strength of SBR 1502-Silica composite and FSBR-silica composite prepared without a silane coupling agent.
Figure 24 shows the results of dynamic properties study of SBR 1502-Silica composite and FSBR-silica composite prepared without a silane coupling agent.
Figure 25 shows the results of a rheological study of SBR 1502-Silica composite and FSBR-silica composite prepared with a silane coupling agent.
Figure 26 shows the results of physical properties study of SBR 1502-Silica composite and FSBR-silica composite prepared with a silane coupling agent.
Figure 27 shows the results of % elongation at break of SBR 1502-Silica composite and FSBR-silica composite prepared with a silane coupling agent.
Figure 28 shows the results of dynamic properties study of SBR 1502-Silica composite and FSBR-silica composite prepared with a silane coupling agent.
DETAILED DESCRIPTION OF THE DISCLOSURE
With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity. The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results. Throughout this specification, the word “comprise”, or variations such as “comprises” or “comprising” or “containing” or “has” or “having”, or “including but not limited to” wherever used, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
Reference throughout this specification to “some embodiments”, “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment may be included in at least one embodiment of the present disclosure. Thus, the appearances of the phrases “in some embodiments”, “in one embodiment” or “in an embodiment” in various places throughout this specification may not necessarily all refer to the same embodiment. It is appreciated that certain features of the disclosure, which are, for

clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.
Throughout this specification, the term “optional” or “optionally” means that the elements recited after optional/optionally such as components of the composition or method steps may or may not be present, and that the description includes embodiments where said elements are present and embodiments in which said elements are not present.
Throughout this specification, the terms ‘functionalized’ and ‘functionalization’ are used interchangeably and are intended to convey the ordinary conventional meaning of the term known to a person skilled in the art in the field of polymer or material science, and intends to cover a process of adding new functions, features, capabilities, or properties to a material by changing the microstructure / backbone of polymer of the material. In the context of rubber employed in the present disclosure, the term is used to cover functionalization of the rubber including reactions of rubber (and its derivatives) with organic and/or inorganic molecules, chemical modification of the rubber surface, and the interaction of various covalent and noncovalent components with rubber. The functionalization of rubber is microstructure modification used to reduce the cohesive force between the rubber and to manipulate the physical and chemical properties of rubber. This functionalization of rubber is also referred to as ‘functionalized rubber’ in the present disclosure. Throughout the present disclosure, the terms ‘functionalized rubber’ and ‘functionalized SBR’, are used interchangeably to refer to styrene butadiene rubber with polar functionality synthesized via emulsion polymerization.
As used herein, the abbreviation ‘SBR’ refers to the styrene butadiene polymer in latex or rubber form.
As used herein, the abbreviation ‘FSBR’ or ‘FESBR’ is used interchangeably and refers to the functionalized styrene butadiene polymer in latex or rubber form.
Throughout this specification, the phrases ‘functionalized styrene butadiene polymer latex’, ‘polymer latex’, ‘latex’, and ‘SBR polymer latex’ are used interchangeably and refer to a suspension of functionalized styrene butadiene polymer of the present invention held in a liquid form.

Throughout this specification, the phrases ‘functionalized styrene butadiene polymer rubber, ‘polymer rubber’, ‘rubber’, and ‘SBR polymer rubber’ are used interchangeably and refer to the solid functionalized styrene butadiene polymer of the present invention post coagulation of the functionalized SBR latex. As used herein, the abbreviations “PHR” and “phr” are used interchangeably and refer to the amount of the indicated component present in the composition of the present invention based on parts per hundred of rubber.
Throughout this specification, the term ‘tyre’ and ‘tire’ are used interchangeably and intend to cover a composition comprising at least one rubber/elastomer.
Throughout this specification, the term “tyre tread” refers to an outer portion of the tyre that makes contact with the road.
Throughout this specification, the term ‘FSBR silica composite’ refers to a composition comprising functionalized styrene butadiene rubber and silica filler. In some embodiments, the FSBR silica composite does not comprise a silane coupling agent.
Mooney Viscosity is defined as the shearing torque resisting rotation of a cylindrical metal disk (or rotor) embedded in rubber within a cylindrical cavity.
Throughout this specification, technical terms such as ‘fuel efficiency’, ‘tensile modulus’, ‘rolling resistance’, ‘abrasion resistance’, ‘abrasion loss’, ‘fatigue failure’, and ‘heat build-up’ are used to describe the properties of a tyre/tyre tread or characteristics of a composition that makes up the tyre/tyre tread, and are intended to convey the ordinary conventional meaning of the terms known to a person skilled in the art.
Styrene butadiene rubber (SBR) compositions comprising silica filler have been disclosed in the art. According to the current understanding in the art, using a silane coupling agent to incorporate silica filler in the SBR compositions is necessary to provide better dispersibility of silica, to reduce filler-filler interaction, and to improve filler-rubber interaction. The inventors of the present disclosure tried incorporating silica filler in an emulsion-based SBR composition comprising polar functionality (FESBR/FSBR) in the absence of a silane coupling agent and surprisingly found that the dynamic properties such as abrasion loss, skid resistance, and rolling resistance of the obtained FSBR composition are comparable to the FSBR composition comprising silica filler incorporated with a silane coupling agent. Thus, the present disclosure provides a FSBR silica composite composition comprising FSBR and silica filler, wherein the composition does not comprise a silane coupling agent.

In some embodiments, the FSBR silica composite composition comprises about 80-120 parts per hundred of rubber (PHR) of functionalized styrene butadiene polymer and about 60-100 PHR of silica, wherein the functionalized styrene butadiene polymer comprises: a) about 45 to 90 PHR of a conjugated diene monomer; b) about 10 to 40 PHR of a vinyl substituted aromatic monomer; and c) about 1 to 20 PHR of a polar co-monomer selected from a group comprising acrylate, propoxylate, sulphonate, and a combination thereof.
In some embodiments, the FSBR silica composite composition comprises about 80-120 PHR, 80-115 PHR, 80-110 PHR, 80-100 PHR, 90-120 PHR, 90-110 PHR, 100-120 PHR, 80 PHR, 85 PHR, 90 PHR, 95 PHR, 100 PHR, 105 PHR, 110 PHR, 115 PHR, or 120 PHR, including values and ranges there between, of functionalized styrene butadiene polymer and about 60-100 PHR, 60-90 PHR, 60-80 PHR, 70-100 PHR, 70-90 PHR, 70-80 PHR, 75-100 PHR, 75-95 PHR, 80-100 PHR, 80-90 PHR, 90-100 PHR, 60 PHR, 70 PHR, 80 PHR, 90 PHR, or 100 PHR, including values and ranges there between, of silica filler.
In some embodiments, the functionalized styrene butadiene polymer comprises:
a) about 45-90 PHR, 45-85 PHR, 45-80 PHR, 45-75 PHR, 45-70 PHR, 45-65 PHR, 50-90 PHR, 50-80 PHR, 50-70 PHR, 55-90 PHR, 55-85 PHR, 60-90 PHR, 60-80 PHR, 70-90 PHR, 80-90 PHR, 45 PHR, 50 PHR, 60 PHR, 70 PHR, 75 PHR, 80 PHR, 85 PHR, or 90 PHR, including values and ranges therebetween, of a conjugated diene monomer;
b) about 10-40 PHR, 10-30 PHR, 10-20 PHR, 15-35 PHR, 15-30 PHR, 20-40 PHR, 20-35 PHR, 20-30 PHR, 30-40 PHR, 10 PHR, 20 PHR, 25 PHR, 30 PHR, or 40 PHR, including values and ranges therebetween, of a vinyl substituted aromatic monomer; and
c) about 1-20 PHR, 1-15 PHR, 1-10 PHR, 1-5 PHR, 5-20 PHR, 5-15 PHR, 5-10 PHR, 10-20 PHR, 10-15 PHR, 15-20 PHR, 1 PHR, 3 PHR, 4 PHR, 5 PHR, 8 PHR, 10 PHR, 12 PHR, 15 PHR, 18 PHR, or 20 PHR, including values and ranges therebetween, of a polar co-monomer selected from a group comprising acrylate, propoxylate, sulphonate, and a combination thereof.
In some embodiments, the conjugated diene monomer of the FSBR is selected from a group comprising 1,3-butadiene, isoprene, 1,3-ethylbutadiene, hexadiene, cyclooctadiene, octadiene, cyclic conjugated dienes, or a combination thereof. In a non-limiting, exemplary embodiment, the conjugated diene monomer of the FSBR is 1,3-butadiene. The values and ranges for the

amount of the conjugated diene monomer described above are applicable to each of these conjugated diene monomers.
In some embodiments, the vinyl substituted aromatic monomer of the FSBR is selected from a group comprising styrene, α-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-cyclohexylstyrene, 4-para tolylstyrene, para-chlorostyrene, 4-tert-butyl styrene, 1-vinylnaphthalene, 2-vinylnapthalene or a combination thereof. In a non-limiting, exemplary embodiment, the vinyl substituted aromatic monomer is styrene. The values and ranges for the amount of the vinyl substituted aromatic monomer described above are applicable to each of these vinyl substituted aromatic monomers.
In some embodiments, the acrylate polar co-monomer is selected from a group comprising butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methacrylate, methyl methacrylates, hydroxyethylmethacrylate, butyl methacrylates, vinyl acrylate, acrylic acid, acrylonitrile, allyl acrylate, acrylamide, or a combination thereof. The values and ranges for the amount of the polar co-monomer described above are applicable to each of these acrylate polar co-monomers.
In some embodiments, the propoxylate polar co-monomer is hydroxyl butyl vinyl ether propoxylate. The values and ranges for the amount of the polar co-monomer described above are applicable to this propoxylate polar co-monomer.
In some embodiments, the sulphonate polar co-monomer is selected from a group comprising styrene sulphonate, 2-acrylamido 2-methylpropane sulphonate, sodium allyl sulphonate and sodium methallyl sulphonate or a combination thereof. The values and ranges for the amount of the polar co-monomer described above are applicable to each of these sulphonate polar co-monomers.
In some embodiments, the polar co-monomer is selected from a group comprising butyl acrylate, 2-ethylhexyl acrylate, hydroxyl butyl vinyl ether propoxylate, and a combination thereof.
In some embodiments of the present disclosure, the polar co-monomer introduces hydroxyl, ether and/or ester functional groups into the styrene butadiene molecular backbone which introduces strong chemical bond and/or hydrogen bonds to facilitate homogenous dispersion and reduce particle-particle interactions of silica filler. The dual hydroxyl O-H and multiple ether linkages present in the rubber composition reacts with silica filler through hydrogen

bonding and gives homogeneous dispersion of silica filler in the polymer matrix which reduces the rolling resistance and carbon foot-prints of tire tread.
The reinforcement of functionalized SBR comprising a polar co-monomer with silica filler shows homogeneous dispersion of silica via chemical bonding with functionalized SBR. Functionalized SBR with polar functionality interacts with silica O-H group via chemical bonds and/or hydrogen bonds and facilitate homogeneous dispersion and reduce particle-particle interactions of silica filler. The homogeneous dispersion of silica filler in the FSBR polymer matrix shows reduced filler-filler interaction and increased rubber-silica interaction which results in an improvement in rolling resistance and tensile properties.
The above advantages of the present FSBR silica composite are further enhanced by the absence of a silane coupling agent. Since the present composite composition does not employ a silane coupling agent, the composition exhibits less scorching and less deterioration of storage and dynamic modulus compared to a composite comprising a silane coupling agent. Further, the synthesis of the present FSBR silica composite is not associated with a release of huge amounts of ethanol since the silane coupling agent is not incorporated thereby making the synthesis process environment-friendly. Furthermore, the inventors observed that even high loading amounts such as 100 PHR of silica can be incorporated into FSBR and the properties of such composites are still comparable to the composites prepared with a silane coupling agent.
In some embodiments, the FSBR is a terpolymer or a tetrapolymer. In some embodiments, the FSBR terpolymer comprises: a) about 45 to 90 PHR of a conjugated diene monomer; b) about 10 to 40 PHR of a vinyl substituted aromatic monomer; and c) about 1 to 20 PHR of a single polar co-monomer selected from a group comprising acrylate, propoxylate, or sulphonate.
In some embodiments, the FSBR tetrapolymer comprises: a) about 45 to 90 PHR of a conjugated diene monomer; b) about 10 to 40 PHR of a vinyl substituted aromatic monomer; and c) about 1 to 20 PHR of a two polar co-monomers selected from a group comprising acrylate, propoxylate, and sulphonate.
In an exemplary, non-limiting embodiment, the FSBR silica composite composition comprises
about 80-120 parts per hundred of rubber (PHR) of functionalized styrene butadiene polymer
and about 60-100 PHR of silica, wherein the functionalized styrene butadiene polymer
comprises:
(i) about 45 to 90 PHR of 1,3-butadiene;

(ii) about 10 to 40 PHR of styrene; and
(iii) about 1 to 20 PHR of a polar co-monomer selected from a group comprising butyl
acrylate, 2-ethylhexyl acrylate, hydroxyl butyl vinyl ether propoxylate, and a combination
thereof.
In an exemplary, non-limiting embodiment of the FSBR, the conjugated diene monomer is 1,3-butadiene, the vinyl substituted aromatic monomer is styrene, and the polar co-monomer is butyl acrylate.
In yet another exemplary, non-limiting embodiment of the FSBR, the conjugated diene monomer is 1,3-butadiene, the vinyl substituted aromatic monomer is styrene, and the polar co-monomer is hydroxyl butyl vinyl ether propoxylate.
In yet another exemplary, non-limiting embodiment of the FSBR, the conjugated diene monomer is 1,3-butadiene, the vinyl substituted aromatic monomer is styrene, and the polar co-monomer is 2-ethylhexyl acrylate.
In some embodiments, the FSBR silica composite composition comprises an additional customary/conventional component/ingredient(s) used in rubber compositions for tyres, especially for tyre treads, selected from a group comprising plasticizer, accelerator, activator, antioxidant, antiozonant, aromatic oil, curing agent, or a combination thereof. These conventional ingredients are added to FSBR latex or FSBR rubber. In some embodiments, the conventional ingredient/additive is at an amount ranging from about 0.1-50 0.1-45, 0.1-40, 0.1-30, 0.1-25, 1-50, 1-45, 1-40, 1-30, 1-20, 2.5-50, 2.5-40, 2.5-30, 2.5-25, 2.5-20, 5-50, 5-40, 5-30, 5-25, 5-20, 10-50, 10-40, 10-30, 20-50, 20-40, 25-50, or 30-50 PHR, including values and ranges therebetween, based on parts per hundred of rubber.
In some embodiments, the plasticizer is selected from a group comprising residual aromatic extract (RAE) oil, naphthenic oil, paraffinic oil, soluble sulphonic acid or a combination thereof.
In some embodiments, the accelerator is selected from a group comprising N- tert-butyl-2-benzothiazyl sulfenamide (TBBS), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N,N-Dicyclohexyl -2- benzothiazole sulfenamide (DCBS), 2-Mercaptobenzothiazole (MBT), Di Thiophosphates, Zinc O,O,O',O'-tetrabutyl bis(phosphorodithioate) (ZDBP), Tetraisobutylthiuram disulphide (IBT), Tetraisobutylthiuram monosulphide (IBM) or a combination thereof.

In some embodiments, the activator is selected from a group comprising zinc oxide, lead oxide, magnesium oxide, stearic acid or a combination thereof.
In some embodiments, the antioxidant is selected from a group comprising poly(1,2-dihydro-2,2,4-trimethyl-quinoline) (TMQ), styrenated phenol, phenyl –ß-napthyl amine (PBN), octylated diphenyl amine (ODPA), p-oriented styrenated diphenyl amine (SDPA), butylated hydroxytoluene (BHT), 4-methyl-6 terlbutyl phenol (BPH), cyclic acetals, or a combination thereof.
In some embodiments, the antiozonant is selected from a group comprising N-1,3-
dimethylbutyl)-N-phenyl-p-phenylenediamine (6PPD), N-isopropyl-N’-phenyl-p-
phenylenediamine (IPPD), N,N'-dixylene-p-phenylenediamine (DTPD), N,N'-Bis(1,4-
dimethylpentyl)-p-phenylenediamine (77PD) or a combination thereof.
In some embodiments, the aromatic oil is selected from a group comprising treated distilled aromatic extract (TDAE), residual aromatic extract (RAE), distilled aromatic extract (DAE), or a combination thereof.
In some embodiments, the curing agent is sulphur.
In an exemplary, non-limiting embodiment, the activator is zinc oxide in an amount of 2 to 4 PHR and stearic acid in an amount of1 to 3 PHR, including values and ranges therebetween; the accelerator is TBBS in an amount of 1 to 2 PHR, including values and ranges therebetween; the antiozonant is 6PPD in an amount of 1 to 3 PHR, including values and ranges therebetween; the antioxidant is TMQ in an amount of 0.5 to 1.5 PHR, including values and ranges therebetween; the aromatic oil is TDAE in an amount of 10 to 30 PHR, including values and ranges therebetween; and the curing agent is sulphur in an amount of 1 to 3 PHR, including values and ranges therebetween, based on parts per hundred of styrene-butadiene rubber (SBR).
The present disclosure also provides a process for preparing the FSBR silica composite composition, comprising:
a) subjecting the conjugated diene monomer, the vinyl substituted aromatic monomer,
and the polar co-monomer to an emulsion polymerization to obtain functionalized
styrene butadiene polymer latex;
b) coagulating the functionalized styrene butadiene polymer latex to obtain the
functionalized styrene butadiene polymer rubber, and

c) adding silica prior to or after said coagulating to obtain the FSBR silica composite composition.
In some embodiments, the step of emulsion polymerization comprises:
a) mixing an emulsifier with water, a modifier, the vinyl substituted aromatic monomer, and the polar co-monomer at a temperature of about 13°C to 15°C to obtain a reaction mixture;
b) adding a catalyst, an activator, and the conjugated diene monomer to the reaction mixer at a temperature of about 6°C to 12°C; and
c) allowing polymerization of the reaction mixture to obtain the functionalized styrene butadiene polymer latex.
In some embodiments, the emulsion polymerization is conducted at a temperature ranging from about 1-20°C, including values and ranges therebetween, such as, about 1-15°C, 1-10°C, 1-5°C, 5-20°C, 5-15°C, 5-10°C, 10-20°C, 10-15°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C¸ 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C or 20°C.
The emulsifier can be anionic, cationic or non-ionic. In some embodiments, the emulsifier comprises an emulsifying agent selected from a group comprising Rosin acid, fatty acid, sodium dodecyl naphthyl methyl sulphonate (DNMS), sodium lauryl sulfate, sodium dioctyl sulfosuccinate, sodium oleate, triethanolamine stearate, ethylenediaminetetraacetic acid (EDTA), potassium chloride, benzalkonium chloride, or a combination thereof.
In some embodiments, the modifier is selected from a group comprising Tert-dodecyl mercaptan (TDM), aldehydes, acids, dibenzyltrithiocarbonate or a combination thereof.
In some embodiments, the catalyst is selected from a group comprising Sodium Formaldehyde Sulfoxylate (SFS), FeSO4, EDTA, CuSO4, K2SO4, NH4SO3, NaHSO3 or a combination thereof.
In some embodiments, the activator is a peroxide.
After completion of the polymerization reaction, the functionalized styrene butadiene polymer formed is in a latex form. The latex is coagulated to obtain solid rubber composition. In some embodiments, the step of coagulation comprises: a) diluting the functionalized styrene butadiene polymer latex with water, b) heating the latex to a temperature of about 50°C to 80°C, c) adding an antioxidant and a flocculent, and d) adding a coagulating agent to the functionalized styrene butadiene polymer latex to obtain the functionalized styrene butadiene polymer rubber.

In some embodiments, the latex after dilution is heated to a temperature of about 50-70°C, 50-60°C, 60-80°C, 60-70°C, 55-75°C, 70-80°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, or 80°C, including values and ranges thereof.
In some embodiments, the coagulating agent is selected from a group comprising an acid, sodium chloride, calcium chloride, or a combination thereof. In some embodiments, the acid employed as a coagulating agent includes, but is not limited to, sulphuric acid, or acids with pKa lower than 4 such as hydrochloric acid, citric acid, perchloric acid, chloroacetic acid, and the like.
Silica filler is added to the FSBR in latex form, i.e., prior to coagulation; or in rubber form, i.e., after coagulation of the latex form. In some embodiments, highly dispersible precipitated silica having high surface area is employed as a filler.
In some embodiments, when precipitated silica is added to FSBR in rubber form, it is compounded with FSBR via four stage mixing. In stage 1, FSBR and silica are mixed at a temperature of about 165 to 170°C to provide better chemical interaction between FSBR polar functionality and silanol group of silica. In stage 2, an aromatic oil with or without silane coupling agent are added to FSBR-silica composite at 140-145 oC. In stage 3, activators such as zinc oxide and stearic acid, an antioxidant, and an antiozonant are added to the composite. In stage 4, sulphur is added as a curing agent and TBBS and DPG – are added as activators to activate curing of the composite.
When silica filler is added to FSBR in latex form, it is important to bring the silica filler particles and latex in close proximity before the coagulation starts externally to obtain a homogeneous distribution of silica filler in co-coagulated matrix. To obtain the same, the filler particles are finely dispersed in emulsion to avoid sedimentation of filler particles to obtain homogeneous dispersion of fillers.
In some embodiments, the process for preparing the FSBR silica composite comprises adding about 0.1-50 PHR of a customary/conventional component/ingredient to the functionalized styrene butadiene latex or rubber. Exemplary classes and specific examples of these conventional ingredients are described above along with exemplary amounts.
The present disclosure also provides a tyre tread composition comprising the FSBR silica composite composition described herein.

The tyre tread is a major contributor to both the tyre rolling resistance and its traction. Although SBR compositions with silica filler are known to decrease rolling resistance and improve traction of tread, prior to the present disclosure, these SBR-silica compositions employed a silane coupling agent. However, the use of silane coupling agents offset some of the advantages provided by silica filler due to the release of sulphur and ethanol by the silane coupling agents. The present disclosure provides for the first time a FSBR silica composite that does not include a silane coupling agent and at the same time, rolling resistance, skid resistance and abrasion loss of the composite is comparable to a FSBR silica composite with a silane coupling agent.
Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based on the description provided herein. The embodiments herein provide various features and advantageous details thereof in the description. Descriptions of well-known/conventional methods and techniques are omitted so as to not unnecessarily obscure the embodiments herein.
Any possible combination of two or more of the embodiments described herein is comprised within the scope of the present disclosure.
The foregoing description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments in this disclosure have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
Any discussion of documents, acts, materials, devices, articles and the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
While the instant disclosure is susceptible to various modifications and alternative forms, specific aspects thereof have been shown by way of examples and drawings and are described

in detail below. However, it should be understood that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and the scope of the invention as defined by the appended claims.
EXAMPLES
The present disclosure is further described with reference to the following examples, which are only illustrative in nature and should not be construed to limit the scope of the present disclosure in any manner.
Example 1: Synthesis of Styrene-Butadiene-Butyl Acrylate Terpolymer (Styrene 30 phr : 1,3-Butadiene 60 phr : Butyl Acrylate 10 phr)
A. Polymerization Reaction: Two liter reactor was purged with nitrogen gas for about 15minutes and JULABO temperature was set to a temperature of about 5°C. In the reactor, emulsifier solution was added followed by adding about 500g of DM water, about 121 g of styrene, about 41 g of butyl acrylate, about 0.802g of tert-dodecyl mercaptan (TDM). The temperature of the reaction mixture was raised to about 13°C. The reactor was pressurized with 1bar pressure and slow agitation of about 200rpm for about 10minutes to 15mintues. Once the temperature of the reaction mixture drop down to a temperature of about 6°C, agitation was stopped and reactor was vent to release the pressure. At about 6°C, the catalyst solution was added, and the flask was rinsed with addition 40g DM water. Additionally, about 0.485g activator PMHP (para methane hydroperoxide) was charged with dilution using about 20g styrene followed by adding about 220g of 1,3-butadiene. After the complete addition, reaction mixture was stirred at about 1100rpm. Initial temperature and pressure of the reaction were noted and monitored for every 15minutes time. The total solid content of the reaction was checked after about 2 hours and further monitored the progress in every minute reaction time. Polymerization was continued till the conversion reaction reached about 70% with about 24% to 25% total solid content. After the completion of reaction, at about 3.5hours, excess 1, 3 butadiene was vent through vent line and latex was removed from reactor. The reaction was quenched using short stop solution to kill the free radicals inside the reaction mixture. The total weight of the terpolymer latex was about 980g.
Following terpolymer compositions were prepared using the polymerization process described above:

a) 1,3-Butadiene (62 phr); styrene (18 phr); Butyl Acrylate (20 phr)
b) 1,3-Butadiene (65 phr); styrene (20 phr); Butyl Acrylate (15 phr)
c) 1,3-Butadiene (65 phr); styrene (25 phr); Butyl Acrylate (10 phr).
B. Coagulation of styrene-butadiene terpolymer latex About 980g of SBR terpolymer latex was transferred in 5 liter beaker equipped with mechanical stirrer. In the latex, about 1000mg DM water was added and heated to a temperature of about 65°C to 70°C with slow agitation of about 200 rpm. Once the temperature reached to about 65°C, antioxidant solution was added and stirred vigorously for about 10minutes. About 90g of 0.5% flocculant (copolymer of Epichlorohydrin and dimethylamine) was added and stirred for about 10minutes. Finally, about 20% sulphuric acid solution was added drop wise with vigorous stirring till the completion of coagulation. Styrene butadiene terpolymer rubber was taken out and washed two times with hot DM water (2 X 500g). The rubber was dried in vacuum oven at a temperature of about 70°C for about 12hours. Weight of the dried SB terpolymer rubber (Styrene-Butadiene-Butyl Acrylate Terpolymer Rubber) was 230g.
EXAMPLE 2: Styrene-Butadiene-2-Ethylhexyl Acrylate Terpolymer Rubber (Styrene 30 phr : 1,3-Butadiene 60 phr : 2-Ethylhexyl Acrylate 10_phr)
A. Polymerization Reaction: Two liter reactor was purged with nitrogen gas for about 15minutes and JULABO temperature was set to a temperature of about 5°C. In the reactor, emulsifier solution was added followed by adding about 500g of DM water, about 121g of styrene, about 41g of 2-Ethylhexyl Acrylate, about 0.802g of tert-dodecyl mercaptan (TDM). The temperature of the reaction mixture was raised to about 13°C. The reactor was pressurized with 1bar pressure and slow agitation of about 200rpm for about 10minutes to 15mintues. Once the temperature of the reaction mixture drop down to a temperature of about 6°C, agitation was stopped and reactor was vent to release the pressure. At about 6°C, the catalyst solution was added, and the flask was rinsed with addition 40g DM water. Additionally, about 0.485g activator PMHP (para methane hydroperoxide) was charged with dilution using about 20g styrene followed by adding about 240g of 1,3-butadiene. After the complete addition, reaction mixture was stirred at about 1100rpm. Initial temperature and pressure of the reaction were noted and monitored for every 15minutes time. The total solid content of the reaction was checked after about 2hours and further monitored the progress in every minute reaction time. Polymerization was continued till the conversion reaction reached about 70% with about 24% to 25% total solid content. After

the completion of reaction, at about 3.5hours, excess 1, 3 butadiene was vent through vent line and latex was removed from reactor. The reaction was quenched using short stop solution to kill the free radicals inside the reaction mixture. The total weight of the terpolymer latex was about 980g.
B. Coagulation of styrene-butadiene terpolymer latex About 980g of SBR terpolymer latex was transferred in 5 liter beaker equipped with mechanical stirrer. In the latex, about 1000mg DM water was added and heated to a temperature of about 65°C to 70°C with slow agitation of about 200rpm. Once the temperature reached to about 65°C, antioxidant solution was added and stirred vigorously for about 10minutes. About 90g of 0.5% flocculant (copolymer of Epichlorohydrin and dimethylamine) was added and stirred for about 10minutes. Finally, about 20% sulphuric acid solution was added drop wise with vigorous stirring till the completion of coagulation. Styrene butadiene terpolymer rubber was taken out and washed two times with hot DM water (2 X 500g). The rubber was dried in vacuum oven at a temperature of about 70°C for about 12hours. Weight of the dried SB terpolymer rubber (Styrene-Butadiene-2-Ethylhexyl Acrylate Terpolymer Rubber) was 230g.
EXAMPLE 3: Styrene-Butadiene-2-Ethylhexyl Acrylate Terpolymer Rubber (Styrene 30 phr : 1,3-Butadiene 60_phr : hydroxyl butyl vinyl ether propoxylate 10 phr)
A. Polymerization Reaction: Two liter reactor was purged with nitrogen gas for about 15minutes and JULABO temperature was set to a temperature of about 5°C. In the reactor, emulsifier solution was added followed by adding about 500g of DM water, about 121g of styrene, about 41g of hydroxyl butyl vinyl ether propoxylate, about 0.802g of tert-dodecyl mercaptan (TDM). The temperature of the reaction mixture was raised to about 13°C. The reactor was pressurized with 1bar pressure and slow agitation of about 200rpm for about 10minutes to 15mintues. Once the temperature of the reaction mixture drop down to a temperature of about 6°C, agitation was stopped and reactor was vent to release the pressure. At about 6°C, the catalyst solution was added, and the flask was rinsed with addition 40g DM water. Additionally, about 0.485g activator PMHP (para methane hydroperoxide) was charged with dilution using about 20g styrene followed by adding about 220g of 1,3-butadiene. After the complete addition, reaction mixture was stirred at about 1100rpm. Initial temperature and pressure of the reaction were noted and monitored for every 15minutes time. The total solid content of the reaction was checked after about 2hours and

further monitored the progress in every minute reaction time. Polymerization was continued till the conversion reaction reached about 70% with about 24% to 25% total solid content. After the completion of reaction, at about 3.5hours, excess 1, 3 butadiene was vent through vent line and latex was removed from reactor. The reaction was quenched using short stop solution to kill the free radicals inside the reaction mixture. The total weight of the terpolymer latex was about 980g.
B. Coagulation of styrene-butadiene terpolymer latex About 980g of SBR terpolymer latex was transferred in 5 liter beaker equipped with mechanical stirrer. In the latex, about 1000mg DM water was added and heated to a temperature of about 65°C to 70°C with slow agitation of about 200rpm. Once the temperature reached to about 65°C, antioxidant solution was added and stirred vigorously for about 10minutes. About 90g of 0.5% flocculant (copolymer of Epichlorohydrin and dimethylamine) was added and stirred for about 10minutes. Finally, about 20% sulphuric acid solution was added drop wise with vigorous stirring till the completion of coagulation. Styrene butadiene terpolymer rubber was taken out and washed two times with hot DM water (2 X 500g). The rubber was dried in vacuum oven at a temperature of about 70°C for about 12hours. Weight of the dried SB terpolymer rubber (Styrene-Butadiene- hydroxyl butyl vinyl ether propoxylate Terpolymer Rubber) was 230g.
Example 4: Synthesis of the Composite of the present disclosure - addition of silica to latex
Functional SBR (FSBR) latex (equivalent to 100 phr rubber) at a temperature of 70 to 75°C was mixed with HD silica dispersion (80 PHR silica) under stirring condition of 500 RPM to prepare a homogenous dispersion. The FSBR latex and silica dispersion was coagulated using dil. H2SO4 as a coagulating agent (as per Coagulation of styrene-butadiene terpolymer latex process). The solid FSBR rubber and silica mixture separated out and dried at vacuum oven. Dried FSBR AND Silica compounded with a silane coupling agent X5OS (12.8 PHR) and DAE oil (22.0 PHR) at internal mixture. Further, Zinc oxide (3.0 PHR), Stearic acid (2.0 PHR) protecting agents 6PPD (2.0 PHR) & TMQ (0.75 PHR) were added in the next step. In the final stage, curing agent soluble Sulphur (1.8 PHR), TBBS (1.7 PHR), DPG (2 PHR) were added. A similar FSBR-silica composite was prepared without adding the silane coupling agent.

Example 5: Synthesis of the Composite of the present disclosure – addition of silica to rubber
FSBR silica composite was prepared by four stage mixing process at elevated temperature. Initially, a temperature of an internal mixer (Baneberry) was set at 130°C at a speed of 60 RPM. Ingredients FSBR (100 PHR), HD silica filler (80 phr) and DAE oil (22 phr) were added to the mixer and mixed. The exotherm raises the temperature to 165 to 170°C. The process was completed in 10 minutes to obtain an effective mixing of FSBR and silica at 165 to 170°C to have better chemical interaction through FSBR polar co-monomer functionality and silanol group on silica surface. In the next stage, the temperature of the internal mixer was set at 110°C. Master 1 (of silica, FSBR, DAE oil composite) and silane coupling agent X50S (12.5 PHR) were mixed at 145°C to obtain Master 2. Further, master 2 was mixed with accelerator activator Zinc oxide (3.0 PHR), Stearic acid (2.0 PHR), antioxidant and antiozonants 6PPD (2.0 PHR) & TMQ (0.75 PHR) at 120°C to obtain Master 3. Finally, Master 3 and curing agents soluble Sulphur (1.8 PHR), TBBS (1.7 PHR), DPG (2 PHR) were mixed at 100-110°C. Thus, FSBR-Silica composites were prepared via four stage mixing. A similar FSBR-silica composite was prepared without adding the silane coupling agent.
Example 6: Comparison of Butyl acrylate based FSBR-Silica Composite with Std SBR and SSBR
For comparative study, the composite of grade SBR 1502 with silica filler was prepared as shown in Table 1. The SBR-Silica composite recipe comprises SBR (100 PHR), HD silica filler (80 PHR), Zinc oxide (3.0 PHR), Stearic acid (2.0 PHR), coupling agent X5OS (12.8 PHR), DAE oil (22.0 PHR), protecting agents 6PPD (2.0 PHR) & TMQ (0.75 PHR) & Curing agent soluble Sulphur (1.8 PHR), TBBS (1.7 PHR), DPG (2 PHR).
SBR1502 (std.) is a commercial grade of emulsion SBR that does not contain a polar functional monomer. It is referred to as ESBR (emulsion SBR) in the figures. SSBR stands for solution based SBR and it also does not contain a polar functional monomer.
Table 1: Compounding of std. SBR, FSBR, SSBR with Silica filler

Ingredients Std. SBR (PHR) FSBR (PHR) SSBR (PHR)
Std. SBR 100 -- --
FSBR -- 100 --

SSBR -- -- 100
HD Silica 80 80 80
X50S 12.8 12.8 12.8
DAE Oil 22 22 22
Zinc Oxide 3 3 3
Stearic Acid 2 2 2
TMQ 0.75 0.75 0.75
6PPD 2 2 2
TBBS 1.7 1.7 1.7
Soluble Sulfur 1.8 1.8 1.8
DPG 2 2 2
Total 228.05 228.05 228.05
Morphology and Performance Studies of SBR-Silica Composite
Polymer-Filler Interaction Study
In the compounding studies, homogeneous mixture of SBR terpolymer with silica was observed. To check the homogeneity and rubber filler interaction, a comparative bound rubber and cross link density studies were performed. These studies basically indicate the filler-filler interaction and filler-polymer interaction in the compounded rubber.
According to comparative bound rubber study, a polymer-Filler interaction in FSBR is substantially higher as compared to ESBR (also referred to as Std. SBR). See Figure 1.
A cross link density study shows higher crosslink density in case of FSBR compared to ESBR. Thus, higher bound rubber and higher cross link density of FSBR-Silica composite reflects better rubber-filler interaction and improved mechanical properties.
Comparative Rheological study of FSBR-Silica Composite
A comparative rheological study of FSBR-Silica composite with SSBR-Silica and SBR 1502-Silica Composites was carried out. Data shows that comparatively faster curing was observed in FSBR-Silica composite than SSBR-silica composite (Table 2 and Figure 3).

Table 2: Comparative rheological study

Parameters SBR 1502 (std) FSBR (Butyl Acrylate) SSBR (NS116)
MH (DN-M) 27.3 27.7 27.3
TS2 (MIN) 3.3 3.4 3.6
T50 (MIN) 6.2 6.2 6.3
T90 (MIN) 12.2 12.4 12.8
In a curing study, a Torque vs Time rheological curve is prepared where torque is the resistance of material to the applied shear. In the above table: a) MH (DN-M) is the maximum torque of the compound on curing at specific temperature and time (minutes); b) TS2 (MIN) is time taken in minutes to raise the torque by two unit above the minimum torque; C) T50 (MIN) is the time taken in minutes to increase the torque to 50% of maximum torque. d) T90 (MIN) is the time taken to increase the torque to 90% of the maximum torque.
Physical Properties Study
A physical properties comparison study was carried out for tensile, modulus and tear strength
properties of FSBR, ESBR 1502 and SSBR silica composites. The modulus of FSBR-Silica
composite was found to be 33% superior to ESBR.
Similarly, the tensile strength of FSBR-silica composite was 27% superior to SSBR and
comparable to ESBR. Tear strength study shows that functional SBR composites show 36%
better tear strength than SSBR and the tear strength of FSBR composite is comparable to ESBR
(Figures 4-6).
Dynamic Study of FSBR-Silica Composite
DIN abrasion loss data indicate superiority of FSBR vulcanizates over ESBR 1502 and SSBR vulcanizates. FSBR composites shows 33% improvement in abrasion property compared to SSBR and 20% improvement compared to ESBR. See Figure 7.
For the performance studies, dynamic properties have been studied by rubber process analyzer (RPA). These studies indicates that at 70 °C, the tan delta (loss factor) of FSBR-Silica

composite is 9% improved than ESBR-silica composite and is similar to SSBR-Silica composite. This indicates that rolling resistance of functionalized SBR rubber is 9% improved than ESBR rubber (Figure 10). Similarly, at 0 °C, the tan delta value indicates the wet traction. Wet skid resistance of FSBR-Silica composite is 6% better than ESBR grade and is similar to SSBR (Figure 8). Similarly dry skid resistance of FSBR is 13% better than ESBR (Figure 9).
Example 7: Vinyl Propoxylate based FSBR Silica Composite
For a comparative study, composites of grade SBR 1502, SSBR, and FSBR with silica filler were prepared. The SBR-Silica composite recipe contains SBR (100 PHR), silica filler (80 PHR), Zinc oxide (2.5 PHR), Stearic acid (1 PHR), coupling agent Si-69 (14 PHR), low PCA oil (TDAE, 30 PHR), curing agent Sulphur (1.8 PHR), TBBS (1.5 PHR) and DPG (0.5 PHR).
Table 4: Compounding of Different SBR Grades with Silica filler

Ingredients FSBR SSBR SBR 1502
FSBR 100 -- --
SSBR -- 100 --
SBR 1502 -- -- 100
Low PCA oil (TDAE) 30 30 30
Silica-High dispersible silica 80 80 80
X50S 14 14 14
Zinc Oxide 2.5 2.5 2.5
St Acid 1 1 1
Soluble Sulfur 1.8 1.8 1.8
TBBS 1.5 1.5 1.5
DPG 0.5 0.5 0.5
Total phr 231.3 231.3 231.3
Comparative Rheological study of FESBR-Silica Composite
A comparative rheological study of FSBR-Silica composite with SSBR-Silica and SBR 1502-Silica Composites was carried out. Data shows that a comparatively faster curing is observed in FSBR-Silica composite than SBR 1502-Silica composite.

Table 5: Comparative rheological study

Parameters FSBR (Propoxylate) SSBR (NS116) SBR 1502 (std)
Min. Torque, dN-m 3.7 2.9 2.7
Max. Torque, dN-m 27.1 26.4 23.9
tC90, Minute 9.9 7.6 10.6
Delta Torque, dN-m 23.4 23.4 21.3
Cure Rate, dN-m/Minute 2.8 3.8 2.9
Physical Properties study of FSBR-silica composite
A comparative modulus study of FSBR-Silica composite with SSBR-Silica and SBR 1502-Silica Composites was performed. Data shows that modulus@100%, 200% and 300% was superior in propoxylate-based FSBR-Silica composite than SBR 1502-Silica composite (Table 6). Similarly, the tensile strength of FSBR-Silica composite was better than SSBR & SBR 1502-Silica composite (Table 7).
Table 6: Modulus study of FSBR, SSBR & SBR 1502 composites

Parameters FSBR (Propoxylate) SSBR (NS116) SBR 1502 (std)
Modulus Elongation @100% 129 113 100
Modulus Elongation @200% 139 112 100
Modulus Elongation @300% 135 112 100
Table 7: Tensile study of FSBR, SSBR & SBR 1502 composites

Parameters FSBR (Propoxylate) SSBR (NS116) SBR 1502 (std)
Tensile Strength 110 104.2 100

Dynamic Properties study
Comparative dynamic properties studies were carried out for the FSBR-Silica composite with SSBR-Silica and SBR 1502-Silica Composites. Data shows that abrasion properties in propoxylate based FSBR-silica composite were superior (8%) than SBR 1502-Silica composite and 28% better than SSBR composite (Table 8).
Similarly, the skid resistance (tan delta at 30 oC) of FSBR-Silica composite was comparable to SSBR and superior (6%) to SBR 1502-Silica composite (Table 8). The rolling resistance (tan delta at 70) of FSBR-Silica composite was superior (5%) than SBR 1502-Silica composite (Table 8).
Table 8: Dynamic study of FSBR, SSBR & SBR 1502 composites

SBR 1502 (std) FSBR (Propoxylate) SSBR (NS116)
Abrasion loss 100 92 118
tanδ @30°C (Traction) 100 106 107
tanδ @70°C (RR) 100 95 93
Example 8: 2-Ethylhexyl Acrylate based FSBR-Silica Composite
Before composite preparation, a comparative Mooney viscosity, Tg properties study of FSBR
(2-ethylhexyl acrylate), SSBR, SBR 1502 rubbers were carried out.
Table 9: Comparative Mooney Viscosity study

SSBR SBR1502 (std) FSBR (EHA)
Mooney Viscosity ML(1+4)@100°C (MU) 71 53 45

Table 10: Comparative Tg (Glass Transition Temperature) study

SSBR SBR1502 (std) FSBR (EHA)
Tg (°C) -25 -52 -56
2-Ethylhexyl Acrylate based FSBR-Silica Composites
SBR 1502, SSBR, and 2-Ethylhexyl Acrylate based FSBR were then reinforced with silica filler for the preparation of rubber-Silica composites. The SBR-Silica composites contain SBR (100 PHR), silica filler (80 PHR), zinc oxide (2.5 PHR), stearic acid (1 PHR), coupling agent Si-69 (14 PHR), low PCA oil (TDAE, 30 PHR), curing agent sulphur (1.8 PHR), TBBS (1.5 PHR) and DPG (0.5 PHR).
Table 11: Compounding of Different SBR Grades with and Silica filler

Ingredients SBR 1502 (PHR) SSBR (PHR) FSBR (EHA) PHR
SBR 1502 100 -- --
SSBR -- 100 --
FSBR -- -- 100
Low PCA oil (TDAE) 30 30 30
HD silica 80 80 80
X50S 14 14 14
Zinc Oxide 2.5 2.5 2.5
St Acid 1 1 1
Soluble Sulfur 1.8 1.8 1.8
TBBS 1.5 1.5 1.5
DPG 0.5 0.5 0.5
Total PHR 231.3 231.3 231.3
Comparative Rheological Study of FSBR-Silica Composite
A comparative rheological study of FSBR-Silica composite was carried out with SSBR-Silica and SBR 1502-Silica Composites. Data shows that comparatively faster curing was observed in FSBR-Silica composite (T90 14.3) than SSBR-Silica composite (T90 29.5) and SBR 1502 (Table 12).

Table 12: Rheological Study (MDR 2000) @160°C/45 min)

SSBR SBR1502 (std) FSBR (EHA)
ML (dN-M) 3.1 4.1 3.8
MH (dN-M) 27.9 32.3 27.8
tc90 (Min) 29.5 15.2 14.3
Final Torque (dN-M) 27.9 32.2 27.7
Physical Properties Study
A comparative modulus study of FSBR-Silica composite with SSBR-Silica and SBR 1502-Silica Composites was performed. Data shows that modulus@100%, 200% and 300% was superior in 2-ethylhexyl acrylate based FSBR-Silica composite than SBR 1502-Silica composite (Table 13). Similarly, the tensile strength of FSBR-Silica composite was better than SSBR & SBR 1502-Silica composite (Table 13).
Dynamic Properties Study
Comparative dynamic properties studies were carried out for FSBR-Silica composite and SSBR-Silica and SBR 1502-Silica Composites. Abrasion resistance (a lower value is better) of 2-ethylhexyl acrylate based FSBR-Silica composite was superior (37%) than SSBR and 16% better than 1502-Silica composites (Table 14).
Data shows that the dry skid resistance (Tan Delta, 30˚C, higher value is better) in 2-ethylhexyl acrylate based FSBR-silica composite was 8.6% better than SBR 1502-Silica composites (Table 14). Similarly, the rolling resistance (tan delta at 70, lower value is better) of FSBR-Silica composite was comparable with SBR 1502 and superior (9%) to SSBR-Silica composite (Table 14).
Table 14: Comparative Dynamic Properties

SSBR SBR1502 (std) FSBR (EHA)
Abrasion loss 62.5 100 83.5
Tan Delta, 30˚C 100 100 108.7

Tan Delta, 70˚C 71.5 100 81.6
Example 9: Butyl acrylate based-FSBR-Silica Composite with a High Loading of Silica without a Silane Coupling Agent
FSBR-silica composites were prepared with a high loading of silica (100 phr) without using a silane coupling agent. FSBR was mixed with silica without a silane coupling at 165-170°C for 6 minutes for better chemical interaction. A two-stage mixing was carried out. For a comparative study, the composite of grade SBR 1502 and FSBR with silica filler were prepared (Table 15). The SBR-silica composite contains SBR (100 PHR), Precipitated silica filler (100 PHR), zinc oxide (3.0 PHR), stearic acid (2 PHR), 6 PPD (2 PHR), Sulphur (1.8 PHR), TMQ (0.9 PHR), & TBBS (1.5 PHR).
Table 15: Compounding of FSBR with silica filler without a silane coupling agent

SBR 1502 (PHR) FSBR (PHR)
SBR 1502 100 -
FSBR - 100
Precipitated Silica 100 100
Low PCA oil (TDAE) 20 20
stearic acid 2 2
ZnO 3 3
6PPD 2 2
TMQ 0.9 0.9
Sulphur 1.8 1.8
TBBS 1.7 1.7
Total 231.4 231.4
Rheological Study
A comparative rheological study of FSBR-Silica composite with SBR 1502-Silica composite was performed. Data shows that a comparatively faster curing was observed in FSBR-Silica composite (T90, 17) than SBR 1502-Silica composite (T90, 24.2) (Table 16).

Table 16: Rheological Study @160°C/30 min)

SBR1502 FSBR
Ts2 3.5 3.7
MH (dN-M) 25.2 33.2
TC90 (Min) 24.2 17.0
Physical Properties study
A comparative modulus study of FSBR-Silica composite with SBR 1502-Silica Composite was performed. Data shows that modulus @100% is superior in FSBR-Silica composite than SBR 1502-Silica composite (Table 17). Similarly, the tensile strength of FSBR-Silica composite was better (55.8% higher) than SBR 1502-Silica composite (Table 17).
Table 17: Physical properties study of FSBR & SBR 1502 composites

Physical Properties (Cured @ 160°C/ 30 min)
SBR1502 FSBR
Mod @100% Elongation (MPa) 3.2 7.8
Tensile Strength (MPa) 13.2 25.3
% Elongation at break 442 355
Comparative Tear Strength Properties study
A comparative tear strength study of FSBR-silica composite with SBR 1502-silica composite was performed. Data shows that the tear strength of FSBR-silica composite was better (5%) than SBR 1502-silica composite (Table 18).
Table 18: Comparative Tear Strength Properties

Tear Strength Properties
SBR1502 FSBR
Tear Strength 100.00 105.00

Dynamic Properties Study
A comparative dynamic properties study for FSBR-Silica composite without a silane coupling agent with SBR 1502-Silica composite without silane coupling was performed. Data shows that dry skid resistance (Tan Delta, 30˚C, higher value is better property) of FSBR-silica composite was superior (11%) to SBR 1502-Silica composites. Abrasion loss of FSBR-silica was 21% better than SBR 1502-silica composite (Table 19). Similarly, the rolling resistance (tan delta at 70, lower value is better) of FSBR-Silica composite was 9% better to SBR 1502-silica composite (Table 19).
Table 19: Comparative Dynamic Properties

Properties SBR1502 FSBR
Abrasion Loss 100 79
Tan Delta, 30˚C (Dry Skid) 100 111
Tan Delta, 70˚C (Rolling Resistance) 100 91
Example 10: Butyl acrylate based-FSBR-Silica Composite with a High Loading of Silica with a Silane Coupling
A FSBR-silica composite was prepared with a high loading of silica (100 phr) with a silane coupling agent. FSBR and Silica were mixed with a silane coupling agent at 160-165°C for 6 min. For a comparative study, the composite of grade SBR 1502 and FSBR with silica filler (Table 20) and a silane coupling agent (16 phr) were prepared. The SBR-silica composite contains SBR (100 PHR), Precipitated silica filler (100 PHR), silane coupling agent (16 phr), zinc oxide (3.0 PHR), stearic acid (2 PHR), 6 PPD (2 PHR), Sulphur (1.8 PHR), TMQ (0.9 PHR), & TBBS (1.5 PHR).
Table 20: Compounding of FSBR with silica filler with a Silane coupling agent

Compounding Recipe SBR 1502 (PHR) FSBR (PHR)
SBR 1502 100 -
FSBR - 100
Precipitated Silica 100 100
Silane Coupling Agent 16 16
Low PCA oil 20 20

stearic acid 2 2
ZnO 3 3
6PPD 2 2
TMQ 0.9 0.9
Sulphur 1.8 1.8
TBBS 1.7 1.7
Total 247.4 247.4
Rheological Study
A comparative rheological study of FSBR-Silica composite with SBR 1502-Silica composite was performed. Data shows that the curing observed in SBR-Silica and FSBR-Silica composite was comparable (Table 21).
Table 21: Rheological Study @160°C/30 min)

SBR1502-Silica FSBR-Silica
Ts2 2.9 3.2
MH (dN-M) 29.1 30.2
TC90 (Min) 11.8 12.1
Physical Properties study
A comparative modulus study of FSBR-Silica composite with SBR 1502-Silica Composite was performed. Data shows that modulus @100% was superior in FSBR-Silica composite than SBR 1502-Silica composite (Table 22). Similarly, the tensile strength of FSBR-Silica composite was better (34% higher) than SBR 1502-Silica composite (Table 22).
Table 22: Physical properties study of FSBR & SBR 1502 composites

Physical Properties (Cured @ 160°C/ 30 min)
SBR1502-Silica FSBR-Silica
Mod @100% Elongation (MPa) 6.8 11.7

Tensile Strength (MPa) 18.3 27.8
% Elongation at break 375 285
Comparative Tear Strength Properties study
A comparative tear strength study of FSBR-silica composite with SBR 1502-silica composite was performed. Data shows that the tear strength of FSBR-silica composite was better (8.2%) than SBR 1502-silica composite (Table 23).
Table 23: Comparative Tear Strength Properties

Tear Strength Properties
SBR1502-Silica FSBR-Silica
Tear Strength 100.0 109.0
Dynamic Properties Study
A comparative dynamic properties study for FSBR-Silica composite with a silane coupling with SBR 1502-Silica composite with a silane coupling was performed. Data shows that dry skid resistance (Tan Delta, 30˚C, higher value is better property) of FSBR-silica composite was superior (12.2%) to SBR 1502-Silica composites. Abrasion loss of FSBR-silica was 23% better than SBR 1502-silica composite (Table 24). Similarly, the rolling resistance (tan delta at 70, lower value is better) of FSBR-Silica composite was 12% better to SBR 1502-silica composite (Table 24).
Table 24: Comparative Dynamic Properties

Properties SBR1502 FSBR
Abrasion Loss 100 77
Tan Delta, 30˚C (Dry Skid) 100 114
Tan Delta, 70˚C (Rolling Resistance) 100 88

Example 11: A comparison of FSBR-Silica Composite with a High Loading of Silica
without a silane coupling agent (Example 9) and with a Silane Coupling Agent
(Example 10)
This example shows a comparison of rheological, physical, and dynamic properties of
FSBR-Silica composites of Example 9 (without a silane coupling agent) and Example 10
(with a silane coupling agent).
Table 25: Compounding of FSBR with silica filler with and without a coupling agent

SBR 1502 (PHR) FSBR-Silica
(PHR) without a
coupling agent FSBR-Silica
(PHR) with a
silane coupling
agent
SBR 1502 100 - -
FSBR - 100 100
Precipitated Silica 100 100 100
Silane
Coupling
Agent - - 16
Low PCA oil (TDAE) 20 20 20
stearic acid 2 2 2
ZnO 3 3 3
6PPD 2 2 2
TMQ 0.9 0.9 0.9
Sulphur 1.8 1.8 1.8
TBBS 1.7 1.7 1.7
Total 231.4 231.4 247.4
Rheological Study
A comparison of rheological study data of Examples 9 and 10.
Table 26: Rheological Study

SBR1502-Silica FSBR-Silica without
a silane coupling
agent FSBR-Silica with a silane coupling agent
Ts2 3.5 3.7 3.2
MH (dN-M) 25.2 33.2 30.2

TC90 (Min) 24.2 17.0 12.1
Physical properties study
A comparison of physical properties study data of Examples 9 and 10.
Table 27: Physical properties study

Physical Properties (Cured @ 160°C/ 30 min)
SBR1502-Silica FSBR-Silica
without a silane
coupling agent FSBR-Silica with
a silane coupling
agent
Mod @100% Elongation (MPa) 3.2 7.8 11.7
Tensile Strength (MPa) 13.2 25.3 27.8
% Elongation at break 442 355 285
Comparative Tear Strength Properties study
A comparison of tear strength study data of Examples 9 and 10.
Table 28: Comparative Tear Strength Properties

Tear Strength Properties
SBR1502-Silica FSBR-Silica without a silane coupling agent FSBR-Silica with a silane coupling agent
Tear Strength 100.00 105.00 109.0
Comparative Dynamic Properties Study
A comparison of dynamic properties study data of Examples 9 and 10.
Table 29: Comparative Dynamic Properties

Properties SBR1502-Silica FSBR-Silica
without a silane
coupling agent FSBR-Silica with
a silane coupling
agent
Abrasion Loss 100 79 77
Tan Delta, 30˚C (Dry Skid) 100 111 114
Tan Delta, 70˚C (Rolling Resistance) 100 91 88

As can be seen from Tables 26-29, the rheological, physical, and dynamic properties of FSBR-Silica composites prepared without a silane coupling agent and with a silane coupling agent are comparable even at a high loading of silica filler such as 100 PHR. Thus, the FSBR-silica composites of the present disclosure prepared without a silane coupling agent are advantageous as they exhibit rheological, physical, and dynamic properties that are similar to the composites with a silane coupling agent and at the same time provide environmental benefits such as no release of sulphur and ethanol. Further, the FSBR-silica composites of the present disclosure prepared without a silane coupling agent are also expected to show lesser scorching and lesser deterioration of storage and dynamic modulus compared to FSBR-silica composites with a silane coupling agent.
Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based on the description provided herein. The embodiments herein provide various features and advantageous details thereof in the description. Descriptions of well-known/conventional methods and techniques are omitted so as to not unnecessarily obscure the embodiments herein.
The foregoing description of the specific embodiments reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments in this disclosure have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
Throughout this specification, the term ‘combinations thereof’ or ‘any combination thereof’ or ‘any combinations thereof’ are used interchangeably and are intended to have the same meaning, as regularly known in the field of patents disclosures.

As regards the embodiments characterized in this specification, it is intended that each embodiment be read independently as well as in combination with another embodiment. For example, in case of an embodiment 1 reciting 3 alternatives A, B and C, an embodiment 2 reciting 3 alternatives D, E and F and an embodiment 3 reciting 3 alternatives G, H and I, it is to be understood that the specification unambiguously discloses embodiments corresponding to combinations A, D, G; A, D, H; A, D, I; A, E, G; A, E, H; A, E, I; A, F, G; A, F, H; A, F, I;
B, D, G; B, D, H; B, D, I; B, E, G; B, E, H; B, E, I; B, F, G; B, F, H; B, F, I; C, D, G; C, D, H;
C, D, I; C, E, G; C, E, H; C, E, I; C, F, G; C, F, H; C, F, I, unless specifically mentioned
otherwise.
While considerable emphasis has been placed herein on the particular features of this disclosure, it will be appreciated that various modifications can be made, and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other modifications in the nature of the disclosure or the preferred embodiments will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.

We Claim:
1. A composition comprising about 80-120 parts per hundred of rubber (PHR) of
functionalized styrene butadiene polymer and about 60-100 PHR of silica, wherein the
functionalized styrene butadiene polymer comprises:
(i) about 45 to 90 PHR of a conjugated diene monomer; (ii) about 10 to 40 PHR of a vinyl substituted aromatic monomer; and (iii) about 1 to 20 PHR of a polar co-monomer selected from a group comprising acrylate, propoxylate, sulphonate, and a combination thereof.
2. The composition as claimed in claim 1, wherein the functionalized styrene butadiene polymer is a terpolymer or a tetrapolymer.
3. The composition as claimed in claim 1 or 2, wherein the conjugated diene monomer is selected from a group comprising 1,3-butadiene, isoprene, 1,3-ethylbutadiene, hexadiene, cyclooctadiene, octadiene, cyclic conjugated dienes, or a combination thereof.
4. The composition as claimed in any one of claims 1-3, wherein the vinyl substituted aromatic monomer is selected from a group comprising styrene, α-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-cyclohexylstyrene, 4-para tolylstyrene, para-chlorostyrene, 4-tert-butyl styrene, 1-vinylnaphthalene, 2-vinylnapthalene or a combination thereof.
5. The composition as claimed in any one of claims 1-4, wherein the acrylate is selected from a group comprising butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methacrylate, methyl methacrylates, hydroxyethylmethacrylate, butyl methacrylates, vinyl acrylate, acrylic acid, acrylonitrile, allyl acrylate, acrylamide, or a combination thereof.
6. The composition as claimed in any one of claims 1-5, wherein the propoxylate is hydroxyl butyl vinyl ether propoxylate.
7. The composition as claimed in any one of claims 1-6, wherein the sulphonate is selected from a group comprising styrene sulphonate, 2-acrylamido 2-methylpropane sulphonate, sodium allyl sulphonate and sodium methallyl sulphonate or a combination thereof.
8. The composition as claimed in claim 1, wherein the conjugated diene monomer is 1,3-butadiene, the vinyl substituted aromatic monomer is styrene, and the polar co-monomer is butyl acrylate.

9. The composition as claimed in claim 1, wherein the conjugated diene monomer is 1,3-butadiene, the vinyl substituted aromatic monomer is styrene, and the polar co-monomer is hydroxyl butyl vinyl ether propoxylate.
10. The composition as claimed in claim 1, wherein the conjugated diene monomer is 1,3-butadiene, the vinyl substituted aromatic monomer is styrene, and the polar co-monomer is 2-ethylhexyl acrylate.
11. The composition as claimed in any one of claims 1-10, wherein the composition comprises an ingredient selected from a group comprising plasticizer, accelerator, activator, antioxidant, antiozonant, aromatic oil, curing agent, or a combination thereof.
12. The composition as claimed in claim 11, wherein the ingredient is present in an amount of about 0.1 PHR to 50 PHR based on parts per hundred of rubber.
13. The composition as claimed in claim 11 or 12, wherein the plasticizer is selected from a group comprising residual aromatic extract (RAE) oil, naphthenic oil, paraffinic oil, soluble sulphonic acid or a combination thereof; the accelerator is selected from a group comprising N- tert-butyl-2-benzothiazyl sulfenamide (TBBS), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N,N-Dicyclohexyl -2- benzothiazole sulfenamide (DCBS), 2-Mercaptobenzothiazole (MBT), Di Thiophosphates, Zinc O,O,O',O'-tetrabutyl bis(phosphorodithioate) (ZDBP), Tetraisobutylthiuram disulphide (IBT), Tetraisobutylthiuram monosulphide (IBM) or a combination thereof; the activator is selected from a group comprising zinc oxide, lead oxide, magnesium oxide, stearic acid or a combination thereof; the antioxidant is selected from a group comprising poly(1,2-dihydro-2,2,4-trimethyl-quinoline) (TMQ), styrenated phenol, phenyl –ß-napthyl amine (PBN), octylated diphenyl amine (ODPA), p-oriented styrenated diphenyl amine (SDPA), butylated hydroxytoluene (BHT), 4-methyl-6 terlbutyl phenol (BPH), cyclic acetals, or a combination thereof; the antiozonant is selected from a group comprising N-1,3-dimethylbutyl)-N-phenyl-p-phenylenediamine (6PPD), N-isopropyl-N’-phenyl-p-phenylenediamine (IPPD), N,N'-dixylene-p-phenylenediamine (DTPD), N,N'-Bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD) or a combination thereof; the aromatic oil is selected from a group comprising treated distilled aromatic extract (TDAE), residual aromatic extract (RAE), distilled aromatic extract (DAE), or a combination thereof; and the curing agent is sulphur.

14. The composition as claimed in claim 13, wherein the activator is zinc oxide in an amount of 2 to 4 PHR and stearic acid in an amount of 1 to 3 PHR, the accelerator is TBBS in an amount of 1 to 2 PHR, the antiozonant is 6PPD in an amount of 1 to 3 PHR, the antioxidant is TMQ in an amount of 0.5 to 1.5 PHR, the aromatic oil is TDAE in an amount of 10 to 30 PHR, and the curing agent is sulphur in an amount of 1 to 3 PHR, based on parts per hundred of styrene-butadiene rubber (SBR).
15. The composition as claimed in any one of claims 1-14, wherein the composition does not comprise a silane coupling agent.
16. A process for preparing the composition as claimed in any one of claims 1-15, comprising:

a) subjecting the conjugated diene monomer, the vinyl substituted aromatic monomer, and the polar co-monomer to an emulsion polymerization to obtain functionalized styrene butadiene polymer latex;
b) coagulating the functionalized styrene butadiene polymer latex to obtain the functionalized styrene butadiene polymer rubber, and
c) adding silica prior to or after said coagulating to obtain the composition.
17. The process as claimed in claim 16, wherein the emulsion polymerization is carried out in
the presence of water, emulsifier and a catalyst, at a temperature ranging from about 1°C to
20°C.
18. The process as claimed in claim 16 or 17, wherein the emulsion polymerization comprises
the steps of:
d) mixing the emulsifier with water, a modifier, the vinyl substituted aromatic monomer, and the polar co-monomer at a temperature of about 13°C to 15°C to obtain a reaction mixture;
e) adding a catalyst, an activator, and the conjugated diene monomer to the reaction mixer at a temperature of about 6°C to 12°C; and
f) allowing polymerization of the reaction mixture to obtain the functionalized styrene butadiene polymer latex.
19. The process as claimed in claim 18, wherein the emulsifier comprises an emulsifying agent
selected from a group comprising Rosin acid, fatty acid, sodium dodecyl naphthyl methyl
sulphonate (DNMS), sodium lauryl sulfate, sodium dioctyl sulfosuccinate, sodium oleate,
triethanolamine stearate, ethylenediaminetetraacetic acid (EDTA), potassium chloride,

benzalkonium chloride, or a combination thereof; the modifier is selected from a group comprising Tert-dodecyl mercaptan (TDM), aldehydes, acids, dibenzyltrithiocarbonate or a combination thereof; the catalyst is selected from a group comprising Sodium Formaldehyde Sulfoxylate (SFS), FeSO4, EDTA, CuSO4, K2SO4, NH4SO3, NaHSO3 or a combination thereof; and the activator is a peroxide.
20. The process as claimed in any one of claims 16-19, wherein the coagulation is carried out
by:
a) diluting the functionalized styrene butadiene polymer latex with water,
b) heating the latex to a temperature of about 50°C to 80°C,
c) adding an antioxidant and a flocculent, and
d) adding a coagulating agent to the functionalized styrene butadiene polymer latex to obtain the functionalized styrene butadiene polymer rubber.

21. The process as claimed in claim 20, wherein the coagulating agent is selected from a group comprising an acid, sodium chloride, calcium chloride, or a combination thereof.
22. The process as claimed in any one of claims 16-21, wherein the process comprises adding about 0.1 to 50 PHR of an ingredient to the functionalized styrene butadiene polymer latex/rubber; wherein the ingredient is selected from a group comprising plasticizer, accelerator, activator, antioxidant, antiozonant, aromatic oil, curing agent, or a combination thereof.
23. A tyre tread comprising the composition as claimed in any one of claims 1-15.