Claims:1. A rubber composition based upon parts by weight per 100 parts by weight of rubber (phr) comprises-
(i) about 20 to 70 PHR of conjugated diene monomer;
(ii) about 10 to 50 PHR of vinyl substituted aromatic monomer; and
(iii) about 1 to 30 PHR of acrylate or propoxylate and their derivatives.

2. The rubber composition as claimed in claim 1, wherein the conjugated diene monomer is selected from a group comprising 1,3-butadiene, isoprene, 1,3-ethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-pentadiene, 1,3-cyclooctadiene and 1,3 octadiene or any combinations thereof.

3. The rubber composition as claimed in claim 1, wherein the vinyl substituted aromatic monomer is selected from a group comprising styrene, a-methyl styrene, vinyl toluene, 3-methyl styrene, 4-methyl styrene, 4-cyclohexylstyrene, 4-para tolylstyrene, para-chlorostyrene, 4-tert-butyl styrene, 1-vinylnaphthalene, 2-vinylnapthalene or any combinations thereof.

4. The rubber composition as claimed in claim 1, wherein the vinyl propoxylate is hydroxyl butyl vinyl ether propoxylate; and acrylate is selected from a group comprising Butyl Acrylate, 2-Ethylhexyl Acrylate and methyl acrylate, ethyl acrylate.

5. The rubber composition as claimed in claim 1, has glass transition temperature (Tg) ranging from about -80°C to 40°C.

6. The rubber composition as claimed in claim 1, has Mooney viscosity ranging from about 25 to 80.

7. The rubber composition as claimed in claim 1 is gel free with minimum cross linking.

8. The rubber composition as claimed in claim 1 is functionalized random polymer with high molecular weight terpolymer functionalization.

9. A process of synthesising the rubber composition as claimed in claim 1, comprising-
subjecting the conjugated diene monomer, vinyl substituted aromatic monomer and n-butyl derivative to polymerization in the presence of water, emulsifier and redox catalyst, at a temperature ranging from about 1°C to 20°C.

10. The process as claimed in claim 9, wherein the emulsifier is added at the onset of the polymerization or added incrementally or proportionally, or a combination thereof, wherein the emulsifier is anionic, cationic or non-ionic, or a combination thereof.

11. The process as claimed in claim 9, wherein the emulsifier is a combination of rosin acid and fatty acid.

12. The process as claimed in claim 9, wherein latex obtained during polymerization is, coagulated with sulfuric acid

13. The process as claimed in claim 9, wherein the rubber composition is synthesized by about 60% to 75% partial conversion of emulsion polymerization.

14. The process as claimed in claim 9, wherein reaction rate during the synthesis of rubber composition is about 25% to 30% times faster than available process for synthesis of regular SBR products.
, Description:TECHNICAL FIELD
The present disclosure relates to composition, particularly to a rubber composition comprising conjugated diene monomer, vinyl substituted aromatic monomer and acrylate or vinyl propoxylate, the said composition is reinforced with filler. The present disclosure further relates to process of synthesising the said rubber composition.

BACKGROUND OF THE DISCLOSURE
Styrene butadiene rubber (SBR) is one of the first synthetic rubber and has occupied leading place among all types of rubber grades. Increase in the demand for SBR in the tyre industry, which covers about 74% of world consumption, has been stimulated by growth of the SBR market.

Currently, automobile tire companies are giving more importance towards the safety of travel, fuel economy and environmental safety. The reduction of rolling resistance of tires has become the preliminary objective for tire industry, as it has close relation to the fuel consumption, hysteresis loss properties of tire tread and carbon dioxide emission (greenhouse gases) of motor vehicles. Dispensability of filler is considered to affect hysteresis loss. The tire tread is a major contributor to both the tire rolling resistance and its traction. Thus, to reduce the rolling resistance of tire tread, numerous approaches are reported in the literature. For example, modified S-SBR copolymers with functional groups at chain ends have been developed via solution polymerization systems to achieve improved interaction with silica or carbon black. These modifications showed reduction in the hysteresis loss of filled compounds. The modified S-SBR copolymers with both primary amino group and alkyoxysilyl group introduced at the same chain-end exhibited lower hysteresis loss properties.

However, there appears to be still a need to improve the properties of the rubber composition, which can efficiently interact well with silica, so that there is lower rolling resistance and improved traction of tread for better performance of tire tread.

The present disclosure aims to disclose a rubber composition with improved properties which is significantly compatible with polar filler for better and homogeneous dispersion, so that there is significantly lower rolling resistance, as a result significantly contributing to fuel efficiency and contributing to improved traction of tread for better performance of tire tread.

SUMMARY OF THE DISCLOSURE
Accordingly, the present invention describes a rubber composition, particularly functionalized rubber composition with the functional group of acrylate or propoxylate and their derivatives.
The rubber composition, based upon parts by weight per 100 parts by weight of rubber (phr), comprising: (i) about 70 to 20 PHR of conjugated diene monomer; (ii) about 10 to 50 PHR of vinyl substituted aromatic monomer; and (iii) about 1 to 30 PHR of acrylate or vinyl propoxylate.

BRIEF DESCRIPTION OF ACCOMPANYING FIGURES
In order that the present disclosure may be readily understood and put into practical effect, reference will now be made to exemplary embodiments as illustrated with reference to the accompanying figures. The figures together with detailed description below, are incorporated in and form part of the specification, and serve to further illustrate the embodiments and explain various principles and advantages, in accordance with the present disclosure where:

FIGURE 1 illustrates Fourier-transform infrared spectroscopy (FT-IR) spectrum of styrene-butadiene-Butyl acrylate terpolymer rubber.

FIGURE 2 illustrates 1H NMR spectrum of styrene-Butadiene-butyl acrylate terpolymer rubber.

FIGURE 3 illustrates Fourier-transform infrared spectroscopy (FT-IR) spectrum of styrene-butadiene- 2-Ethylhexyl Acrylate terpolymer rubber.

FIGURE 4 illustrates 1H NMR spectrum of styrene-Butadiene- 2-Ethylhexyl Acrylate terpolymer rubber.

FIGURE 5 illustrates Fourier-transform infrared spectroscopy (FT-IR) spectrum of styrene-butadiene-hydroxyl butyl vinyl ether propoxylate terpolymer rubber.

FIGURE 6 illustrates 1H NMR spectrum of styrene-Butadiene- hydroxyl butyl vinyl ether propoxylate terpolymer rubber.

DETAILED DESCRIPTION
The following terms are defined herein
Parts per hundred rubber (PHR) is a term used by rubber chemists to define parts of any non-elastomer material per hundred parts of elastomer. This is preferred versus an expression of the raw ingredient as a percentage of the total compound weight.

“Glass transition tg, is the gradual and reversible transition in amorphous materials, from a hard and relatively brittle "glassy" state into a viscous or rubbery state as the temperature is increased.[1] An amorphous solid that exhibits a glass transition is called a glass. The reverse transition, achieved by supercooling a viscous liquid into the glass state, is called vitrification.”
Mooney Viscosity is defined as the shearing torque resisting rotation of a cylindrical metal disk (or rotor) embedded in rubber within a cylindrical cavity.

The tread of a tire refers to the patterns on its rubber circumference that makes contact with the road.
Rubber composition refers to rubber which has been blended or mixed with various ingredients and materials described herein.

In an embodiment of the present disclosure describes a rubber composition, which is a terpolymer comprising conjugated diene monomer, vinyl substituted aromatic monomer and acrylate or propoxylate.

In an embodiment of the present disclosure the rubber composition, based upon parts by weight per 100 parts by weight of rubber (phr), comprises-
About 20 to 70 PHR of conjugated diene monomer;
About 10 to 50 PHR of vinyl substituted aromatic monomer; and
About 1 to 30 PHR of acrylate or vinyl propoxylate.

In an embodiment of the present disclosure, the conjugated diene monomer is selected from a group comprising 1,3-butadiene, isoprene, ethylbutadiene, -pentadiene, -hexadiene, pentadiene, cyclooctadiene and octadiene or any combinations thereof.

In an embodiment of the present disclosure, the conjugated diene monomer is 1,3 butadiene.

In an embodiment of the present disclosure, the rubber composition will contain repeat units derived from about 40 to 70 weight percent of the conjugated diene.

In another embodiment of the present disclosure, the rubber composition will contain repeat units derived from about 40 weight percent, about 45 weight percent, about 50 weight percent, about 55 weight percent , about 60 weight percent , about 65 weight percent , about 70 weight percent, of the conjugated diene.

In an embodiment of the present disclosure, the vinyl substituted aromatic monomer is selected from a group comprising styrene, a-methyl styrene, vinyl toluene, 3-methyl styrene, 4-methyl styrene, 4-cyclohexylstyrene, 4-para- tosylstyrene, para-chlorostyrene, 4-tert-butyl styrene, 1-vinylnaphthalene, 2-vinylnapthalene or any combinations thereof.

In an embodiment of the present disclosure, the vinyl substituted aromatic monomer is styrene.

In an embodiment of the present disclosure, the acrylate is selected from a group comprising Butyl Acrylate, Methyl acrylate and 2-Ethylhexyl Acrylate.

In an embodiment of the present disclosure, the vinyl propoxylate is hydroxyl butyl vinyl ether propoxylate.

In an embodiment of the present disclosure, the rubber composition will contain repeat units derived from about 10 to 50 weight percent of the vinyl substituted aromatic monomer.

In another embodiment of the present disclosure, the rubber composition contains repeat units derived from about 10 weight percent, about 15 weight percent, about 20 weight percent, about 25 weight percent, about 30 weight percent, about 35 weight percent, about 40 weight percent or about 45 weight percent, of the vinyl substituted aromatic monomer.

In an embodiment of the present disclosure, the rubber composition will contain repeat units derived from 1 to 30 weight percent of acrylate or vinyl propoxylate.

In another embodiment of the present disclosure, the rubber composition will contain repeat units derived from about 1weight percent, about 5 weight percent, about 10 weight percent, about 15 weight percent or about 20 weight percent, of acrylate or vinyl propoxylate.

In an embodiment of the present disclosure, the Tg of the rubber composition is ranging from about -80 oC to 40 °C.

In another embodiment of the present disclosure, the Tg of the rubber composition is about -30°C, about -80°C, about -60°C, about -40°C, about -10°C, about 0°C, about 10°C, about 20°C, about 30°C.

In an embodiment of the present disclosure, the Mooney viscosity of the rubber composition is ranging from about 25 to 80.

In another embodiment of the present disclosure, the Mooney viscosity of the rubber composition is about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75 or about 80.

In an embodiment of the present disclosure, the acrylate or vinyl propoxylate introduces hydroxyl, ether or ester functional groups into the styrene butadiene molecular backbone which introduces strong chemical bond and/or hydrogen bonding 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 would reduce the rolling resistance and carbon footprints of tire tread.

In an embodiment of the present disclosure, the rubber composition comprising conjugated diene monomer, vinyl substituted aromatic monomer and acrylate or vinyl propoxylate and reinforced with silica filler, demonstrates improved dynamic properties, mechanical and rheological properties of vulcanizates and significantly decreases rolling resistance which increases the fuel economy of tire having the said rubber composition.

In an embodiment of the present disclosure, the rubber composition of the present disclosure is a functionalized terpolymer, functionalized by acrylate or vinyl propoxylate.

In an embodiment of the present disclosure, the rubber composition reinforced with fillers including but not limited to silica filler can be modified or unmodified silica filler.

In an embodiment of the present disclosure, the rubber composition causes about 8% to 32% improvement in rolling resistance without sacrificing traction and wear.

In another embodiment of the present disclosure, the rubber composition causes about 8%, about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about 22%, about 24%, about 26%, about 28%, about 30% or about 32% improvement in rolling resistance without sacrificing traction and wear.

In an embodiment of the present disclosure, the rubber composition is devoid of gel

In another embodiment of the present disclosure, the rubber composition has minimum of 300 ppm gel formation.

In an embodiment of the present disclosure, the rubber composition comprises minimum cross linking with gel content of about 300 ppm, whereas the commercially available rubber composition has gel content of about 1500 ppm to 6000 ppm.

In an embodiment of the present disclosure, the rubber composition is high molecular weight terpolymer functionalized product, having molecular weight ranging from about 4 lacs to 10 lacs.

In an embodiment of the present disclosure, the rubber composition is functionalized random polymer. The randomization of the polymer in the composition can be witnessed by the NMR characterization illustrated in figures 2, 4 and 6.

The present disclosure further describes a process of synthesising the rubber composition.

In an embodiment of the present disclosure, the process of synthesising the rubber composition comprises, charging of water, at least one of the conjugated diene monomers, at least one of the vinyl aromatic monomer, at least one of the acrylate or vinyl propoxylate, polymerization initiator and emulsifier. The polymerization is conducted at a temperature ranging from about 1°C to 20°C.

In an embodiment of the present disclosure, the emulsifier is added at the onset of the polymerization or may be added incrementally, or proportionally as the reaction proceeds. The emulsifier can be anionic, cationic or non-ionic. Fatty acid and rosin acid-based soaps are used.

In an embodiment of the present disclosure, latexes obtained during the polymerization can be coagulated with acids including but not limited to sulphuric acid or acids with pka lower than 4 can be used.

In an embodiment of the present disclosure, the process of synthesising the rubber composition involves emulsion polymerization at cold condition having temperature ranging from about 1°C to 20°C.

In another embodiment, the process of synthesising the rubber composition involves emulsion polymerization at cold condition having temperature of about 1°C about 2°C, about 3°C, about 4°C, about 5°C, about 6°C, about 7°C¸ about 8°C, about 9°C, about 10°C, about 11°C, about 12°C, about 13°C, about 14°C, about 15°C, about 16°C, about 17°C, about 18°C, about 19°C or about 20°C.

In an embodiment of the present disclosure, the process of synthesising the rubber composition employs redox based catalyst system.

In an embodiment of the present disclosure, the process of synthesis of the rubber composition causes 60% to 75% partial conversion of emulsion polymerization, thereby avoiding the formation of gel. During the reaction, the monomers are recovered and reused after partial conversion.

In an embodiment of the present disclosure, during the process of synthesis of rubber composition redox type of catalyst system was employed and that the reaction rate during the synthesis of the rubber composition is about 25% to 30% times faster than known process available for synthesis of SBR products.

Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based upon the description provided. The embodiments 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. The examples provided herein are intended merely to facilitate an understanding of ways in which the embodiments provided may be practiced and to further enable those of skill in the art to practice the embodiments provided. Accordingly, the following examples should not be construed as limiting the scope of the embodiments.

EXAMPLES

Materials and Methods:
The experiments are performed in one and two liter reactors purged under inert nitrogen atmosphere.
1, 3-butadiene was purchased from Taiyo Nippon Sanso India; styrene was purchased from SD Fine Chemicals; butyl acrylate, 2-Ethylhexyl acrylate were purchased from Sigma-Aldrich; ; rosin acid, fatty acid, PMHP, TDM, 40% EDTA, synthetic soap, FeSO4.7H2O, SFS and short stop were used.
NMR measurement and Gradient pulse diffusion NMR analysis were carried out using bruker (400MHz) spectrometers in CDCl3 solvent. Perkin Elmer frontier FT-IR spectrometer was used for IR measurement.

Chemical Preparation
Fatty Soap Preparation (12%)
Dilute solution of about 12% fatty soap prepared by saponification of fatty acid with 49% KOH (wt/wt) in DM water. In about 250ml scotch bottle, about 88 g of DM water was taken and heated to a temperature of about 70 to 90°C. about 12g of fatty soap was added portion wise under vigorous stirring condition. Saponification of fatty acid were carried out with about 49% KOH. Addition of about 49% KOH was continued till the pH of the soap solution reached to about 10.4 to 10.9. Total solid content and pH of the fatty soap were about 12.2% and 10.5, respectively.

Rosin Soap preparation (31%)
About 31% of rosin soap was prepared by saponification of rosin with 49% KOH (wt/wt) in DM water. In about 250ml scotch bottle with magnetic needle, about 67g DM water was taken and heated to 100 to 120°C and about 22g of 40% EDTA was added. About 31g of rosin soap was added portion wise under vigorous stirring condition. Saponification of rosin acid were carried out with about 49% KOH till the pH of the soap solution reached to 10.5 to 11. Total solid content and pH of the fatty soap were about 31% and about 10.8, respectively.

Emulsifier Preparation
In about 500ml side neck conical flask under nitrogen flow, about 50g DM water was taken and about 0.201g of 40% EDTA followed by about 1.415g of KCl were added. Soap solutions prepared were added in about 70:30 ratio of fatty soap and rosin soap, respectively. Thus, about 117.5g of 12.2% fatty soap and about 21.g of 31% rosin soap were added in prepared mixture in conical flask. Finally, about 1.44g of synthetic soap (45% DNMS) was added. The pH of the emulsifier solution was about 10.3 and pH of the DM water used in the emulsifier was found to be about 9.8.

Catalyst solution preparation
In about 250ml side neck conical flask under nitrogen flow, about 40g DM water and about 0.405 g of 40% EDTA were taken. Further, about 0.177g of FeSO4.7H2O and about 0.207g of SFS were added. Catalyst solution was kept under nitrogen atmosphere till the addition.

Short stop solution
In about 250ml scotch bottle, about 160g of DM water was taken. About 20g of IPHA and about 4gm of synthetic soap (45% DNMS) was added.

Preparation of Antioxidant Solution
In about 100g scotch bottle, about 19.5 g of DM water was taken and heated to a temperature of about 80°C followed by about 6.1g of 12.2% fatty soap was added. Under stirring condition, about 10g of styreneated phenol was added. Antioxidant solution was kept for heating at a temperature of about 70°C with continuous stirring for about 30 minutes.

EXAMPLE 1: Synthetic Procedure for Styrene-Butadiene-Butyl Acrylate Terpolymer; (Styrene 35 phr: 1,3-Butadiene 55 phr: Butyl Acrylate 10 phr)
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 butyl acrylate, about 0.802g of 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 200 to 300 rpm for about 10 to 15mintues. Once the temperature of the reaction mixture drops down to a temperature of about 6°C, agitation was stopped, and reactor was vent to release the pressure. At about 6 to 12°C, the catalyst solution was added, and the flask was rinsed with addition 40g DM water. Additionally, about 0.485g activator PMHP was charged followed by adding about 220g of 1,3-butadiene. After the complete addition, reaction mixture was stirred at about 500 to 1200 rpm. Initial temperature and pressure of the reaction were noted and monitored for every 15 to 30 minutes 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 65% to 80% with about 24% to 28% 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.

Coagulation of styrene-butadiene terpolymer latex
SBR terpolymer latex was transferred in 5 liter beaker equipped with mechanical stirrer. In the latex, about 1000g DM water was added and heated to a temperature of about 60°C to 80°C with slow agitation of about 200 to 300rpm. Once the temperature reached to about 65 to 70°C, antioxidant solution was added and stirred vigorously for about 10minutes. About 90g of 0.5% flocculant was added and stirred for about 10minutes. Finally, about dilute 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.

The Mooney viscosity of the Styrene-Butadiene-Butyl Acrylate Terpolymer Rubber was assessed, and it was found to be 41. Further, the Styrene-Butadiene-Butyl Acrylate Terpolymer Rubber was characterized by Fourier-transform infrared spectroscopy (FT-IR), FT-IR (cm-1): 2915, 2847, 1731, 1703, 1493, 1434, 1158, 963, 909, 758, 698 (illustrated in figure 1) and Proton nuclear magnetic resonance, 1H NMR (400 MHz, CDCl3): d 7.23-7.11 (m, 5H, Styrene), 5.59-5.53 (m, CH=CH2), 4.43-4.35 (d, -CH=CH-), 5.0-4.93 (dd, -CH=CH2), 4.09-4.06 (m, 2H, -COOCH2), 2.56 (s, 1H, styrenic proton), 2.37-1.97 (m, aliphatic protons), 1.27 (m, 2H) ppm (illustrated in figure 2).

EXAMPLE 2: Styrene-Butadiene-2-Ethylhexyl Acrylate Terpolymer Rubber; (Styrene 35 phr: 1,3-Butadiene 55 phr: 2-Ethylhexyl Acrylate 10 phr)
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 TDM. The temperature of the reaction mixture was raised to about 13 to 15°C. The reactor was pressurized with 1bar pressure and slow agitation of about 200 to 300 rpm for about 10minutes to 15mintues. Once the temperature of the reaction mixture drops down to a temperature of about 6°C, agitation was stopped, and reactor was vented to release the pressure. At about 6 to 12°C, the catalyst solution was added, and the flask was rinsed with addition 40g DM water. Additionally, about 0.485g activator PMHP was charged followed by adding about 220g of 1,3-butadiene. After the complete addition, reaction mixture was stirred at about 500 to 1200 rpm. 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 65% to 80% 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.

Coagulation of styrene-butadiene terpolymer latex
SBR terpolymer latex was transferred in 5 liter beaker equipped with mechanical stirrer. In the latex, about 1000g DM water was added and heated to a temperature of about 60°C to 80°C with slow agitation of about 200 to 300rpm. Once the temperature reached to about 65°C, antioxidant solution was added and stirred vigorously for about 10minutes. About 90g of 0.5% flocculant was added and stirred for about 10minutes. Finally, about dilute 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.

The Mooney viscosity of the Styrene-Butadiene-2-Ethylhexyl Acrylate Terpolymer Rubber was assessed, and it was found to be 43. Further, the Styrene-Butadiene-2-Ethylhexyl Acrylate Terpolymer Rubber was characterized by Fourier-transform infrared spectroscopy (FT-IR), FT-IR (cm-1): 2915, 2847, 1730, 1702, 1493, 450, 1434, 1296, 1158, 963, 998, 909, 758 (illustrated in figure 3) and Proton nuclear magnetic resonance, 1H NMR ((400 MHz, CDCl3): d 7.27-7.07 (m, 5H, styrene), 5.57-5.53 (m, CH=CH2), 4.43-4.39 (d, -CH=CH-), 5.0-4.93 (dd, -CH=CH2), 3.98 (broad peak, 2H, -COOCH2), 2.56 (s, 1H, styrenic proton), 2.28-0.90 (m, aliphatic protons). (illustrated in figure 4).

EXAMPLE 3: Styrene-Butadiene- hydroxyl butyl vinyl ether propoxylate Terpolymer Rubber; (Styrene 35 phr: 1,3-Butadiene 55 phr: hydroxyl butyl vinyl ether propoxylate 10 phr)
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 TDM). The temperature of the reaction mixture was raised to about 10°C. The reactor was pressurized with 1bar pressure and slow agitation of about 200 to 300 rpm for about 10minutes to 15mintues. Once the temperature of the reaction mixture drops 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 was charged followed by adding about 220g of 1,3-butadiene. After the complete addition, reaction mixture was stirred at about 500 to 1200 rpm. 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 65 to 80% 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.

Coagulation of styrene-butadiene terpolymer latex
SBR terpolymer latex was transferred in 5 liter beaker equipped with mechanical stirrer. In the latex, about 1000g DM water was added and heated to a temperature of about 65°C to 70°C with slow agitation of about 200 to 300rpm. Once the temperature reached to about 65°C, antioxidant solution was added and stirred vigorously for about 10minutes. About 90g of 0.5% flocculant was added and stirred for about 10minutes. Finally, dilute 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.

The Mooney viscosity of the Styrene-Butadiene-hydroxyl butyl vinyl ether propoxylate Terpolymer Rubber was assessed, and it was found to be 63. Further, the Styrene-Butadiene- hydroxyl butyl vinyl ether propoxylate Terpolymer Rubber was characterized by Fourier-transform infrared spectroscopy (FT-IR), FT-IR (cm-1): 3383, 2916, 2848, 1493, 1450, 1016, 963, 909, 698, 676 (illustrated in figure 5) and Proton nuclear magnetic resonance, 1H NMR (400 MHz, CDCl3): d 7.31-7.13 (m, 5H, styrene), 5.57-5.53 (m, CH=CH2), 4.43-4.36 (d, -CH=CH-), 5.01-4.93 (dd, -CH=CH2), 3.67-3.42 (broad m, 22H, -OCH2), 2.57 (s, 1H, styrenic proton), 2.39-0.92 (m, aliphatic protons). (illustrated in figure 6).