# US 2014/0155543 A1 · Process for the preparation of 1,3-butadiene and styrene copolymers and use thereof in vulcanizable elastomeric compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0155543 A1 - Document ID: US20140155543A1 - Status: Published application - Kind: A1 - Application number: 14/127,339 - Filed: 2012-06-21 - Published: 2014-06-05 - Earliest claimed: 2011-06-29 - Assignees: Versalis S.P.A. - Inventors: Luca Soddu; Gabriele Veneri - Web page: https://patentgrep.com/patent/US20140155543A1 ## CPC - C08C 19/42: reacting with metals or metal-containing groups - C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton - C08F 236/10: with vinyl-aromatic monomers - C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract A process for the preparation of a 1,3-butadiene and styrene copolymer comprising the following steps: a) anionically polymerizing a blend comprising from 5% by weight to 40% by weight of styrene and from 60% by weight to 95% by weight of 1,3-butadiene, with respect to the overall weight of the mixture, in the presence of at least one hydrocarbon solvent, of at least one lithium-based catalyst having the general formula LiR1 wherein R1 represents a linear or branched C3-C10 alkyl group, and of least one polar modifier; b) optionally, reacting the copolymer obtained in step (a) with at least one chain-end monomer selected from 1,3-butadiene, styrene and α-methylstyrene; c) reacting from 10% by weight to 70% by weight, preferably from 20% by weight to 50% by weight, of the lithium-terminated polymeric chains present in the copolymer obtained in step (a) or in step (b), with at least one coupling agent selected from liquid polyepoxides having at least three reactive sites capable of reacting with the carbon-lithium chain-ends; d) optionally, reacting the copolymer obtained in step (c) with at least one chain-end monomer selected from 1,3-butadiene, styrene and a-methylstyrene; e) reacting the linear polymeric chains remaining in the copolymer obtained in step (c) or in step (d), with at least one tin compound having the general formula XSn(R2)3 wherein X represents a halogen atom such as, for example, chlorine and R2 represents a linear or branched C1-C10 alkyl group. ## Claims ### Claim 1 A process for the preparation of a 1,3-butadiene and styrene copolymer comprising the following steps: a) anionically polymerizing a blend comprising from 5% by weight to 40% by weight of styrene and from 60% by weight to 95% by weight of 1,3-butadiene, with respect to the overall weight of the mixture, in the presence of at least one hydrocarbon solvent, of at least one lithium-based catalyst having the general formula LiR1 wherein R1 represents a linear or branched C3-C10 alkyl group, and of least one polar modifier; b) optionally, reacting the copolymer obtained in step (a) with at least one chain-end monomer selected from 1,3-butadiene, styrene and α-methylstyrene; c) reacting from 10% by weight to 70% by weight of the lithium-terminated polymeric chains present in the copolymer obtained in step (a) or in step (b), with at least one coupling agent selected from liquid polyepoxides having at least three reactive sites capable of reacting with the carbon-lithium chain ends; d) optionally, reacting the copolymer obtained in step (c) with at least one chain-end monomer selected from 1,3-butadiene, styrene and α-methylstyrene; e) reacting the linear polymeric chains remaining in the copolymer obtained in step (c) or in step (d), with at least one tin compound having the general formula XSn(R2)3 wherein X represents a halogen atom and R2 represents a linear or branched C1-C10 alkyl group. ### Claim 2 (depends on 1) The process according to claim 1, wherein said anionic polymerization is carried out at a temperature ranging from 0° C. to 150° C. ### Claim 3 (depends on 1) The process according to claim 1, wherein said polar modifier is tetrahydrofurfurylethyl ether (THFAethyl). ### Claim 4 (depends on 3) The process according to claim 3, wherein said polar modifier is used in the reaction mixture in a quantity ranging from 500 ppm to 1,000 ppm. ### Claim 5 (depends on 1) The process according to claim 1, wherein in step (b) said reactive monomer is used in a quantity ranging from 0% by weight to 10% by weight. ### Claim 6 (depends on 1) The process according to claim 1, wherein said coupling agent is selected from epoxidated vegetable oils. ### Claim 7 (depends on 6) The process according to claim 6, wherein said epoxidated vegetable oils are selected from epoxidated soybean oil, epoxidated linseed oil, or mixtures thereof. ### Claim 8 (depends on 1) The process according to claim 1, wherein said tin compound is selected from tin trimethyl chloride, tin tributyl chloride, tin tripentyl chloride, tin trioctyl chloride, or mixtures thereof. ### Claim 9 (depends on 8) The process according to claim 8, wherein said tin compound is tin trioctyl chloride. ### Claim 10 (depends on 1) A vulcanizable elastomeric composition comprising at least one copolymer of 1,3-butadiene and styrene obtained according to claim 1, at least one filler selected from carbon black, silica, or mixtures thereof, and at least one vulcanizing agent. ### Claim 11 (depends on 10) The vulcanizable elastomeric composition according to claim 10, wherein said filler is present in a quantity ranging from 5 phr to 500 phr. ### Claim 12 (depends on 10) A vulcanized manufactured product obtained from the vulcanization of the vulcanizable elastomeric composition according to claim 10. ### Claim 13 (depends on 12) The vulcanized manufactured product according to claim 12, which is a tyre for road vehicles. ### Claim 14 (depends on 13) The vulcanized manufactured product according to claim 13, which is a tyre tread for road vehicles.