# US 12,110,354 B2 · Production method for aromatic vinyl-diene copolymer and production method for rubber composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,110,354 B2 - Document ID: US12110354B2 - Status: Granted - Kind: B2 - Application number: 17/271,097 - Filed: 2019-08-22 - Published: 2021-08-12 - Granted: 2024-10-08 - Earliest claimed: 2018-08-24 - Assignees: The Yokohama Rubber Co., Ltd. - Applicants: The Yokohama Rubber Co., LTD. - Inventors: Kazuya Uenishi; Yu Shinke; Yoshihiro Kameda; Masaki Sato; Ayaki Kazariya; Hideaki Sawa - Web page: https://patentgrep.com/patent/US12110354B2 ## CPC - C08C 19/22: Incorporating nitrogen atoms into the molecule - C08F 236/10: with vinyl-aromatic monomers - C08C 19/25: Incorporating silicon atoms into the molecule - C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton - C08F 4/48: selected from lithium, rubidium, caesium or francium {(C08F4/461 takes precedence)} - C08K 3/013: Fillers, pigments or reinforcing additives - B60C 1/0016: {Compositions of the tread} - B60C 1/0025: {Compositions of the sidewalls} - C08F 2410/01: Additive used together with the catalyst, excluding compounds containing Al or B - C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES ## Abstract An object of the present invention is to provide a method of producing a copolymer that produces an aromatic vinyl-diene copolymer having a low glass transition temperature, and a method of producing a rubber composition using the method. The subject method produces an aromatic vinyl-diene copolymer having a content of repeating units derived from an aromatic vinyl in an amount of 18 mass % or greater, and among repeating units derived from a diene, a proportion of a vinyl structure of 8 mol % or less, a proportion of a 1,4-trans structure of 60 mol % or less, and a proportion of a 1,4-cis structure from 40 to 95 mol %, the method including copolymerizing a monomer containing an aromatic vinyl and a diene using an initiator prepared with an organolithium compound, an alkylaluminum, a metal alcoholate, and at least one polar compound selected from the group consisting of water and an alcohol. ## Claims ### Claim 1 A method of producing an aromatic vinyl-diene copolymer, the aromatic vinyl-diene copolymer being a copolymer of an aromatic vinyl and a diene, and the aromatic vinyl-diene copolymer having a content of repeating units derived from an aromatic vinyl in an amount of 18 mass % or greater, and among repeating units derived from a diene, a proportion of a vinyl structure of 8 mol % or less, a proportion of a 1,4-trans structure of 60 mol % or less, and a proportion of a 1,4-cis structure from 40 to 95 mol %, the method of producing the aromatic vinyl-diene copolymer comprising copolymerizing a monomer containing an aromatic vinyl and a diene using an initiator, the initiator being prepared with an organolithium compound, an alkylaluminum, a metal alcoholate, and at least one polar compound comprising water. ### Claim 2 A method of producing an aromatic vinyl-diene copolymer, the aromatic vinyl-diene copolymer being a copolymer of an aromatic vinyl and a diene, the aromatic vinyl-diene copolymer having a content of repeating units derived from an aromatic vinyl in an amount of 18 mass % or greater, among repeating units derived from a diene, a proportion of a vinyl structure of 8 mol % or less, a proportion of a 1,4-trans structure of 60 mol % or less, and a proportion of a 1,4-cis structure from 40 to 95 mol %, and the aromatic vinyl-diene copolymer having a terminal that is modified with at least one electrophile selected from the group consisting of titanium halide, tin halide, cyclic silazane, alkoxysilane, epoxide, amine, ketone, and a compound represented by Formula (N) below, the method of producing the aromatic vinyl-diene copolymer comprising: copolymerizing a monomer containing an aromatic vinyl and a diene using an initiator, the initiator being prepared with an organolithium compound, an alkylaluminum, a metal alcoholate, and at least one polar compound comprising water; and then terminating the polymerization using the electrophile: where in Formula (N), R1 represents a hydrogen atom or an alkyl group, and R2 represents an alkylene group. ### Claim 3 (depends on 1) The method of producing an aromatic vinyl-diene copolymer according to claim 1, wherein a proportion of an amount of the polar compound with respect to an amount of the organolithium compound in terms of molar ratio is from 1/15 to 1/1 . ### Claim 4 (depends on 1) A method of producing a rubber composition comprising: producing an aromatic vinyl-diene copolymer by using the method of producing an aromatic vinyl-diene copolymer according to claim 1, and mixing the aromatic vinyl-diene copolymer as obtained with a filler, and obtaining a rubber composition. ### Claim 5 (depends on 2) The method of producing an aromatic vinyl-diene copolymer according to claim 2, wherein a proportion of an amount of the polar compound with respect to an amount of the organolithium compound in terms of molar ratio is from 1/15 to 1/1 . ### Claim 6 (depends on 2) A method of producing a rubber composition comprising: producing an aromatic vinyl-diene copolymer by using the method of producing an aromatic vinyl-diene copolymer according to claim 2, and mixing the aromatic vinyl-diene copolymer as obtained with a filler, and obtaining a rubber composition. ### Claim 7 (depends on 3) A method of producing a rubber composition comprising: producing an aromatic vinyl-diene copolymer by using the method of producing an aromatic vinyl-diene copolymer according to claim 3, and mixing the aromatic vinyl-diene copolymer as obtained with a filler, and obtaining a rubber composition. ### Claim 8 (depends on 5) A method of producing a rubber composition comprising: producing an aromatic vinyl-diene copolymer by using the method of producing an aromatic vinyl-diene copolymer according to claim 5, and mixing the aromatic vinyl-diene copolymer as obtained with a filler, and obtaining a rubber composition.