# US 11,897,988 B2 · Hydrogenated styrene/conjugated diolefin copolymer, foaming material thereof, and application thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,897,988 B2 - Document ID: US11897988B2 - Status: Granted - Kind: B2 - Application number: 17/286,919 - Filed: 2019-10-29 - Published: 2021-12-02 - Granted: 2024-02-13 - Earliest claimed: 2018-10-30 - Assignees: China Petroleum & Chemical Corporation - Applicants: China Petroleum & Chemical Corporation - Inventors: Hongwen Liang; Xiaojun Mo; Wangming Li; Chaozhou Liu; Fan Yang; Zheng Kang; Xu Wang; Zhenyin She - Web page: https://patentgrep.com/patent/US11897988B2 ## CPC - C08F 236/10: with vinyl-aromatic monomers - A43B 13/04: Plastics, rubber or vulcanised fibre - C08F 8/04: Reduction, e.g. hydrogenation - C08F 236/06: Butadiene - C08J 9/122: {Hydrogen, oxygen, CO2, nitrogen or noble gases} - C08J 2203/06: CO2, N2 or noble gases - C08J 2203/08: Supercritical fluid - C08J 2309/06: Copolymers with styrene - C08J 2325/10: with conjugated dienes - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - A43B: CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract Disclosed are a hydrogenated styrene/conjugated diolefin copolymer, a foaming material thereof, and application thereof. The copolymer contains a styrene structure unit and a hydrogenated conjugated diolefin structure unit; by taking the total content of the copolymer as a reference, the content of the styrene structure unit is 15-50 wt %, the content of 1,2-polymerization structure unit in the hydrogenated conjugated diolefin structure unit is 8-32%, the degree of randomness of the styrene structure unit in the hydrogenated conjugated diolefin structure unit is 30-80%, and the degree of hydrogenation of conjugated diolefin in the copolymer is 85-100%. The tensile strength at break of the hydrogenated styrene/conjugated diolefin copolymer is 30-60 MPa, the elongation at break is 300-600%, and the hardness (Shore A) is 70-98. Moreover, a foaming body having excellent performance including more than 60% rebound and less than 30% compression deformation can be manufactured by using a supercritical carbon dioxide foaming process. ## Claims ### Claim 1 A hydrogenated styrene/conjugated diolefin copolymer, wherein the copolymer comprises a styrene-based structural unit represented by Formula 1, a hydrogenated conjugated diene-based structural unit represented by Formula 2, and a hydrogenated conjugated diene-based structural unit represented by Formula 3, wherein R1, R2, R3, R4, R5, R6, R7, R8, and R9 are respectively H, C1-C3 alkyl, and R10 is H or C1-C4 alkyl; the content of the styrene-based structural unit is 15-50 wt %, based on the total amount of the copolymer; the content of the hydrogenated conjugated diene-based structural unit represented by Formula 3 is 8-32 wt %, based on the total amount of the hydrogenated conjugated diene-based structural unit represented by Formula 2 and the hydrogenated conjugated diene-based structural unit represented by Formula 3, the randomness degree of the styrene-based structural unit in the hydrogenated conjugated diene-based structural unit is 30-80%, and the hydrogenation degree of the conjugated diolefin in the copolymer is 85-100%. ### Claim 2 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the content of the styrene-based structural unit is 25-35 wt %, based on the total amount of the copolymer; the content of the hydrogenated conjugated diene-based structural unit represented by Formula 3 is 10-30 wt %, based on the total amount of the hydrogenated conjugated diene-based structural unit represented by Formula 2 and the hydrogenated conjugated diene-based structural unit represented by Formula 3; the randomness degree of the styrene-based structural unit in the hydrogenated conjugated diene-based structural unit is 35-75%, and the hydrogenation degree of the conjugated diolefin in the copolymer is 95-100%. ### Claim 3 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the hydrogenated styrene/conjugated diolefin copolymer has a crystallization temperature of 18° C. or more measured by DSC, and an enthalpy not less than 1.7 J/g. ### Claim 4 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein a micro-region structure formed by the styrene-based structural unit represented by Formula 1 and a micro-region structure formed by the hydrogenated conjugated diolefin structural unit represented by Formula 2 and the hydrogenated conjugated diolefin structural unit represented by Formula 3 coexist in a columnar, spherical and lamellar distribution. ### Claim 5 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the styrene-based structural unit represented by Formula 1, the hydrogenated conjugated diolefin structural unit represented by Formula 2, and the hydrogenated conjugated diolefin structural unit represented by Formula 3 are a structural unit represented by the following Formula 1-1, a structural unit represented by the following Formula 2-1, and a structural unit represented by the following Formula 3-1, respectively ### Claim 6 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer according to claim 1, wherein the copolymer has a number average molecular weight within a range of 30,000-500,000, as measured by gel chromatography. ### Claim 7 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the copolymer has a tensile strength at an elongation 300% of 8 MPa or more; a tensile strength at break of 30 Mpa or more; an elongation at break within a range of 300-600%; a Shore A hardness being 80 or more, and a Melt FLow Rate at 200° C., 5 kg within a range of 0-8 g/10 min. ### Claim 8 (depends on 1) A foaming material obtained by foaming the hydrogenated styrene/conjugated diolefin copolymer of claim 1. ### Claim 9 (depends on 8) The foaming material of claim 8, wherein the foaming material has a rebound elasticity within a range of 58-65% measured according to the standard ASTM-D2632, and a compression deformation within a range of 20-28% measured according to the standard GB/T6669-2008. ### Claim 10 (depends on 8) The foaming material of claim 8, wherein the foaming is supercritical carbon dioxide foaming or supercritical nitrogen gas foaming. ### Claim 11 (depends on 1) A method for preparing foamed shoe soles, the method comprising utilizing the hydrogenated styrene/conjugated diolefin copolymer of claim 1. ### Claim 12 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the content of the styrene-based structural unit is 18-45 wt %, based on the total amount of the copolymer. ### Claim 13 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the content of the hydrogenated conjugated diene-based structural unit represented by Formula 3 is 12-25 wt %, based on the total amount of the hydrogenated conjugated diene-based structural unit represented by Formula 2 and the hydrogenated conjugated diene-based structural unit represented by Formula 3. ### Claim 14 (depends on 2) The hydrogenated styrene/conjugated diolefin copolymer of claim 2, wherein the content of the hydrogenated conjugated diene-based structural unit represented by Formula 3 is 12-25 wt %, based on the total amount of the hydrogenated conjugated diene-based structural unit represented by Formula 2 and the hydrogenated conjugated diene-based structural unit represented by Formula 3. ### Claim 15 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the hydrogenated styrene/conjugated diolefin copolymer has a crystallization temperature of 18-70° C. measured by DSC, and an enthalpy of 2-25 J/g. ### Claim 16 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer according to claim 1, wherein the copolymer has a number average molecular weight within a range of 40,000-200,000, as measured by gel chromatography. ### Claim 17 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer according to claim 1, wherein the copolymer has a number average molecular weight within a range of 50,000-80,000, as measured by gel chromatography. ### Claim 18 (depends on 1) The hydrogenated styrene/conjugated diolefin copolymer of claim 1, wherein the copolymer has a tensile strength at an elongation 300% of 10-20 Mpa; a tensile strength at break of 30-60 MPa; an elongation at break within a range of 350-500%; a Shore A hardness being within a range of 80-98, and a Melt Flow Rate at 200 C., 5 kg within a range of 1-2 g/10 min. ### Claim 19 (depends on 8) The foaming material of claim 8, wherein the foaming material is obtained by physically foaming.