# US 8,772,415 B2 · Hydrogenated block copolymers and crosslinking compositions containing the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,772,415 B2 - Document ID: US8772415B2 - Status: Granted - Kind: B2 - Application number: 12/375,672 - Filed: 2007-08-07 - Published: 2010-04-08 - Granted: 2014-07-08 - Earliest claimed: 2006-08-08 - Assignees: Asahi Kasei Chemicals Corporation - Applicants: Yasuhiro Kusanose; Masahiro Fujiwara; Daisuke Shimizu - Inventors: Yasuhiro Kusanose; Masahiro Fujiwara; Daisuke Shimizu - Web page: https://patentgrep.com/patent/US8772415B2 ## CPC - C08F 8/04: Reduction, e.g. hydrogenation - C08F 297/04: polymerising vinyl aromatic monomers and conjugated dienes - C08L 51/006: {grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds} - C08L 53/025: {modified} - C08L 67/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) - C08L 69/00: Compositions of polycarbonates; Compositions of derivatives of polycarbonates - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract The disclosure provides a hydrogenated straight-chain block copolymer, obtained by selective hydrogenation of a straight-chain block copolymer. ## Claims ### Claim 1 A hydrogenated straight-chain block copolymer, obtained by selective hydrogenation of a straight-chain block copolymer comprising: i. at least two polymer blocks A, on both terminals thereof, which each comprise a vinyl aromatic monomer unit as a main component and which may be the same or different from each other; ii. at least two polymer blocks B, internally in relation to the polymer blocks A, which each comprise a conjugated diene monomer unit having 5 or more carbon atoms as a main component and which may be the same or different from each other; and iii. one or more polymer blocks selected from a. one or more polymer blocks C which each comprise a conjugated diene monomer unit having 4 or more carbon atoms as a main component and which may be the same or different from each other, b. one or more random copolymer blocks D which each comprise a conjugated diene monomer unit having 4 or more carbon atoms (d-1) and a vinyl aromatic monomer unit (d-2) as main components and which may be the same or different, and c. a combination of the polymer blocks C and D, wherein: a. the polymer block A has a weight-average molecular weight M of 21,000 or more; b. the polymer block B has a hydrogenation rate of 50% or less for olefinic unsaturated double bonds; c. the polymer blocks C and D have a hydrogenation rate of 80% or more for olefinic unsaturated double bonds; d. the block copolymer comprises 10% by weight to 85% by weight of the vinyl aromatic monomer unit; e. the block copolymer has contents of 10% by weight to 70% by weight of A, 1% by weight to 15% by weight of B, 0% by weight to 85% by weight of C, 0% by weight to 85% by weight of D and 25% by weight to 85% by weight of C+D, based on 100% by weight of the total of A+B+C+D; and f. the A, B, C, and D are arranged linearly. ### Claim 2 (depends on 1) The hydrogenated block copolymer according to claim 1, obtained by hydrogenation of a block copolymer comprising 2% by weight to 80% by weight of the random copolymer block D. ### Claim 3 (depends on 1) The hydrogenated block copolymer according to claim 1, obtained by hydrogenation of a block copolymer comprising 2% by weight to 80% by weight of the polymer block C. ### Claim 4 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the random copolymer D has a ratio of 30% by weight or more for the vinyl aromatic monomer unit (d-2) with respect to 100% by weight of the random copolymer D. ### Claim 5 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the polymer block C has a vinyl bond amount of 15% to 80% in the whole conjugated diene. ### Claim 6 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the polymer block D has a vinyl bond amount of 10% to 50% in the whole conjugated diene. ### Claim 7 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the conjugated diene of the polymer block B is isoprene. ### Claim 8 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the conjugated dienes of the polymer block C and the polymer block D are 1,3-butadiene. ### Claim 9 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the conjugated diene of the polymer block B is isoprene; and the conjugated dienes of the polymer block C and the polymer block D are 1,3-butadiene, and wherein the block copolymer is hydrogenated using a compound comprising a titanocene compound as a hydrogenation catalyst; 90% or more of 1,3-butadiene of the polymer block C and the polymer block D is hydrogenated; and 90% or more of 1,4-bonds in isoprene of the polymer block B is not hydrogenated, and the hydrogenation rate of 3,4-bonds therein is 50% or less. ### Claim 10 (depends on 1) The hydrogenated block copolymer according to claim 1, obtained by hydrogenation of the block copolymer comprising three or more polymer blocks B and at least one polymer block B as an internal block. ### Claim 11 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the terminal block parts of the hydrogenated block copolymer comprise the polymer block A; and the hydrogenated block copolymer is a straight-chain block copolymer represented by the general formula shown below: H—(S—H)n, or a straight-chain block copolymer represented by the general formula shown below: [(H—S)k]m—X,[H—(S—H)k]m—X, wherein H denotes a block copolymer of A-B or B-A, or a random copolymer of A/B, and H's may be the same or different; S denotes a homoblock of C or a homoblock of D, or a block copolymer of C-D or D-C, and may contain 10% by weight or less of the B block, and S's may be the same or different; n and k are each an integer of 1 to 5, and m is an integer of 2 to 6; X denotes a residue of a coupling agent or a residue of a polyfunctional initiator; and when the polymer blocks A to D are each present in a plural number in the copolymer, the respective structures such as molecular weights and compositions may be each the same or different. ### Claim 12 (depends on 1) The hydrogenated block copolymer according to claim 1, having a weight-average molecular weight of 30,000 to 2,000,000 in terms of polystyrene. ### Claim 13 (depends on 1) The functionalized hydrogenated block copolymer according to claim 1, wherein the polymer block B containing residual olefinic unsaturated double bonds comprises a functional group. ### Claim 14 (depends on 1) A dynamic crosslinking composition comprising 10 to 300 parts by weight of a thermoplastic resin and 0.01 to 30 parts by weight of a crosslinking agent with respect to 100parts by weight of the hydrogenated block copolymer or the functionalized hydrogenated block copolymer according to claim 1. ### Claim 15 (depends on 14) A dynamically crosslinked body, obtained by melting and kneading the dynamic crosslinking composition according to claim 14 at a high temperature. ### Claim 16 (depends on 1) A crosslinking and foaming composition comprising the hydrogenated block copolymer or the functionalized hydrogenated block copolymer according to claim 1, a crosslinking agent, and a foaming agent. ### Claim 17 (depends on 16) A crosslinked and foamed body, obtained by crosslinking and foaming the crosslinking and foaming composition according to claim 16. ### Claim 18 (depends on 13) A functionalized hydrogenated block copolymer resin composition, comprising the functionalized hydrogenated block copolymer (E) according to claim 13, and a polar thermoplastic resin (F) having a functional group reactive with the component (E), and/or a rubbery polymer (F) having a functional group reactive with the component (E), wherein the formulation ratio (weight ratio) of the component(s) (E) to the component (F) is 1/99 to 99/1. ### Claim 19 (depends on 18) The functionalized hydrogenated block copolymer resin composition according to claim 18, wherein the component (F) is at least one polar thermoplastic resin selected from polyester resins, polyamide resins, polycarbonate resins, polyurethane resins, polyphenylene ether resins and polyoxymethylene resins. ### Claim 20 A method of manufacturing a dynamic crosslinking composition comprising selectively hydrogenating a straight-chain block copolymer comprising: at least two polymer blocks A which each comprise a vinyl aromatic monomer unit as a main component and which may be the same or different from each other; at least two polymer blocks B which each comprise a conjugated diene monomer unit having 5 or more carbon atoms as a main component and which may be the same or different from each other; and one or more polymer blocks C which each comprise a conjugated diene monomer unit having 4or more carbon atoms as a main component and which may be the same or different from each other; and/or one or more random copolymer blocks D which each comprise a conjugated diene monomer unit having 4 or more carbon atoms (d-1) and a vinyl aromatic monomer unit (d-2) as main components and which may be the same or different, wherein the polymer block A has a weight-average molecular weight M of 21,000 or more; the polymer block B has a hydrogenation rate of 50% or less for olefinic unsaturated double bonds; the polymer blocks C and D have a hydrogenation rate of 80% or more for olefinic unsaturated double bonds; the block copolymer comprises 10% by weight to 85% by weight of the vinyl aromatic monomer unit; the block copolymer has contents of 10% by weight to 70% by weight of A, 1% by weight to 15% by weight of B, 0% by weight to 85% by weight of C, 0% by weight to 85% by weight of D and 25% by weight to 85% by weight of C+D, based on 100% by weight of the total of A+B+C+D; and the A, B, C, and D are arranged linearly. ### Claim 21 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the hydrogenated straight-chain block copolymer excludes the polymer block D. ### Claim 22 (depends on 20) The method according to claim 20, wherein the hydrogenated straight-chain block copolymer excludes the polymer block D. ### Claim 23 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the hydrogenated straight-chain block copolymer excludes the polymer block D. ### Claim 24 (depends on 20) The method according to claim 20, the hydrogenated straight-chain block copolymer excludes the polymer block D. ### Claim 25 (depends on 1) The hydrogenated block copolymer according to claim 1, wherein the hydrogenated straight-chain block copolymer consists of the polymer blocks A, the polymer blocks B, and the one or more polymer blocks C and/or the one or more random copolymer blocks D. ### Claim 26 (depends on 20) The method according to claim 20, wherein the hydrogenated straight-chain block copolymer consists of the polymer blocks A, the polymer blocks B, and the one or more polymer blocks C and/or the one or more random copolymer blocks D.