# US 5,352,743 A · Solid elastomeric block copolymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,352,743 A - Document ID: US5352743A - Status: Granted - Kind: A - Application number: 08/143,718 - Filed: 1993-11-01 - Granted: 1994-10-04 - Earliest claimed: 1990-01-16 - Assignees: Mobil Oil Corporation - Inventors: Thomas S. Coolbaugh; Frederick C. Loveless; Demetreos N. Matthews - Web page: https://patentgrep.com/patent/US5352743A ## CPC - C08L 53/00: Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers - C08F 8/00: Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) - C08F 8/04: Reduction, e.g. hydrogenation - C08F 8/44: Preparation of metal salts or ammonium salts - C08F 8/46: Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation - C08F 236/04: conjugated - C08F 297/02: using a catalyst of the anionic type - C08F 297/04: polymerising vinyl aromatic monomers and conjugated dienes - C08F 297/046: {polymerising vinyl aromatic monomers and isoprene, optionally with other 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 53/02: of vinyl-aromatic monomers and conjugated dienes - C08L 53/025: {modified} - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract There are disclosed novel, solid, elastomeric block copolymers with improved resistance to cold flow wherein either 1) the terminal blocks are each a polymer (I polymer) of at least one conjugated diene I, e.g., isoprene, which contains at least five carbon atoms with at least one of each pair of double-bonded carbon atoms in the polymerized diene I units being additionally single-bonded to two carbon atoms; at least one middle or interior block is a hydrogenated polybutadiene (B polymer); and at least one middle or interior block is an essentially straight chain polyethylene (E polymer) resulting from the hydrogenation of a polybutadiene composed of at least 80% of 1,4-units; or 2) the terminal blocks are random IB copolymers of at least one diene I as previously defined and hydrogenated butadiene, and at least one middle or interior block is a straight chain polyethylene (E polymer) as previously defined. The hydrogenated butadiene units in the B polymer or random IB polymer blocks are composed of no more than about 65% of 1,4-units and at least about 35% of 1,2-units. The foregoing block copolymers may be prepared by selectively hydrogenating substantially all the butadiene units of a precursor block copolymer wherein the precursor blocks of the straight chain polyethylene blocks units are polybutadiene blocks in which at least about 80% of the butadiene units are 1,4-units. A sufficient number of I units in the I polymer blocks or random IB copolymer blocks retain their unsaturation on selective hydrogenation to enable the vulcanization of the block copolymer. ## Claims ### Claim 1 A solid elastomeric star-branched block copolymer wherein either 1) blocks on the free ends of the branches are each a polymer of at least one conjugated diene I (I polymer), said diene containing at least five carbon atoms with at least one of each pair of double-bonded carbon atoms in the polymerized diene I units being additionally single-bonded to two carbon atoms; at least one interior block of each branch is a hydrogenated polybutadiene (B polymer); and at least one interior block of each branch is an essentially straight chain polyethylene (E polymer) resulting from the hydrogenation of a polybutadiene composed of at least 80% of 1,4-units; or 2) the blocks on the free ends of the branches are each a random IB copolymer of at least one diene I and hydrogenated butadiene (B), and at least one interior block of each branch is an essentially straight chain polyethylene (E polymer) as previously defined, the hydrogenated butadiene units in said B polymer or random IB copolymer blocks being composed of not more than about 65% of 1,4-units and at least about 35% of 1,2-units and said B polymer or random IB copolymer blocks containing no more than about 10% of polyethylene crystallinity, and the number of unsaturated polymerized diene I units in said I polymer or random IB polymer blocks being sufficient to vulcanize said block copolymer. ### Claim 2 (depends on 1) The star-branched block copolymer of claim 1 which has been subjected to a vulcanization treatment. ### Claim 3 (depends on 1) The star-branched block copolymer of claim 1 wherein the branches are composed of the blocks of category 1) and comprise about 1 to 50 wt. % of I polymer blocks, about 50 to 98 wt. % of B polymer blocks, and about 1 to 30 wt. % of E polymer blocks, all based on the total weight of said block copolymer. ### Claim 4 (depends on 1) The star-branched block copolymer of claim 1 wherein the branches are composed of the blocks of category 2) and comprise an average of about 70 to 99 wt. % of random IB copolymer blocks, and about 1 to 30 wt. % of E polymer blocks, all based on the total weight of block copolymer, with the polymerized I units being an average of about 1 to 50 wt. % of each random IB copolymer block, and the remainder being polymerized butadiene (B). ### Claim 5 (depends on 1) The star-branched block copolymer of claim 1 with each branch being a triblock copolymer wherein the outermost block is said I polymer, the central block is said E polymer, and the innermost block is said B polymer, and wherein the average total molecular number of polymerized I units in all the branches is in the range of about 15 to 735, the average total molecular number of polymerized E units in all the branches is in the range of about 37 to 1111, and the average total molecular number of polymerized B units in all the branches is in the range of about 370 to 1815, all values being per 100,000 M.W. ### Claim 6 (depends on 5) The star-branched block copolymer of claim 5 wherein I is isoprene. ### Claim 7 (depends on 5) The star-branched block copolymer of claim 5 which has been subjected to a vulcanization treatment. ### Claim 8 (depends on 1) The star-branched block copolymer of claim 1 with each branch being a triblock copolymer wherein the outermost block is said I polymer, the central block is said B polymer, and the innermost block is said E polymer, and wherein the average total molecular number of polymerized I units in all the branches is in the range of about 15 to 735, the average total molecular number of polymerized B units in all the branches is in the range of about 370 to 1815, and the average total molecular number of polymerized E units in all the branches is in the range of about 37 to 1111, all values being per 100,000 M.W. ### Claim 9 (depends on 8) The star-branched block copolymer of claim 8 wherein I is isoprene. ### Claim 10 (depends on 9) The star-branched block copolymer of claim 9 which has been subjected to a vulcanization treatment. ### Claim 11 (depends on 1) The star-branched block copolymer of claim 1 with each branch being a diblock copolymer wherein the external block is said random IB copolymer, and the internal block is said E polymer, and wherein the average total molecular number of polymerized I units in all the branches is in the range of about 15 to 735, the average total molecular number of polymerized B units in all the branches is in the range of about 370 to 1815, and the average molecular number of polymerized E units in all the branches is in the range of about 37 to 1111, all values being per 100,000 M.W. ### Claim 12 (depends on 11) The star-branched block copolymer of claim 11 wherein I is isoprene. ### Claim 13 (depends on 12) The star-branched block copolymer of claim 12 which has been subjected to a vulcanization treatment. ### Claim 14 (depends on 1) A sulfonated polymer produced by a method comprising sulfonating the star-branched block copolymer of claim 1, followed by neutralization of the thus formed polymeric sulfonic acid with metal ions or amines. ### Claim 15 (depends on 1) A maleated polymer produced by a method comprising contacting the star-branched block copolymer of claim 1 with maleic anhydride. ### Claim 16 A precursor star-branched block copolymer wherein either 1) the blocks on the free ends of the branches are each a polymer of at least one conjugated diene I, said diene containing at least 5 carbon atoms with at least one of each pair of double-bonded carbon atoms in the polymerized diene I units being additionally single-bonded to two carbon atoms; at least one interior block of each branch is a polybutadiene composed of not more than about 65% of 1,4-units and at least about 35% of polymerized 1,2-units; and at least one interior block of each branch is a polybutadiene composed of at least about 80% of 1,4-units; or 2) the blocks on the free ends of the branches are each a random copolymer of at least one diene I and butadiene wherein the polymerized butadiene units are composed of not more than about 65% of 1,4-units and at least about 35% of 1,2-units and at least one interior block of each branch is a polybutadiene composed of at least about 80% of polymerized 1,4-units. ### Claim 17 (depends on 16) A star-branched block copolymer in accordance with category 1) of claim 16 wherein each branch is a triblock composed of said diene I polymer block as outermost block, a middle block of said second named polybutadiene and an innermost block of said first named polybutadiene. ### Claim 18 (depends on 17) The star-branched block copolymer of claim 17 wherein said diene I is isoprene. ### Claim 19 (depends on 16) A star-branched block copolymer in accordance with category 1) of claim 16 wherein each branch is a triblock composed of said diene I polymer block as outermost block, a middle block of said first named polybutadiene and an innermost block of said second named polybutadiene. ### Claim 20 (depends on 19) The star-branched block copolymer of claim 19 wherein said diene I is isoprene. ### Claim 21 (depends on 16) A star-branched block copolymer in accordance with category 2) of claim 16 wherein each branch is a diblock composed of said random copolymer as outer block and said polybutadiene as inner block. ### Claim 22 (depends on 21) The star-branched block copolymer of claim 21 wherein said diene I is isoprene. ### Claim 23 (depends on 1) A halogenated polymer produced by a method comprising halogenating the star-branched block copolymer of claim 1.