# US 10,370,475 B2 · Elastomeric compounds having increased cold flow resistance and methods producing the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,475 B2 - Document ID: US10370475B2 - Status: Granted - Kind: B2 - Application number: 15/187,237 - Filed: 2016-06-20 - Published: 2016-10-13 - Granted: 2019-08-06 - Earliest claimed: 2010-07-02 - Assignees: Bridgestone Corporation - Applicants: Bridgestone Corporation - Inventors: Xiao-Dong Pan; Zengquan Qin; Yuan-Yong Yan - Web page: https://patentgrep.com/patent/US10370475B2 ## CPC - C08F 236/10: with vinyl-aromatic monomers - C08K 3/04: Carbon - C08K 5/0091: {Complexes with metal-heteroatom-bonds} - C08K 5/098: Metal salts of carboxylic acids - C08L 91/00: Compositions of oils, fats or waxes; Compositions of derivatives thereof - C08L 91/06: Waxes - 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) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Elastomeric compounds having increased cold flow resistance may be obtained by utilizing from 10-100 phr of a functionalized rubbery polymer containing specified types of functionalizing units, at least 0.01 phr of a multivalent metal organic salt and 0-90 phr of at least one additional rubbery polymer. ## Claims ### Claim 1 An elastomeric composition comprising: (a) from 10 to 100 phr of a rubbery polymer having at least one functionalized terminus with functionality comprising a functionalizing terminating compound comprising an aryl group having at least one aromatic ring, and the at least one aromatic ring bears at least two directly-bonded —OR groups, where R is hydrogen or a hydrolyzable protecting group, with the proviso that at least 30% of the —OR groups are hydrolyzed; (b) at least 0.01 phr of a multivalent metal organic salt; and (c) from 0 to 90 phr of at least one additional rubbery polymer, wherein the rubbery polymer having at least one functionalized terminus contains monomers selected from conjugated diene compounds optionally in combination with monomers selected from vinyl aromatic compounds. ### Claim 2 (depends on 1) The elastomeric composition as claimed in claim 1, wherein the at least one additional rubbery polymer of (c) is selected from the group consisting of natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, butyl rubber, neoprene, ethylene-propylene rubber, EPDM, nitrile rubber, silicone rubber, fluoroelastomers, ethylene-acrylic rubber, ethylene-vinyl acetate rubber, epichlorohydrin rubber, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, tetrafluoroethylenepropylene rubber, and combinations thereof. ### Claim 3 (depends on 1) The elastomeric composition as claimed in claim 1, where the at least one aromatic ring bears between two and five directly-bonded —OR groups. ### Claim 4 (depends on 1) The elastomeric composition as claimed in claim 1, where at least two —OR groups are directly bonded to adjacent carbon atoms. ### Claim 5 (depends on 1) The elastomeric composition as claimed in claim 1, where R1 is derived from dihydroxybenzaldehyde. ### Claim 6 (depends on 1) The elastomeric composition as claimed in claim 1, where the multivalent metal organic salt is selected from the group of salts consisting of Fe2+, Fe3+, Al3+, Ca2+, Mn2+, Mn3+, Mn4+, Mn7+, Co2+, Ni2+, Zn2+, Cu2+, Ga3+, Zr4+, Ti3+, Ti4+, Mg2+, Cr2+, Cr3+, Cr6+, V3+, V4+, V5+, Sn2+, Sn4+, Pt2+, and combinations thereof. ### Claim 7 (depends on 1) The elastomeric composition as claimed in claim 1, further comprising at least one filler selected from the group consisting of carbon black, fumed or precipitated silica, clay, metal oxide, metal hydroxide, metal sulfide, metal silicate, metal carbonate, dual phase or multi-phase composite particles, and combinations thereof. ### Claim 8 (depends on 1) The elastomeric composition as claimed in claim 1, where the multivalent metal organic salt is present in an amount of 0.1 phr to 10 phr. ### Claim 9 (depends on 1) A tire having at least one component comprised of the elastomeric composition as claimed in claim 1. ### Claim 10 An elastomeric composition comprising: (a) from 10 to 100 phr of a rubbery polymer having at least one functionalized terminus with functionality comprising a functionalizing terminating compound comprising an aryl group having at least one aromatic ring, and the at least one aromatic ring bears at least two directly-bonded —OR groups, where R is hydrogen or a hydrolyzable protecting group, with the proviso that at least 30% of the —OR groups are hydrolyzed; (b) from 0.01 phr to 10 phr of a multivalent metal organic salt; (c) from 0 to 90 phr of at least one additional rubbery polymer selected from natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, butyl rubber, neoprene, ethylene-propylene rubber, EPDM, nitrile rubber, silicone rubber, fluoroelastomers, ethylene-acrylic rubber, ethylene-vinyl acetate rubber, epichlorohydrin rubber, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, or tetrafluoroethylenepropylene rubber; and (d) from 5 to 200 phr of at least one filler selected from carbon black, fumed or precipitated silica, clay, metal oxide, metal hydroxide, metal sulfide, metal silicate, or metal carbonate, wherein the rubbery polymer having at least one functionalized terminus contains monomers selected from conjugated diene compounds optionally in combination with monomers selected from vinyl aromatic compounds. ### Claim 11 (depends on 10) The elastomeric composition as claimed in claim 10, where the at least one aromatic ring bears between two and five directly-bonded —OR groups. ### Claim 12 (depends on 10) The elastomeric composition as claimed in claim 10, where the at least one aromatic ring bears at least two —OR groups that are directly bonded to adjacent carbon atoms. ### Claim 13 (depends on 10) The elastomeric composition as claimed in claim 10, where the functionalizing unit is derived from dihydroxybenzaldehyde. ### Claim 14 (depends on 10) The elastomeric composition as claimed in claim 10, where the multivalent metal organic salt is selected from the group of salts consisting of Fe2+, Fe3+, Al3+, Ca2+, Mn2+, Mn3+, Mn4+, Mn7+, Co2+, Ni2+, Zn2+, Cu2+, Ga3+, Zr4+, Ti3+, Ti4+, Mg2+, Cr2+, Cr3+, Cr6+, V3+, V4+, V5+, Sn2+, Sn4+, Pt2+, and combinations thereof. ### Claim 15 An elastomeric composition comprising: (a) from 10 to 100 phr of a rubbery polymer having at least one functionalized terminus with functionality comprising a functionalizing terminating compound comprising an aryl group having at least one aromatic ring, and the at least one aromatic ring bears at least two directly-bonded —OR groups, where R is hydrogen or a hydrolyzable protecting group, with the proviso that at least 30% of the —OR groups are hydrolyzed, (b) at least 0.01 phr of a multivalent metal organic salt; (c) from 0 to 90 phr of at least one additional rubbery polymer; and (d) from 5 to 200 phr of at least one filler selected from carbon black, fumed or precipitated silica, clay, metal oxide, metal hydroxide, metal sulfide, metal silicate, or metal carbonate, wherein the rubbery polymer having at least one functionalized terminus contains monomers selected from conjugated diene compounds optionally in combination with monomers selected from vinyl aromatic compounds. ### Claim 16 (depends on 15) The elastomeric composition as claimed in claim 15, wherein the at least one additional rubbery polymer of (c) is selected from the group consisting of natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, butyl rubber, neoprene, ethylene-propylene rubber, EPDM, nitrile rubber, silicone rubber, fluoroelastomers, ethylene-acrylic rubber, ethylene-vinyl acetate rubber, epichlorohydrin rubber, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, tetrafluoroethylenepropylene rubber, and combinations thereof. ### Claim 17 (depends on 15) The elastomeric composition as claimed in claim 15, where the at least one aromatic ring bears between two and five directly-bonded —OR groups. ### Claim 18 (depends on 15) The elastomeric composition as claimed in claim 15, where at least two —OR groups are directly bonded to adjacent carbon atoms. ### Claim 19 (depends on 15) The elastomeric composition as claimed in claim 15, where the multivalent metal organic salt is present in an amount of 0.1 phr to 10 phr.