# US 11,111,338 B2 · Terminal-functionalized polymer and related methods > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,338 B2 - Document ID: US11111338B2 - Status: Granted - Kind: B2 - Application number: 16/708,555 - Filed: 2019-12-10 - Published: 2020-04-09 - Granted: 2021-09-07 - Earliest claimed: 2014-12-30 - Assignees: Bridgestone Corporation - Applicants: Bridgestone Corporation - Inventors: Yuan-Yong Yan - Web page: https://patentgrep.com/patent/US11111338B2 ## CPC - C08G 77/442: containing vinyl polymer sequences - C08L 83/10: Block- or graft-copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00) - C08F 230/085: {the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes} - Y02T 10/86: Optimisation of rolling resistance, e.g. weight reduction - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - 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 - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION ## Abstract Disclosed herein are terminal-functionalized polymers functionalized with silicon-containing functionalizing agents, rubber compositions including the polymers, methods for improving the cold flow resistance of a polymer, methods for improving the filler dispersion of a silica-filled rubber composition, and processes for preparing the terminal-functionalized polymer. ## Claims ### Claim 1 A rubber composition comprising: 10-100 phr of a terminal-functionalized polymer having the following formula (II): wherein P is a polymer chain comprising at least one type of conjugated-diene monomer; Ra and Rc are the same or different and each is independently selected from vinyl-containing groups, Rb is selected from: (i) an alkyl group having 1 to 20 carbons, (ii) a cycloalkyl group having 3 to 20 carbons, and (iii) an alkylaryl group having 7 to 20 carbons; and n is 2 to 20; silica filler; no more than about 10 phr of oil; and a cure package. ### Claim 2 (depends on 1) The rubber composition of claim 1, wherein the terminal-functionalized polymer chain further comprises at least one vinyl aromatic monomer unit. ### Claim 3 (depends on 1) The rubber composition of claim 1, wherein the portion of the terminal-functionalized polymer other than P has a molecular weight of 500 to about 10,000 grams/mole. ### Claim 4 (depends on 1) The rubber composition of claim 1, wherein the vinyl-containing groups are selected from the group consisting of vinyltriethoxysilane oligomeric hydrolysate, vinyltriethoxysilanepropyltriethoxysilane oligomeric co-hydrolysate, vinyltrimethoxysilane oligomeric hydrolysate, and combinations thereof. ### Claim 5 (depends on 1) The rubber composition of claim 1, wherein silica filler is present in a total amount of 5 to 200 phr. ### Claim 6 (depends on 5) The rubber composition of claim 5, wherein the silica filler has a surface area, as measured by a BET method, of 32 to 400 m2/g. ### Claim 7 (depends on 6) The rubber composition of claim 6, wherein the surface area of the silica filler is 100 to 200 m2/g. ### Claim 8 (depends on 6) The rubber composition of claim 6, wherein the surface area of the silica filler is 220 to 400 m2/g. ### Claim 9 (depends on 5) The rubber composition of claim 5, wherein the terminal-functionalized polymer is not oil-extended. ### Claim 10 (depends on 1) The rubber composition of claim 1, wherein silica filler is present in a total amount of 100 to 150 phr. ### Claim 11 (depends on 10) The rubber composition of claim 10, wherein the terminal-functionalized polymer is not oil-extended. ### Claim 12 (depends on 1) The rubber composition of claim 1, wherein the terminal-functionalized polymer is not oil-extended. ### Claim 13 (depends on 1) The rubber composition of claim 1, wherein the terminal-functionalized polymer is present in an amount of 30 to 90 phr. ### Claim 14 (depends on 1) The rubber composition of claim 1, wherein the terminal-functionalized polymer is present in amount of about 40 to about 60 phr. ### Claim 15 (depends on 1) The rubber composition of claim 1, further comprising a carbon black filler. ### Claim 16 (depends on 15) The rubber composition of claim 15, wherein the carbon black filler is present in an amount of no more than 5 phr. ### Claim 17 (depends on 15) The rubber composition of claim 15, wherein the carbon black filler is present in an amount of 5 to 100 phr. ### Claim 18 A rubber composition comprising: about 40 to about 60 phr of a terminal-functionalized polymer having the following formula (II): wherein P is a polymer chain comprising at least one type of conjugated-diene monomer; Ra and Rc are the same or different and each is independently selected from H, alkyl groups having 1 to 20 carbons, cycloalkyl groups having 3 to 20 carbons, alkylaryl groups having 7 to 20 carbons, and vinyl-containing groups, Rb is selected from: (i) an alkyl group having 1 to 20 carbons, (ii) a cycloalkyl group having 3 to 20 carbons, and (iii) an alkylaryl group having 7 to 20 carbons; and n is 2 to 20; silica filler; no more than about 10 phr of oil; and a cure package. ### Claim 19 (depends on 18) The rubber composition of claim 18, wherein the portion of the terminal-functionalized polymer other than P has a molecular weight of about 500 to about 10,000 grams/mole. ### Claim 20 (depends on 19) The rubber composition of claim 19, wherein the terminal-functionalized polymer chain further comprises at least one vinyl aromatic monomer unit. ### Claim 21 (depends on 18) The rubber composition of claim 18, wherein Ra and RC are vinyl-containing groups. ### Claim 22 (depends on 18) The rubber composition of claim 18, wherein the vinyl-containing groups are selected from the group consisting of vinyltriethoxysilane oligomeric hydrolysate, vinyltriethoxysilanepropyltriethoxysilane oligomeric co-hydrolysate, vinyltrimethoxysilane oligomeric hydrolysate, and combinations thereof. ### Claim 23 (depends on 18) The rubber composition of claim 18, wherein silica filler is present in a total amount of 5 to 200 phr. ### Claim 24 (depends on 23) The rubber composition of claim 23, wherein the silica filler has a surface area, as measured by a BET method, of 32 to 400 m2/g. ### Claim 25 (depends on 24) The rubber composition of claim 24, wherein the surface area of the silica filler is 100 to 200 m2/g. ### Claim 26 (depends on 24) The rubber composition of claim 24, wherein the surface area of the silica filler is 220 to 400 m2/g. ### Claim 27 (depends on 23) The rubber composition of claim 23, wherein the terminal-functionalized polymer is not oil-extended. ### Claim 28 (depends on 18) The rubber composition of claim 18, wherein silica filler is present in a total amount of 100 to 150 phr. ### Claim 29 (depends on 28) The rubber composition of claim 28, wherein the terminal-functionalized polymer is not oil-extended. ### Claim 30 (depends on 18) The rubber composition of claim 18, wherein the terminal-functionalized polymer is not oil-extended. ### Claim 31 (depends on 18) The rubber composition of claim 18, further comprising a carbon black filler. ### Claim 32 (depends on 31) The rubber composition of claim 31, wherein the carbon black filler is present in an amount of no more than 5 phr. ### Claim 33 (depends on 31) The rubber composition of claim 31, wherein the carbon black filler is present in an amount of 5 to 100 phr.