# US 2017/0283516 A1 · Processes for preparing aminosilane functionalized polymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2017/0283516 A1 - Document ID: US20170283516A1 - Status: Published application - Kind: A1 - Application number: 15/620,443 - Filed: 2017-06-12 - Published: 2017-10-05 - Earliest claimed: 2010-12-30 - Assignees: Bridgestone Corporation - Applicants: Bridgestone Corporation - Inventors: David F. Lawson; Terrence E. Hogan; Christine Rademacher; David M. Roggeman; Fuminori Ota - Web page: https://patentgrep.com/patent/US20170283516A1 ## CPC - C08C 19/25: Incorporating silicon atoms into the molecule - C08C 19/22: Incorporating nitrogen atoms into the molecule - C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton - C08F 4/48: selected from lithium, rubidium, caesium or francium {(C08F4/461 takes precedence)} - C08F 8/42: Introducing metal atoms or metal-containing groups - C08F 36/04: conjugated - C08F 36/06: Butadiene - C08F 236/10: with vinyl-aromatic monomers - C08L 9/06: Copolymers with styrene - C08L 15/00: Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) - C08L 19/006: {Rubber characterised by functional groups, e.g. telechelic diene polymers} - C08L 25/10: with conjugated dienes - B60C 1/00: Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition - Y02T 10/86: Optimisation of rolling resistance, e.g. weight reduction - C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS - 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) - B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION ## Abstract Metallated aminosilane compounds for use as functional initiators in anionic polymerizations and processes for producing an aminosilane-functionalized polymer using the metallated aminosilane compounds to initiate anionic polymerization of at least one type of anionically polymerizable monomer. Preferred use of the metallated aminosilane compounds results in rubber compositions for use in tires comprising an aminosilane functionalized polymer. ## Claims ### Claim 1 A metallated aminosilane compound for initiating an anionic polymerization comprising the reaction product of (1) at least one metallating agent, and (2) at least one alkylaminosilane compound having the formula where n is a whole number selected from the group consisting of 0-2, and m is a whole number selected from the group consisting of 1-3, with the proviso that the sum of m and n equals 3; where T is a methyl, ethyl, propyl, or allylic group; where each R4 and R5 is independently a hydrocarbyl group; where each R6 is independently a hydrocarbylene; and where one or more R5 may form a bridge between two nitrogen atoms when m is greater than 1. ### Claim 2 (depends on 2) The metallated aminosilane compound of claim 2, where the at least one metallating agent is selected from the group consisting of hydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbyl potassium compounds, and hydrocarbyl magnesium compounds, and combinations thereof. ### Claim 3 (depends on 1) The metallated aminosilane compound of claim 1, where the at least one metallating agent comprises a first component and a second component, where the first component is a Lewis base and the second component is selected from the group consisting of hydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbyl potassium compounds, hydrocarbyl magnesium compounds, and combinations thereof. ### Claim 4 (depends on 1) The metallated aminosilane compound of claim 1, where the at least one metallating agent comprises a first component and a second component, where the first component is selected from the group consisting of alkali metal alkoxide, alkali metal arylsulfonate, and combinations thereof, and where the second component is selected from the group consisting of hydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbyl potassium compounds, hydrocarbyl magnesium compounds, and combinations thereof. ### Claim 5 (depends on 1) The metallated aminosilane compound of claim 1, where the at least one alkylaminosilane compound is selected from the group consisting of bis(dialkylamino)phenylmethylsilane, bis(hexamethyleneimino)phenylmethylsilane, tris(dialkylamino)allylsilane, and combinations thereof. ### Claim 6 (depends on 1) The metallated aminosilane compound of claim 1, where the reaction product is generated in the absence of any monomers selected from the group consisting of conjugated diene monomers, monovinyl aromatic monomers, and combinations thereof. ### Claim 7 (depends on 1) A process for producing an aminosilane-functionalized polymer comprising the steps of: (a) providing a pre-formed initiator by preparing the metallated aminosilane compound of claim 1, and (b) polymerizing at least one type of anionically polymerizable monomer by using the metallated aminosilane compound to initiate the polymerization. ### Claim 8 (depends on 7) The process of claim 7, where the at least one type of anionically polymerizable monomer is selected from the group consisting of conjugated diene monomers and monovinyl aromatic monomers. ### Claim 9 (depends on 7) The process of claim 7, where the metal to amino silane compound ratio is between 0.8 and 1.2. ### Claim 10 A polymer comprising residue from an initiator, where the initiator comprises the reaction product of (1) at least one metallating agent, and (2) at least one alkylaminosilane compound having the formula where n is a whole number selected from the group consisting of 0-2, and m is a whole number selected from the group consisting of 1-3, with the proviso that the sum of m and n equals 3; where T is a methyl, ethyl, propyl, or allylic group; where each R4 and R5 is independently a hydrocarbyl group; where each R6 is independently a hydrocarbylene; and where one or more R5 may form a bridge between two nitrogen atoms when m is greater than 1. ### Claim 11 (depends on 10) The polymer of claim 10, where the at least one metallating agent is selected from the group consisting of hydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbyl potassium compounds, and hydrocarbyl magnesium compounds, and combinations thereof. ### Claim 12 (depends on 10) The polymer of claim 10, where the at least one metallating agent comprises a first component and a second component, where the first component is a Lewis base and the second component is selected from the group consisting of hydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbyl potassium compounds, hydrocarbyl magnesium compounds, and combinations thereof. ### Claim 13 (depends on 10) The polymer of claim 10, where the at least one metallating agent comprises a first component and a second component, where the first component is selected from the group consisting of alkali metal alkoxide, alkali metal arylsulfonate, and combinations thereof, and where the second component is selected from the group consisting of hydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbyl potassium compounds, hydrocarbyl magnesium compounds, and combinations thereof. ### Claim 14 (depends on 10) The polymer of claim 10, where the at least one alkylaminosilane compound is selected from the group consisting of bis(dialkylamino)phenylmethylsilane, bis(hexamethyleneimino)phenylmethylsilane, tris(dialkylamino)allylsilane, and combinations thereof. ### Claim 15 (depends on 7) A rubber composition for use in tires comprising: (a) from 10 to 100 phr of a polymer formed by the process of claim 7, where the at least one anionically polymerizable monomer is selected from the group consisting of conjugated diene monomers, monovinyl aromatic monomers, and combinations thereof; (b) from 90 to 0 phr of at least one rubbery polymer; and (c) from 5 to 200 phr of at least one filler. ### Claim 16 (depends on 15) The rubber composition of claim 15, where the at least one filler comprises silica. ### Claim 17 (depends on 15) The rubber composition of claim 15, where the silica is present in an amount from 10 to 150 phr. ### Claim 18 (depends on 10) A rubber composition for use in tires comprising: (a) from 10 to 100 phr of the polymer of claim 10; (b) from 90 to 0 phr of at least one rubbery polymer; and (c) from 5 to 200 phr of at least one filler. ### Claim 19 (depends on 18) The rubber composition of claim 18, where the at least one filler comprises silica. ### Claim 20 (depends on 18) The rubber composition of claim 18, where the silica is present in an amount from 10 to 150 phr.