# US 8,541,509 B2 · Polymers functionalized with protected oxime compounds > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,541,509 B2 - Document ID: US8541509B2 - Status: Granted - Kind: B2 - Application number: 13/309,958 - Filed: 2011-12-02 - Published: 2012-03-29 - Granted: 2013-09-24 - Earliest claimed: 2006-12-17 - Assignees: Bridgestone Corporation - Applicants: Steven Luo; Yuan-Yong Yan; Jason T. Poulton; Eiju Suzuki - Inventors: Steven Luo; Yuan-Yong Yan; Jason T. Poulton; Eiju Suzuki - Web page: https://patentgrep.com/patent/US8541509B2 ## CPC - C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton - C08L 19/006: {Rubber characterised by functional groups, e.g. telechelic diene polymers} - C08L 9/00: Compositions of homopolymers or copolymers of conjugated diene hydrocarbons - C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract A method for preparing a functionalized polymer, the method comprising the steps of (i) polymerizing conjugated diene monomer by employing a lanthanide-based catalyst to form a reactive polymer, and (ii) reacting the reactive polymer with a protected oxime compound. ## Claims ### Claim 1 A method for preparing a functionalized polymer, the method comprising the steps of: (i) polymerizing conjugated diene monomer by employing a lanthanide-based catalyst to form a reactive polymer; and (ii) reacting the reactive polymer with a protected oxime compound, where the protected oxime compound is defined by the formula I or II where R2 and R3 are each independently a hydrogen atom or a mono-valent organic group, R4 is a mono-valent organic group, and R5 is divalent organic group, where said step of reacting the reactive polymer with a protected oxime compound occurs before the reactive polymer is quenched. ### Claim 2 (depends on 1) The method of claim 1, where the protected oxime is defined by the formula I. ### Claim 3 (depends on 2) The method of claim 2, where R2 or R3 is a hydrogen atom. ### Claim 4 (depends on 2) The method of claim 2, where R2 or R3 is an alkyl group. ### Claim 5 (depends on 2) The method of claim 2, where R2 or R3 is a cycloalkyl group. ### Claim 6 (depends on 2) The method of claim 2, where R2 or R3 is an aryl group. ### Claim 7 (depends on 2) The method of claim 2, where R2 or R3 is a bicyclic or polycyclic aryl group. ### Claim 8 (depends on 2) The method of claim 2, where R2 or R3 is a heterocyclic group. ### Claim 9 (depends on 2) The method of claim 2, where R2 or R3 is a hydrocarbyl group. ### Claim 10 (depends on 1) The method of claim 1, where the protected oxime is defined by the formula II. ### Claim 11 (depends on 10) The method of claim 10, where R5 is a hydrocarbylene group. ### Claim 12 (depends on 11) The method of claim 11, where R5 includes a heteroatom. ### Claim 13 (depends on 1) The method of claim 1, where the molar ratio of the protected oxime compound to the lanthanide metal of the lanthanide-based catalyst is from about 1:1 to about 200:1. ### Claim 14 (depends on 1) The method of claim 1, where the lanthanide-based catalyst is formed by combining a lanthanide compound, an alkylating agent, and optionally a halogen-containing compound, with the proviso that the lanthanide compound or the alkylating agent includes a labile halogen atom in the absence of the optional halogen-containing compound. ### Claim 15 (depends on 14) The method of claim 14, where the alkylating agent includes an aluminoxane and an organoaluminum compound represented by the formula AlRnX3-n, where each R, which may be the same or different, is a mono-valent organic group that is attached to the aluminum atom via a carbon atom, where each X, which may be the same or different, is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group, and where n is an integer of 1 to 3. ### Claim 16 A functionalized polymer prepared by a method comprising the steps of: (i) polymerizing conjugated diene monomer by employing a lanthanide-based catalyst to form a reactive polymer; and (ii) reacting the reactive polymer with a protected oxime compound, where the protected oxime compound is defined by the formula I or II where R2 and R3 are each independently a hydrogen atom or a mono-valent organic group, R4 is a mono-valent organic group, and R5 is divalent organic group, where said step of reacting the reactive polymer with a protected oxime compound occurs before the reactive polymer is quenched. ### Claim 17 (depends on 16) The functionalized polymer of claim 16, where the conjugated diene monomer is 1,3-butadiene, and the reactive polymer prepared therefrom is a reactive cis-1,4-polybutadiene. ### Claim 18 (depends on 1) The method of claim 1, where the protected oxime compound is an O-hydrocarbyloxime. ### Claim 19 (depends on 1) The method of claim 1, where the protected oxime compound is an O-acyloxime. ### Claim 20 (depends on 1) The method of claim 1, where the protected oxime compound is an O-sulfonyloxime. ### Claim 21 (depends on 1) The method of claim 1, where the protected oxime compound is an O-silyloxime. ### Claim 22 (depends on 16) The functionalized polymer of claim 16, where the protected oxime compound is an O-hydrocarbyloxime. ### Claim 23 (depends on 16) The functionalized polymer of claim 16, where the protected oxime compound is an O-acyloxime. ### Claim 24 (depends on 16) The functionalized polymer of claim 16, where the protected oxime compound is an O-sulfonyloxime. ### Claim 25 (depends on 16) The functionalized polymer of claim 16, where the protected oxime compound is an O-silyloxime. ### Claim 26 (depends on 1) The method of claim 1, where R2 and R3 are each independently a hydrogen atom or a hydrocarbyl group, R4 is a hydrocarbyl group, and R5 is a hydrocarbylene group. ### Claim 27 (depends on 16) The functionalized polymer of claim 16, where R2 and R3 are each independently a hydrogen atom or a hydrocarbyl group, R4 is a hydrocarbyl group, and R5 is a hydrocarbylene group. ### Claim 28 (depends on 26) The method of claim 26, where R2 and R3 are each independently a hydrogen atom, an alkyl group, or an aryl group, R4 is an alkyl group or an aryl group, and R5 is an alkylene group. ### Claim 29 (depends on 27) The functionalized polymer of claim 27, where R2 and R3 are each independently a hydrogen atom, an alkyl group, or an aryl group, R4 is an alkyl group or an aryl group, and R5 is an alkylene group.