# US 10,370,478 B2 · Method for producing alkenyl ether polymer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,478 B2 - Document ID: US10370478B2 - Status: Granted - Kind: B2 - Application number: 15/572,384 - Filed: 2016-05-02 - Published: 2018-05-03 - Granted: 2019-08-06 - Earliest claimed: 2015-05-08 - Assignees: Maruzen Petrochemical Co., Ltd. - Applicants: Maruzen Petrochemical Co., Ltd. - Inventors: Shinji Sugihara - Web page: https://patentgrep.com/patent/US10370478B2 ## CPC - C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent} - C08F 4/40: Redox systems - C08F 16/26: Monomers containing oxygen atoms in addition to the ether oxygen - C08F 18/08: Vinyl acetate - C08F 216/1416: {Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether} - C08F 218/08: Vinyl acetate - C08F 2438/03: Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] - C08F 2800/10: as molar percentages - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract To provide a method for producing a polymer that is capable of providing an alkenyl ether polymer having a molecular weight, a molecular weight distribution, and a composition that are controlled, with a vinyl ether having a hydroxyl group, and a block copolymer thereof. To provide a polymer obtained by the method as a macro chain transfer agent capable of performing reversible addition fragmentation chain transfer polymerization. Livingness can be imparted to radical polymerization of a hydroxyl group-containing vinyl ether by performing the radical polymerization in the presence of a particular RAFT agent and a radical polymerization initiator, and a block copolymer with another radically polymerizable vinyl monomer can be obtained by using the resulting living polymer as a macro chain transfer agent capable of performing reversible addition fragmentation chain transfer polymerization. ## Claims ### Claim 1 A method for producing an alkenyl ether polymer, comprising at least performing living radical polymerization of an alkenyl ether having a hydroxyl group represented by formula (2): wherein R3, R4, and R5 each independently represent a hydrogen atom or an alkyl group; R6 represents a linear or branched alkylene group or an alkylene group comprising an alicyclic structure; and p represents 1, 2, or 3, in the presence of a dithiocarbamate ester represented by formula (1) as a chain transfer agent and a radical polymerization initiator: wherein Q1 represents a functional group capable of activating vinyl carbon for free radical addition through detachment as a radical; and R1 and R7 each independently represent an alkyl group, an aryl group, or a nitrogen-containing heterocyclic group, in which R1 and R2 may be bonded to each other to form a heterocyclic ring. ### Claim 2 (depends on 1) The method according to claim 1, wherein the functional group represented by Q1 is a group represented by formula (1a): wherein X1 represents a cyano group, an aryl group, an alkoxycarbonyl group, a carboxyl group, or an N-substituted carbamoyl group; and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, —(CH2)k—OH, or —(CH2)k—COOY, wherein Y represents a hydrogen atom or an N-succinimidyl group; and k represents an integer of from 1 to 5. ### Claim 3 (depends on 1) The method according to claim 1, wherein the radical polymerization initiator is an azo compound. ### Claim 4 (depends on 1) The method according to claim 1, wherein the alkenyl ether represented by the formula (2) and a radically polymerizable vinyl monomer that is different therefrom are copolymerized. ### Claim 5 (depends on 4) The method according to claim 4, wherein the radically polymerizable vinyl monomer is at least one monomer selected from the group consisting of styrene and a styrene derivative, (meth)acrylic acid and a (meth)acrylic acid derivative, (meth)acrylamide and a (meth)acrylamide derivative, (meth)acrylonitrile, isoprene, 1,3-butadiene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, N-vinylindole, N-vinylphthalimide, N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylcaprolactam. ### Claim 6 A macro chain transfer agent comprising at least an end structure comprising a dithiocarbamate group represented by formula (3): wherein R1 and R2 each independently represent an alkyl group, an aryl group, or a nitrogen-containing heterocyclic group, or R1 and R2 may be bonded to each other to form a heterocyclic ring, and a repeating unit derived from a hydroxyl group-containing alkenyl ether represented by formula (4): wherein R3, R4, and R3 each independently represent a hydrogen atom or an alkyl group; R6 represents a linear or branched alkylene group or an alkylene group comprising an alicyclic structure; and p represents 1, 2, or 3. ### Claim 7 (depends on 6) The macro chain transfer agent according to claim 6, wherein the macro chain transfer agent is capable of performing reversible addition fragmentation chain transfer polymerization. ### Claim 8 A macro chain transfer agent capable of performing reversible addition fragmentation chain transfer polymerization represented by formula (5): wherein Q2 represents a functional group capable of activating vinyl carbon for free radical addition through detachment as a radical; R1 and R2 each independently represent an alkyl group, an aryl group, or a nitrogen-containing heterocyclic group, or R1 and R2 may be bonded to each other to form a heterocyclic ring; R3, R4, and R5 each independently represent a hydrogen atom or an alkyl group; R6 represents a linear or branched alkylene group or an alkylene group compromising an alicyclic structure; n represents a number of repetition of an alkenyl ether unit; and p represents 1, 2, or 3. ### Claim 9 (depends on 8) The macro chain transfer agent according to claim 8, wherein the functional group represented by Q2 is a group represented by formula (5a): wherein X2 represents a cyano group, an aryl group, an alkoxycarbonyl group, a carboxyl group, or an N-substituted carbamoyl group; and Rc and Rd each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, —(CH2)k—OH, or —(CH2)k—COOY, wherein Y represents a hydrogen atom or an N-succinimidyl group; and k represents an integer of from 1 to 5. ### Claim 10 (depends on 6) A method for producing a block copolymer, comprising polymerizing a radically polymerizable vinyl monomer through living radical polymerization in the presence of the macro chain transfer agent according to claim 6 and a radical polymerization initiator. ### Claim 11 (depends on 10) The method according to claim 10, wherein the radical polymerization initiator is an azo compound. ### Claim 12 (depends on 10) The method according to claim 10, wherein the radically polymerizable vinyl monomer is at least one monomer selected from the group consisting of styrene and a styrene derivative, (meth)acrylic acid and a (meth)acrylic acid derivative, (meth)acrylamide and a (meth)acrylamide derivative, (meth)acrylonitrile, isoprene, 1,3-butadiene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, N-vinylindole, N-vinylphthalimide, N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylcaprolactam.