# US 5,710,211 A · Process for producing vinyl alcohol polymer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,710,211 A - Document ID: US5710211A - Status: Granted - Kind: A - Application number: 08/684,484 - Filed: 1996-07-19 - Granted: 1998-01-20 - Earliest claimed: 1995-08-01 - Assignees: Kuraray Co., Ltd. - Inventors: Toshiaki Sato; Naoki Fujiwara; Atsushi Jikihara - Web page: https://patentgrep.com/patent/US5710211A ## CPC - C08F 8/34: Introducing sulfur atoms or sulfur-containing groups - C08F 218/08: Vinyl acetate - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract According to the present invention, there are provided a process for producing a vinyl alcohol polymer comprising reaction of a vinyl ester polymer (A) having an epoxy group with a compound (B) having a thiol or thioester group and hydrolysis thereof, said hydrolysis being conducted during or after said reaction; and a process for producing a vinyl alcohol polymer comprising reaction of a vinyl ester polymer (C) having a thiol or thioester group with a compound (D) having an epoxy group and hydrolysis thereof, said hydrolysis being conducted during or after said reaction. According to the present invention, it is possible to efficiently introduce into PVA various functional groups having excellent reactivity, crosslinkability, ionic interactivity, water-solubility, interfacial physical properties, low-temperature flexibility, etc., under relatively mild reaction conditions. According to the present invention, in addition, it is possible to introduce into PVA such various functional groups, which could not be obtained by conventional methods. ## Claims ### Claim 1 A process for producing a vinyl alcohol polymer, comprising: reacting a vinyl acetate polymer (A) having an epoxy group with a compound (B) having a thiol or thioester group; and hydrolyzing the polymer, said hydrolysis being conducted during or subsequent to the reaction of compound (B) with the polymer (A). ### Claim 2 (depends on 1) The process of claim 1, wherein the epoxy group content of the vinyl acetate polymer (A) ranges from 0.01 to 30 mol %. ### Claim 3 (depends on 2) The process of claim 2, wherein said epoxy group content ranges from 0.02 to 20 mol %. ### Claim 4 (depends on 1) The process of claim 1, wherein the viscosity average molecular weight (Mv) of said vinyl acetate polymer (A) ranges from 10.sup.3 to 2,000.times.10.sup.3. ### Claim 5 (depends on 1) The process of claim 1, wherein, during the preparation of vinyl acetate polymer (A), vinyl acetate monomer is copolymerized with at least one other copolymerizable monomer selected from the group consisting of olefins, unsaturated acids (salts thereof), acrylamides, methacrylamides, N-vinylamides, vinylcyanides, vinylethers, vinylhalides, vinylsilanes, allyl acetate, allyl chloride, allyl alcohol and dimethylallyl alcohol. ### Claim 6 (depends on 1) The process of claim 1, wherein said compound (B), having a thiol or thioester group, is an alkanethiol, a thiol having a double bond, an aromatic thiol, a phenol-containing thiol, a heterocyclic thiol, a thiol containing a hydroxyl group, a thiol having a carboxyl group, a thiol having a sulfonic acid group, a thiol having an amino group, a thiocarboxylic acid, a thiol having a fluorine-containing group, a thiol having a silyl group and 3-mercaptopropylboronic acid. ### Claim 7 (depends on 1) The process of claim 1, wherein said compound (B) is a polyalkyleneglycol, vinyl acetate (co)polymer, vinyl pivalate (co)polymer, methyl methacrylate (co)polymer, styrene (co)polymer, N-butylacrylate (co)polymer or other vinyl polymer having a thiol or thioester group. ### Claim 8 (depends on 1) The process of claim 1, wherein the concentration of polymer (A) in a solvent solution ranges from 5 to 90% and the amount of compound (B) is such that the mol ratio of the thiol or thioester group to the concentration of epoxy groups ranges from 1.0 to 5.0. ### Claim 9 (depends on 1) The process of claim 1, wherein said hydrolysis reaction is conducted at a temperature of 0.degree. C. to 180.degree. C., said reaction solution containing a catalyst in a mol ratio amount relative to the concentration of vinylester units ranging from 0.001 to 1.2. ### Claim 10 A process for producing a vinyl alcohol polymer, comprising: reacting a vinyl acetate polymer (C) having a thiol or thioester group with a compound (D) having an epoxy group; and hydrolyzing the polymer, said hydrolysis being conducted as the reaction proceeds or subsequent to the reaction. ### Claim 11 (depends on 10) The process of claim 10, wherein the thiol or thioester group content of the vinyl acetate polymer (C) ranges from 0.01 to 30 mol %. ### Claim 12 (depends on 11) The process of claim 11, wherein said thiol or thioester group content ranges from 0.02 to 20 mol %. ### Claim 13 (depends on 10) The process of claim 10, wherein the viscosity-average molecular weight (Mv) of said vinyl acetate polymer (C) ranges from 10.sup.3 to 2,000.times.10.sup.3. ### Claim 14 (depends on 10) The process of claim 10, wherein said compound (B), having an epoxy group, is methylglycidyl ether, ethyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, methanol(POE)n glycidyl ether (n=1 to 30), phenol(POE).sub.n glycidyl ether (n=1 to 30), lauryl alcohol(POE).sub.n glycidyl ether (n=1 to 30), methanol(POP).sub.n glycidyl ether (n=1 to 30), neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, (POE)N diglycidyl ether (n=1 to 30), (POP).sub.n diglycidyl ether, (n=1 to 70), (polyoxytetramethylene glycol).sub.n diglycidyl ether (n=1 to 30), resorcinol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, sorbital polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerin-polyglycerol polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether, hydroquinone diglycidyl ether, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, butadiene monoepoxide, butadiene dioxide, 1,2-epoxy-5-hexene, 1,5-hexadiene dioxide, 1,2-epoxy-7-octene, 1,7-octadiene dioxide, 1,2-epoxy-9-decene, 1,9-decadiene dioxide, allyl glycidyl ether, methallyl glycidyl ether, 8-hydroxy-6,7-epoxy-1-octene, 8-acetoxy-6,7-epoxy-1-octene, N-(2,3-epoxy)propylacrylamide, N-(2,3-epoxy)propylmethacrylamide, 4-acrylamidophenyl glycidyl ether, 3-acrylamidophenyl glycidyl ether, 4-methacrylamidophenyl glycidyl ether, 3-methacrylamidophenyl glycidyl ether, N-glycidoxymethylacrylamide, N-glycidoxymethylmethacrylamide, N-glycidoxyethylacrylamide, N-glycidoxyethylmethacrylamide, N-glycidoxypropylacrylamide, N-glycidoxypropylmethacrylamide, N-glycidoxybutylacrylamide, N-glycidoxybutylmethacrylamide, 4-acrylamidomethyl-2,5-dimethylphenyl glycidyl ether, 4-methacrylamidomethyl-2,5-dimethylphenyl glycidyl ether, acrylamidopropyldimethyl(2,3-epoxy)propylammonium chloride, methacrylamidopropyldimethyl(2,3-epoxy)propylammonium chloride, 3-perfluorobutyl-1,2-epoxypropane, 3-perfluorohexyl-1,2-epoxypropane, 3-perfluorooctyl-1,2-epoxypropane, 3-perfluorodecyl-1,2-epoxypropane, 3-(perfluoro-2-methylbutyl)-1,2-epoxypropane, 3-(perfluoro-2-methylhexyl)-1,2-epoxypropane, 3-(perfluoro-2-methyloctyl)-1,2-epoxypropane, 3-perfluoro-3-methyldecyl)-1,2-epoxypropane, 3-(1H,1H,5H-octafluoropentyloxy)-1,2-epoxypropane, 3-(1H,1H,5H-dodecafluoroheptyloxy)-1,2-epoxypropane, 3-(1H,1H,5H-hexadecafluorononyloxy)-1,2-epoxypropane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride and glycidyl methacrylate. ### Claim 15 (depends on 10) The process of claim 10, wherein said compound (D) is a bisphenol A epoxy resin, a bisphenol S epoxy resin or a bisphenol F epoxy resin. ### Claim 16 (depends on 10) The process of claim 10, wherein the concentration of vinyl acetate polymer (C) in a solvent solution ranges from 5 to 90% and the molar ratio of the concentration of epoxy groups in compound (D) to the concentration of thiol or thioester groups in polymer (C) ranges from 1.0 to 5.0. ### Claim 17 (depends on 12) The process of claim 12, wherein the reaction temperature ranges from 0.degree. C. to 250.degree. C. for a time ranging from 0.01 hours to 20 hours.