# US 2019/0169337 A1 · Endcapped fluoropolymers for coating applications and processes of producing same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169337 A1 - Document ID: US20190169337A1 - Status: Published application - Kind: A1 - Application number: 16/199,909 - Filed: 2018-11-26 - Published: 2019-06-06 - Earliest claimed: 2017-12-01 - Assignees: Honeywell International Inc. - Applicants: Honeywell International Inc. - Inventors: Gang Xu; Wanchao Jiang; Siyuan Zhang; Linlin Duan; Zhe Ding - Web page: https://patentgrep.com/patent/US20190169337A1 ## CPC - C08F 214/188: {with non-fluorinated vinyl ethers} - C08F 214/182: {Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28} - C08K 5/09: Carboxylic acids; Metal salts thereof; Anhydrides thereof - C09D 7/20: Diluents or solvents - C09D 127/12: containing fluorine atoms - C08F 218/04: Vinyl esters - C08F 2800/10: as molar percentages - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) ## Abstract A process of producing an endcapped fluorocopolymer including the forming of a fluorocopolymer by copolymerization of: (1) one or more hydrofluoroolefin monomer(s) selected from the group consisting of hydrofluoroethylenes, hydrofluoropropenes, hydrofluorobutenes, hydrofluoropentenes and combinations of these; (2) one or more vinyl ester monomer(s); and (3) one or more vinyl ether monomer(s), wherein at least a portion of said vinyl ether monomer is a hydroxyl group-containing vinyl ether monomer; and at the end of copolymerization, reacting a radical transfer agent, preferably methanol, with the fluorocopolymer to produce the endcapped fluorocopolymer, preferably containing ether end groups. ## Claims ### Claim 1 A process of producing an endcapped fluorocopolymer, the process comprising: forming a fluorocopolymer by copolymerization of: (1) one or more hydrofluoroolefin monomer(s) selected from the group consisting of hydrofluoroethylenes, hydrofluoropropenes, hydrofluorobutenes, hydrofluoropentenes and combinations of these; (2) one or more vinyl ester monomer(s); and (3) one or more vinyl ether monomer(s), wherein at least a portion of said vinyl ether monomer is a hydroxyl group-containing vinyl ether monomer; and at the end of copolymerization, reacting a radical transfer agent with the fluorocopolymer to produce an endcapped fluorocopolymer. ### Claim 2 (depends on 1) The process of claim 1, wherein the radical transfer agent is reacted with the fluorocopolymer at a temperature that is greater than a copolymerization temperature. ### Claim 3 (depends on 1) The process of claim 1, wherein the radical transfer agent is methanol, and the endcapped fluorocopolymer contains ether end groups. ### Claim 4 (depends on 1) The process of claim 1, wherein the one or more hydrofluoroolefin monomer(s) is selected from hydrofluoropropenes. ### Claim 5 (depends on 4) The process of claim 4, wherein the one or more hydrofluoroolefin monomer(s) is selected from 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, and combinations thereof. ### Claim 6 (depends on 5) The process of claim 5, wherein the one or more hydrofluoroolefin monomer(s) is 1,3,3,3-tetrafluoropropene. ### Claim 7 (depends on 6) The process of claim 6, wherein the 1,3,3,3-tetrafluoropropene comprises trans-1,3,3,3-tetrafluoropropene. ### Claim 8 (depends on 1) An endcapped fluorocopolymer produced by the process of claim 1. ### Claim 9 A process of producing an endcapped fluorocopolymer, the process comprising: forming a fluorocopolymer by copolymerization of: (1) from about 40 mol % to about 60 mol % hydrofluoropropene monomers; (2) from about 5 mol % to 45 mol % of vinyl ester, vinyl ether or a mixture thereof; wherein the vinyl ester has the formula CH2═CR1—O(C═O)XR2 wherein x is 1, R1 is a hydrogen or a methyl group, and R2 is selected from the group consisting of an unsubstituted straight-chain, branched-chain or alicyclic alkyl group having 1 to 12 carbon atoms; and wherein the vinyl ether has the formula CH2═CR3—OR4, wherein R3 is a hydrogen or a methyl group, and R4 is selected from the group consisting of an unsubstituted straight-chain, branched-chain or alicyclic alkyl group having 1 to 12 carbon atoms; and (3) from about 3 mol % to about 30 mol % of hydroxyalkyl vinyl ether having the formula CH2═CR3—O—R5—OH, where R3 is a hydrogen or a methyl group, and R5 is selected from the group consisting of a C2 to C12 unsubstituted straight-chain, branched-chain or alicyclic alkyl group having from 3 to 5 carbons; and at the end of copolymerization, reacting a radical transfer agent with the fluorocopolymer to produce an endcapped fluorocopolymer; wherein the mol % are based on the total of the monomers. ### Claim 10 (depends on 9) The process of claim 9, wherein the hydrofluoropropene monomers are from about 45 mol % to about 55 mol %. ### Claim 11 (depends on 9) The process of claim 9, wherein the hydrofluoropropene monomers are about 50 mol %. ### Claim 12 (depends on 9) The process of claim 9, wherein the hydrofluoropropene monomers are selected from the group consisting of HFO-1234ze, HFO-1234yf and combinations of these. ### Claim 13 (depends on 9) The process of claim 9, wherein the hydrofluoropropene monomers are trans-HFO-1234ze. ### Claim 14 (depends on 9) The process of claim 9, wherein the radical transfer agent is reacted with the fluorocopolymer at a temperature that is greater than a copolymerization temperature. ### Claim 15 (depends on 9) The process of claim 9, wherein the radical transfer agent is methanol, and the endcapped fluorocopolymer contains ether end groups. ### Claim 16 (depends on 9) The process of claim 9, wherein the vinyl ester, vinyl either or mixture thereof comprise from about 10 mol % to about 40 mol %. ### Claim 17 (depends on 9) The process of claim 9, wherein the vinyl ester, vinyl either or mixture thereof comprise from about 20 mol % to about 40 mol %. ### Claim 18 (depends on 9) The process of claim 9, wherein the hydroxyalkyl vinyl ether comprises from about 3 mol % to about 20 mol %. ### Claim 19 (depends on 9) The process of claim 9, wherein the hydroxyalkyl vinyl ether comprises from about 3 mol % to about 10 mol %. ### Claim 20 (depends on 9) An endcapped fluorocopolymer produced by the process claim 9. ### Claim 21 A coating composition comprising: (i) one or more endcapped fluorocopolymers formed by the following process: forming a fluorocopolymer by copolymerization of (1) first monomer(s) consisting essentially of trans-HFO-1234ze in an amount of from about 40 mol % to about 60 mol %, (2) second monomer(s) comprising: A) vinyl ester monomer represented by formula CH2═CR1—O(C═O)XR2 wherein x is 1 and wherein R1 is either hydrogen or a methyl group and wherein R2 is an unsubstituted branched-chain alkyl group having 6 to 8 carbon atoms including at least one tertiary or at least one quaternary carbon atom, wherein said vinyl ester monomer is present in an amount of from about 5 mol % to about 45 mol; and B) vinyl ether monomer(s), represented by formula CH2═CR3—O—R4, wherein R3 is either hydrogen or a methyl group and wherein R4 is selected from the group consisting of a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms, said vinyl ether monomer(s) preferably being present in amounts of from about 10 mol % to about 40 mol %; and (3) third monomer(s) consisting of hydroxyalkyl vinyl ether represented by the formula CH2═CR3—O—R5—OH, where R3 is either hydrogen or a methyl group and R5 is selected from the group consisting of a substituted or unsubstituted straight-chain or branched-chain C3 to C5 alkyl, wherein the amount of said third monomer is preferably from about 3 mol % to about 30 mol %; and at the end of copolymerization, reacting the fluorocopolymer with methanol at a temperature that is greater than a copolymerization temperature to produce an endcapped fluorocopolymer containing ether end groups; and (ii) a carrier comprising one or more VOC compounds; wherein the coating composition comprises not greater than about 30% by weight of said carrier.