# US 10,370,462 B2 · Melt-processable perfluoropolymers having improved thermal and mechanical properties after heating treatment > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,462 B2 - Document ID: US10370462B2 - Status: Granted - Kind: B2 - Application number: 15/316,083 - Filed: 2015-06-02 - Published: 2017-04-20 - Granted: 2019-08-06 - Earliest claimed: 2014-06-05 - Assignees: Solvay Specialty Polymers Italy S.P.A. - Applicants: Solvay Specialty Polymers Italy S.P.A. - Inventors: Pasqua Colaianna; Valeriy Kapelyushko; Mattia Bassi; Marco Mirenda; Vincenzo Arcella - Web page: https://patentgrep.com/patent/US10370462B2 ## CPC - C08F 6/00: Post-polymerisation treatments (C08F8/00 takes precedence; of conjugated diene rubbers C08C) - B29C 71/02: Thermal after-treatment {(B29C71/0063 and B29C71/0072 take precedence)} - C08F 6/28: Purification - C08F 214/26: Tetrafluoroethene - C08F 214/262: {with fluorinated vinyl ethers} - C08F 214/265: {with non-fluorinated comonomers} - C08J 7/08: {Heat treatment} - B29C 35/045: {using gas or flames} - B29C 2071/022: {Annealing} - C08J 2327/18: Homopolymers or copolymers of tetrafluoroethylene - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract The invention mainly pertains to a method for heat treating a composition [composition (C)] which contains at least one melt-processible perfluoropolymer [polymer (F)] formed of tetrafluoroethylene (TFE) copolymer with one or more perfluorinated comonomers [comonomer (F)] containing at least one unsaturation of ethylene type in amounts from 0.5% to 13% by weight, preferably from 0.6% to 11% by weight, and more preferably from 0.8% to 9% by weight; said polymer (F) possessing reactive end groups comprising at least one of the group consisting of hydrogen atoms, oxygen atoms and ethylenically unsaturated double bonds in an amount of at least 4.5 mmol/kg, the process comprising at least the step of heat-treating the composition (C) at a temperature of at least 260° C. ## Claims ### Claim 1 A method for heat treating a composition (C) which contains at least one melt-processible perfluoropolymer [polymer (F)], the process comprising at least the step of heat-treating the composition (C) at a temperature of at least 260° C., wherein polymer (F) is formed of tetrafluoroethylene (TFE) copolymer with one or more perfluorinated comonomers [comonomer (F)] containing at least one ethylene unsaturation in amounts from 0.5% to 13% by weight, and wherein polymer (F) possesses reactive end groups comprising at least one of the group consisting of hydrogen atoms, oxygen atoms and ethylenically unsaturated double bonds in an amount of at least 4.5 mmol/kg. ### Claim 2 (depends on 1) The method according to claim 1, wherein said comonomer (F) is selected from: C3-C8 perfluoroolefins; CF2═CFORf perfluoroalkylvinylethers (PAVE), wherein Rf is a C1-C6 perfluoroalkyl; CF2═CFOX perfluorooxyalkylvinylethers wherein X is a C1-C12 perfluorooxyalkyl having one or more ether groups; or perfluorodioxoles. ### Claim 3 (depends on 2) The method according to claim 2, wherein said comonomer (F) is selected from the following comonomers: PAVEs selected from perfluoromethylvinylether (PMVE of formula CF2═CFOCF3), perfluoroethylvinylether (PEVE of formula CF2═CFOC2F5), perfluoropropylvinylether (PPVE of formula CF2═CFOC3F7), or mixtures thereof; perfluoromethoxy vinyl ether (MOVE) of general formula CF2═CFOCF2ORf2, wherein Rf2 is a linear or branched C1-C6 perfluoroalkyl group, cyclic C5-C6 perfluoroalkyl group, a linear or branched C2-C6 perfluoroxyalkyl group; and perfluorodioxoles having the following formula: wherein X1 and X2, equal to or different from each other, are selected from F or CF3. ### Claim 4 (depends on 3) The method according to claim 3, wherein said comonomer (F) is selected from PMVE, PEVE, PPVE, MOVE, or combinations thereof. ### Claim 5 (depends on 4) The method according to claim 4, wherein polymer (F) is a TFE copolymer consisting essentially of: (a) from 0.5 to 8% by weight of recurring units derived from PPVE; (b) recurring units derived from TFE, in such an amount that the sum of the percentages of the recurring units (a) and (b) is equal to 100% by weight. ### Claim 6 (depends on 1) The method according to claim 1, wherein polymer (F) comprises recurring units derived from at least one C3-C8 perfluoroolefin. ### Claim 7 (depends on 6) The method according to claim 6, wherein polymer (F) is a TFE copolymer consisting essentially of: (a) from 0 to 6% by weight of recurring units derived from PMVE; (b) from 0.4 to 5% by weight of recurring units derived from one or more than one fluorinated PAVE comonomer different from PMVE; (c) from 0 to 6% by weight of recurring units derived from at least one C3-C8 perfluoroolefin; and (d) recurring units derived from TFE, in such an amount that the sum of the percentages of the recurring units (a), (b), (c) and (d) is equal to 100% by weight. ### Claim 8 (depends on 1) The method according to claim 1, wherein composition (C) contains polymer (F) as the sole component. ### Claim 9 (depends on 1) The method according to claim 1, wherein the temperature of heat treatment for composition (C) is at least 270° C. ### Claim 10 (depends on 1) The method according to claim 1, said process further comprising a step of processing in the molten state the composition (C), so as to provide a solid shaped article, and consequently heat treating said composition (C) under the form of said solid shaped article. ### Claim 11 (depends on 1) The method according to claim 1, wherein polymer (F) is formed of tetrafluoroethylene (TFE) copolymer with one or more comonomer (F) containing at least one unsaturation of ethylene type in amounts from 0.6% to 11% by weight. ### Claim 12 (depends on 1) The method according to claim 1, wherein polymer (F) is formed of tetrafluoroethylene (TFE) copolymer with one or more comonomer (F) containing at least one unsaturation of ethylene type in amounts from 0.8% to 9% by weight. ### Claim 13 (depends on 3) The method according to claim 3, wherein Rf2 is —CF2CF3, —CF2CF2OCF3, or —CF3. ### Claim 14 (depends on 3) The method according to claim 3, wherein X1 and X2 are each F. ### Claim 15 (depends on 5) The method according to claim 5, wherein polymer (F) is a TFE copolymer consisting essentially of: (a) from 0.7 to 6% by weight of recurring units derived from PPVE; (b) recurring units derived from TFE, in such an amount that the sum of the percentages of the recurring units (a) and (b) is equal to 100% by weight. ### Claim 16 (depends on 7) The method according to claim 7, wherein polymer (F) is a TFE copolymer consisting essentially of : (a) from 0 to 6% by weight of recurring units derived from PMVE; (b) from 0.4 to 5% by weight of recurring units derived from PEVE and/or PPVE; (c) from 0 to 6% by weight of recurring units derived from hexafluoropropylene (HFP); and (d) recurring units derived from TFE, in such an amount that the sum of the percentages of the recurring units (a), (b), (c) and (d) is equal to 100% by weight. ### Claim 17 (depends on 9) The method according to claim 9, wherein the temperature of heat treatment for composition (C) is at least 310° C.