# US 12,110,383 B2 · Crosslinkable blends of VDF copolymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,110,383 B2 - Document ID: US12110383B2 - Status: Granted - Kind: B2 - Application number: 17/264,956 - Filed: 2019-08-07 - Published: 2022-11-17 - Granted: 2024-10-08 - Earliest claimed: 2018-08-09 - Assignees: Solvay Specialty Polymers Italy S.P.A. - Applicants: Solvay Specialty Polymers Italy S.P.A. - Inventors: Julio A. Abusleme; Ségolène Brusseau - Web page: https://patentgrep.com/patent/US12110383B2 ## CPC - C08F 220/20: of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} - C08L 27/16: Homopolymers or copolymers or vinylidene fluoride - B29C 71/02: Thermal after-treatment {(B29C71/0063 and B29C71/0072 take precedence)} - C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof - C08J 3/246: {Intercrosslinking of at least two polymers} - C08F 214/225: {with non-fluorinated comonomers} - C08J 2327/16: Homopolymers or copolymers of vinylidene fluoride - C08J 2427/16: Homopolymers or copolymers of vinylidene fluoride - C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure - C08L 2312/00: Crosslinking - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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 present invention pertains to blends of crosslinkable vinylidene fluoride copolymers comprising recurring units derived from hydrophilic monomers, said blend being useful for producing shaped articles characterized by improved performances. ## Claims ### Claim 1 A crosslinkable composition (C) comprising: A) at least one fluoropolymer [polymer (FA)] comprising: (i) recurring units derived from vinylidene fluoride (VDF) monomer; (ii) recurring units derived from at least one hydroxyl group-containing vinyl monomer (HA), wherein the total amount of recurring units (ii) in said polymer (FA) is of at most 10.0% by moles, with respect to the total moles of recurring units of polymer (FA); said polymer (FA) being characterized by a fraction of randomly distributed units (HA) of at least 40%; and B) at least one a fluoropolymer [polymer (FB)], different from polymer (FA), comprising: (i) recurring units derived from vinylidene fluoride (VDF) monomer; (iii) recurring units derived from at least one carboxyl group-containing vinyl monomer (CA); wherein the total amount of recurring units (iii) in said polymer (FB) is of at most 10.0% by moles, with respect to the total moles of recurring units of polymer (FB); said polymer (FB) being characterized by a fraction of randomly distributed units (CA) of at least 40%; and further comprising at least one acidic crosslinking catalyst. ### Claim 2 (depends on 1) The composition (C) of claim 1 wherein the hydroxyl group-containing vinyl monomer (HA) is a compound of formula (I): wherein: R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom, a halogen atom, and a C1-C3 hydrocarbon group and ROH is a C2-C10 hydrocarbon chain moiety comprising at least one hydroxyl group and possibly containing in the chain one or more oxygen atoms, carbonyl groups or carboxy groups. ### Claim 3 (depends on 2) The composition (C) of claim 2 wherein monomer (HA) is a compound of formula (Ia): wherein: R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and R′OH is a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group. ### Claim 4 (depends on 3) The composition (C) of claim 3 wherein monomer (HA) of formula (Ia) is selected from the group consisting of hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl acrylate (HPA), and mixtures thereof. ### Claim 5 (depends on 1) The composition (C) of claim 1 wherein the carboxyl group-containing vinyl monomer (CA) is a compound of formula (II): wherein: R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and RH is a C2-C10 hydrocarbon moiety comprising at least one carboxyl group. ### Claim 6 (depends on 1) The composition (C) of claim 1 wherein (CA) is a compound of formula (Ila): wherein R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and R′H is a hydrogen or a C1-C5 hydrocarbon moiety comprising at least one carboxyl group. ### Claim 7 (depends on 6) The composition (C) of claim 6 wherein monomer (CA) is selected from the group consisting of acrylic acid (AA), (meth) acrylic acid and mixtures thereof. ### Claim 8 (depends on 1) The composition (C) according to claim 1 wherein polymer (FA) further comprises recurring units derived from one or more fluorinated comonomers (CF) different from VDF. ### Claim 9 (depends on 1) The composition (C) according to claim 1 wherein polymer (FB) further comprises recurring units derived from one or more fluorinated comonomers (CF) different from VDF. ### Claim 10 (depends on 1) The composition (C) according to claim 1 wherein: polymer (FA) comprises: at least 70% by moles of vinylidene fluoride (VDF), from 0.1% to 3.0% by moles of at least one hydroxyl group-containing vinyl monomer (HA); optionally from 0.5 to 3.0% by moles of recurring units derived from at least one fluorinated comonomer (CF), and polymer (FB) comprises: at least 70% by moles of vinylidene fluoride (VDF), from 0.1% to 3.0% by moles of at least one carboxyl group-containing vinyl monomer (CA); optionally from 0.5 to 3.0% by moles of recurring units derived from at least one fluorinated comonomer (CF). ### Claim 11 (depends on 1) The composition (C) of claim 1 wherein the acidic crosslinking catalyst is a Lewis acid selected from the group consisting of boron trifluoride, aluminum chloride, zinc chloride, stannous chloride, antimony trichloride, ferric chloride, boron trifluoridedimethyl ether complex, boron trifluoride-diethyl ether complex, boron trifluoride-dipropyl ether complex and antimony trioxide. ### Claim 12 (depends on 1) A process for preparing a crosslinked fluoropolymer (XLF) comprising the step of submitting a composition (C) according to claim 1 to a heat treatment at a temperature comprised between 130° C. and 250° C. ### Claim 13 (depends on 12) A shaped article comprising the crosslinked fluoropolymer (XLF) obtained according to the process of claim 12. ### Claim 14 (depends on 1) A method for making a shaped article comprising the crosslinked fluoropolymer (XLF), the method comprising: A) processing a composition (C) according to claim 1 into a shaped article; B) thermally treating the shaped article provided in step (a) at a temperature comprised between 130° C. and 250° C. ### Claim 15 (depends on 1) The composition (C) of claim 1 wherein monomer (HA) is selected from the group consisting of hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl acrylate (HPA), hydroxyethylhexyl(meth)acrylate, and mixtures thereof.