CN113549289A - 一种聚偏二氟乙烯的增强配混物 - Google Patents
一种聚偏二氟乙烯的增强配混物 Download PDFInfo
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- CN113549289A CN113549289A CN202110832699.8A CN202110832699A CN113549289A CN 113549289 A CN113549289 A CN 113549289A CN 202110832699 A CN202110832699 A CN 202110832699A CN 113549289 A CN113549289 A CN 113549289A
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- Prior art keywords
- fibers
- polyvinylidene fluoride
- fluoropolymer
- compound
- reinforced compound
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 56
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 52
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 229920001059 synthetic polymer Polymers 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- -1 perfluorobutylethylene, pentafluoropropylene, 3,3, 3-trifluoro 1-propene Chemical class 0.000 claims description 9
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- FXPHNQAHHHWMAV-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)OC=C FXPHNQAHHHWMAV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- WZEOZJQLTRFNCU-UHFFFAOYSA-N trifluoro(trifluoromethoxy)methane Chemical compound FC(F)(F)OC(F)(F)F WZEOZJQLTRFNCU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 2
- XVKFQTALPDUTNS-UHFFFAOYSA-N 2-chloro-1,3,4,4,5,6,6,7,8,8,8-undecafluoro-3-(trifluoromethyl)oct-1-ene Chemical compound FC(C(F)(F)F)C(C(C(C(C(F)(F)F)(C(=CF)Cl)F)(F)F)F)(F)F XVKFQTALPDUTNS-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical class C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 description 19
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000001530 fumaric acid Substances 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
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- 239000004094 surface-active agent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 2
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical class 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
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- 229940047670 sodium acrylate Drugs 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
-
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Abstract
本发明涉及一种聚偏二氟乙烯的增强配混物,包含如下步骤:S1:在低于35℃的温度下,取长度小于25毫米的短切多组分纤维10‑25%与包含羧酸类接枝的官能化的含氟聚合物的基质混合合成聚合物;S2:加热,将温度保持在60‑90℃,将聚合物中的水分散性磺基聚酯去除,形成配混物。本发明提供了良好的粘合性以提高性能,又改善了纤维束在含氟聚合物基质内的分布。
Description
技术领域
本发明涉及增强热塑性配混物技术领域,尤其涉及一种聚偏二氟 乙烯的增强配混物。
背景技术
已知含氟聚合物,例如基于偏二氟乙烯CF2=CH2(VDF)的含氟 聚合物具有出色的机械稳定性能,非常好的化学惰性,较低的表面能, 电化学稳定性和良好的耐老化性。这些品质在各种最终用途应用中得 到了利用。糟糕的是,由于其惰性,很难将含氟聚合物与其他材料结 合。
官能团已被添加到含氟聚合物中,以增加与其他材料的粘合性, 增加一定水平的亲水性和润湿性,并提供反应性位点,例如用于交联 和随后的化学改性。官能团已经通过几种方式添加,例如通过官能单 体与含氟单体的直接共聚,以及通过聚合后接枝机理,例如将马来酸 酐接枝到聚偏二氟乙烯均聚物或共聚物上(如US7,241,817中所述), 以形成可得自阿科玛公司(ArkemaInc.)的ADX树脂。WO2013/110740 和US7351498还描述了通过单体接枝或通过共聚来使含氟聚合物官 能化。
已知纤维在许多类型的聚合物复合材料中用作增强材料。长纤维 可以用聚合物或预聚物浸渍,该聚合物或预聚物用作将纤维保持在一 起的粘合剂。用聚合物粘合剂浸泡或喷涂长纤维,然后通常将其缠绕 到模具上以形成结构,将其编织成互锁的狭窄结构,或者将其置于封 闭的模具中。然后将涂覆或浸渍有聚合物的纤维固结以形成最终制 品。由长纤维制成的制品通常包含至少45重量%,优选大于50重 量%,并且经常大于60至70重量%的纤维。
在连续纤维制品中,制品的性质受纤维性质支配,聚合物充当粘 合剂以将纤维保持在一起。
US8883898公开了用已被官能化的含氟聚合物浸渍连续纤维,所 述官能化优选通过用马来酸酐接枝来进行。
短纤维,也称为短切纤维股、短切股或纤维束,包含许多股线, 通常为2,000至10,000根单独的纤维,每根直径约3至10微米,并 通过聚合物上胶剂粘结在一起,基于纤维的重量,上胶剂的量通常为 约1至5%。然后将这些束或粗纱切成约2至15mm的长度,更典型的是2至8mm的长度。这些束形成自由流动的材料,该材料可以进 料至挤出机以进行配混,而不会释放游离纤维。未上胶或游离的纤维 不能有效地用于如本发明的聚合物配混物中,尤其是当短切纤维的长 度增加时。因此,在本发明中需要具有上胶的短切纤维以与含氟聚合 物配混。然后将小束纤维作为增强材料添加到聚合物基质中,以提高 基质的刚度。通常包含5至25重量%,优选8至20重量%的纤维束 的制品的性能由基质聚合物的性能决定。例如,尽管50重量%的连 续碳纤维复合材料的拉伸强度在碳纤维的方向上可以为约 250,000psi,但是具有15%短碳纤维的复合材料的拉伸强度可以为 15,000psi。
已经针对不同的聚合物基质开发了不同的纤维上胶剂,以改善上 胶纤维与基质聚合物之间的相容性。不幸的是,当前的纤维上胶剂与 含氟聚合物的相容性差。没有良好的相容性,因此在纤维与含氟聚合 物基质之间没有良好的分布和良好的粘合性,使用纤维增强材料的好 处还没有得到充分实现。
令人惊讶地,现已发现,当将含氟聚合物用羧酸类极性官能团接 枝时,与不含接枝含氟聚合物的含氟聚合物复合材料相比,含接枝含 氟聚合物和短纤维束的含氟聚合物基质具有增强的拉伸强度和挠曲 强度。使用不同类型的纤维(碳纤维,玻璃纤维)以及许多不同类型的 上胶剂,已发现了出色的结果。尽管不受任何特定理论的束缚,但据 信接枝的羧酸官能团与上胶剂和/或纤维形成某种类型的结合,这既 提供了良好的粘合性以提高性能,又改善了纤维束在含氟聚合物基质 内的分布。
发明内容
鉴于背景技术存在的不足,本发明涉及一种聚偏二氟乙烯的增强 配混物,根据上述问题,设计了一种混配物,既提供了良好的粘合性 以提高性能,又改善了纤维束在含氟聚合物基质内的分布。
本发明涉及一种聚偏二氟乙烯的增强配混物,包含如下步骤:S1: 在低于35℃的温度下,取长度小于25毫米的短切多组分纤维10-25% 与包含羧酸类接枝的官能化的含氟聚合物的基质混合合成聚合物; S2:加热,将温度保持在60-90℃,将聚合物中的水分散性磺基聚酯 去除,形成配混物。
进一步的,所述短切多组分纤维包含至少一种水分散性磺基聚酯 和至少一种与所述水分散性磺基聚酯不混溶的水不分散性合成聚合 物。
进一步的,所述接枝的含氟聚合物是均聚物,或者具有大于50 重量%的偏二氟乙烯的共聚物,或者包含乙烯和四氟乙烯单体单元的 共聚物。
进一步的,所述含氟聚合物是热塑性均聚物和共聚物,所述共聚 物具有按重量计大于90%重量的含氟单体单元。
进一步的,可用于形成含氟聚合物的含氟单体包括但不限于:偏 二氟乙烯、四氟乙烯、三氟乙烯、氯三氟乙烯、六氟丙烯、氟乙烯、 六氟异丁烯、全氟丁基乙烯、五氟丙烯、3,3,3-三氟1丙烯、2三氟甲 基3,3,3三氟丙烯、氟化乙烯基醚、包括全氟甲基醚、全氟乙基乙烯 基醚、全氟丙基乙烯基醚、全氟丁基乙烯基醚、长链全氟化乙烯基醚、 氟化间二氧化环戊烯、C4和更高碳的部分氟化或全氟化的α烯烃、 C3和更高碳的部分氟化或全氟化的环烯烃。
进一步的,所述羧酸类接枝的含氟聚合物包含马来酸酐作为接枝 官能团。
进一步的,所述短切多组分纤维选自下组:碳纤维,玻璃纤维, 芳族聚酰胺纤维,聚酰胺纤维,PEKK,PEEK,二氧化硅纤维,碳纳 米管,以及它们的混合物。
本发明的有益效果:当将含氟聚合物用羧酸类极性官能团接枝 时,与不含接枝含氟聚合物的含氟聚合物复合材料相比,含接枝含氟 聚合物和短纤维束的含氟聚合物基质具有增强的拉伸强度和挠曲强 度。提供了良好的粘合性以提高性能,又改善了纤维束在含氟聚合物 基质内的分布。
具体实施方式
以下将对本发明实施例中的技术方案进行清楚、完整的描述和讨 论,显然,这里所描述的仅仅是本发明的一部分实例,并不是全部的 实例,基于本发明中的实施例,本领域普通技术人员在没有做出创造 性劳动的前提下所获得的所有其他实施例,都属于本发明的保护范 围。
为了便于对本发明实施例的理解,下面将以具体实施例为例作进 一步的解释说明,且各个实施例不构成对本发明实施例的限定。
本发明的实施例1:S1:在低于35℃的温度下,取长度小于25 毫米的短切多组分纤维10-25%与包含羧酸类接枝的官能化的含氟聚 合物的基质混合合成聚合物;S2:加热,将温度保持在60-90℃,将 聚合物中的水分散性磺基聚酯去除,形成配混物。所述短切多组分纤 维包含至少一种水分散性磺基聚酯和至少一种与所述水分散性磺基 聚酯不混溶的水不分散性合成聚合物。
含氟聚合物:
可用于本发明的含氟聚合物是热塑性均聚物和共聚物,所述共聚 物具有按重量计大于50重量%的含氟单体单元,优选大于65重量%, 更优选大于75重量%,最优选大于90重量%的一种或多种含氟单体。 可用于形成含氟聚合物的含氟单体包括但不限于:偏二氟乙烯(VDF 或VF2),四氟乙烯(TFE),三氟乙烯(TrFE),氯三氟乙烯(CTFE),六 氟丙烯(HFP),氟乙烯(VF),六氟异丁烯(HFIB),全氟丁基乙烯(PFBE), 五氟丙烯,3,3,3-三氟1丙烯,2三氟甲基3,3,3三氟丙烯,氟化乙烯 基醚,包括全氟甲基醚(PMVE),全氟乙基乙烯基醚(PEVE),全氟丙 基乙烯基醚(PPVE),全氟丁基乙烯基醚(PBVE),长链全氟化乙烯基 醚,氟化间二氧化环戊烯,C4和更高碳的部分氟化或全氟化的α烯 烃,C3和更高碳的部分氟化或全氟化的环烯烃,以及它们的组合。
特别优选的含氟聚合物是聚偏二氟乙烯(PVDF)均聚物和共聚 物,例如来自阿科玛公司的树脂,以及乙烯-四氟乙烯(ETFE)共聚物。 尽管本发明适用于所有含氟聚合物及其共聚物,但偏二氟乙烯聚合物 将用于说明本发明。本领域普通技术人员将理解并且能够将对PVDF 的特定叙述应用于这些其他热塑性聚合物,这些被认为是在本发明的 范围内并且在本发明中实施。
本发明中使用的PVDF通常通过本领域已知的方法,使用水性自 由基乳液聚合来制备,但是也可以使用悬浮聚合、溶液聚合和超临界 CO2聚合方法。在一般的乳液聚合方法中,向反应器中加入去离子水、 能够在聚合过程中乳化反应物质的水溶性表面活性剂和任选的石蜡 防污剂。在一个优选的实施方式中,表面活性剂是非氟表面活性剂, 并且产生的最终产物是不含氟表面活性剂的。对混合物进行搅拌和脱 氧。然后将预定量的链转移剂CTA引入反应器中,将反应器温度升 高至所需水平,并将偏二氟乙烯(和可能的一种或多种共聚单体)进料 至反应器中。一旦引入了偏二氟乙烯的初始进料并且反应器中的压力 已经达到所需水平,就引入引发剂乳液或溶液以开始聚合反应。反应 温度可根据所用引发剂的特性而变化,本领域技术人员将知道如何调 整。温度通常为约30℃至150℃,优选约60℃至120℃。一旦 在反应器中达到所需的聚合物量,将停止单体进料,但是任选地继续 引发剂进料以消耗残留单体。排出残余气体(包含未反应的单体),从 反应器回收胶乳。
PVDF聚合产生的胶乳通常具有10至60重量%,优选10至50 重量%的固体含量。通常通过喷雾干燥、凝结或其他已知方法将胶乳 减小为粉末形式,以产生干粉。
接枝的含氟聚合物:
本发明复合材料的含氟聚合物基质包含一定量的已被不饱和羧 酸类官能单体接枝(如US7,241,817中所述)的含氟聚合物。接枝过程 涉及以下步骤:
a)将含氟聚合物与不饱和单体熔融混合;
b)将a)中获得的混合物形成膜、片、颗粒或粉末;
c)在无空气的情况下,将步骤b)的产物暴露于剂量为1-15Mrad 的光子(γ)或电子(β)辐射;和
d)任选地处理在c)中获得的产物,以除去未接枝到含氟聚合物上 的全部或部分不饱和单体。
所获得的接枝含氟聚合物可以就这样使用,或者作为与相同但未 接枝的含氟聚合物或另一种含氟聚合物的混合物使用。基质中接枝含 氟聚合物的含量为1至100重量%,优选为3至50重量%,最优选 为5至20重量%。
可用的不饱和羧酸类单体的实例包括具有2至20个碳原子的羧 酸,例如丙烯酸,甲基丙烯酸,马来酸,富马酸和衣康酸;这些酸的 官能衍生物,包括但不限于不饱和羧酸的酸酐、酯衍生物、酰胺衍生 物、酰亚胺衍生物和金属盐(例如碱金属盐)。还可以提及十一碳烯酸; 具有4-10个碳原子的不饱和二羧酸及其官能衍生物,特别是它们的 酸酐,是特别优选的接枝单体。
其他接枝单体的实例包括不饱和羧酸的C1-C8烷基酯或缩水甘 油酯衍生物,例如丙烯酸甲酯,甲基丙烯酸甲酯,丙烯酸乙酯,甲基 丙烯酸乙酯,丙烯酸丁酯,甲基丙烯酸丁酯,丙烯酸缩水甘油酯,甲 基丙烯酸缩水甘油酯,马来酸单乙酯,马来酸二乙酯,富马酸单甲酯, 富马酸二甲酯,衣康酸单甲酯和衣康酸二乙酯;不饱和羧酸的酰胺衍 生物,例如丙烯酰胺,甲基丙烯酰胺,马来酸的单酰胺,马来酸的二 酰胺,马来酸的N-单乙酰胺,马来酸的N,N-二乙酰胺,马来酸的N- 单丁酰胺,马来酸的N,N-二丁酰胺,富马酸的单酰胺,富马酸的二 酰胺,富马酸的N-单乙酰胺,富马酸的N,N-二乙酰胺,富马酸的N- 单丁酰胺和富马酸的N,N-二丁酰胺;不饱和羧酸的酰亚胺衍生物, 例如马来酰亚胺,N-丁基马来酰亚胺和N-苯基马来酰亚胺;以及不 饱和羧酸的金属盐,例如丙烯酸钠,甲基丙烯酸钠,丙烯酸钾和甲基 丙烯酸钾。
有利地,马来酸酐用作接枝单体。
步骤a)在任何混合设备中进行,例如在热塑性塑料工业中使用的 挤出机或混合机中进行。
关于含氟聚合物和不饱和单体的比例,按重量计,含氟聚合物的 比例有利地为90至99.9%,不饱和单体相应地为0.1至10%。优选 地,含氟聚合物的比例为92至99.0%,而不饱和单体相应地为1.0 至8%,更优选地为1至5重量%的不饱和接枝单体。
关于步骤c),将在步骤b)之后回收的产物有利地包装在聚乙烯袋 中,将空气排出,然后将袋封闭。关于辐射方法,同样可以使用电子 辐射(通常称为β辐射)和光子辐射(通常称为γ辐射)。有利地,剂量 在2至6Mrad之间,优选地在3至5Mrad之间。
关于步骤d),可以通过任何方式除去未接枝的单体。相对于在步 骤c)开始时存在的单体,接枝单体的比例为50至100%。可以用对 含氟聚合物和接枝官能团呈惰性的溶剂进行洗涤操作。例如,当将马 来酸酐用于接枝时,可以将氯苯用于洗涤。也可以更简单地对步骤 c)中回收的产物进行真空脱气。
纤维:
可用于形成短切纤维束的纤维包括但不限于碳纤维,玻璃纤维, 芳族聚酰胺纤维,聚酰胺纤维,PEEK或PEKK纤维,碳纳米管,以 及它们的混合物。
短切纤维束已经被上胶。上胶剂不仅用于将纤维粘附到束中的其 他纤维上,还用作短切纤维束与聚合物基质的相容剂。
PYROFILTM短切纤维可从三菱人造丝有限公司 (MitsubishiRayonCo.,Ltd.)购得。标准的小丝束PYROFILTM短切纤 维可以包含选自下组的上胶剂:聚氨酯、聚酰胺、环氧树脂、水或水 分散性聚酰胺。大多数制造商没有描述他们使用的上胶剂类型,因此 尚不清楚使用的是哪种上胶剂。进一步的细节以及标准大丝束和中模 量丝束碳纤维如下详细描述:
短切碳纤维也可从立邦高分子产业有限公司 (NipponPolymerSangyoCo.,Ltd.)获得。可以购买已上胶的碳纤维, 上胶剂包括聚氨酯,环氧树脂和聚氨酯,环氧树脂,烯烃,丙烯酸类, 或丙烯酸类和聚氨酯。上胶剂可具有各种浓度。立邦高分子产业有限 公司的上胶剂可以是1.5重量%、3重量%或5重量%的上胶剂。下 表提供了有关立邦高分子产业有限公司的更多详细信息:
最后应说明的是:以上所述实施例,仅为本发明的具体实施方式, 用以说明本发明技术方案,而非对其限制,本发明的保护范围并不局 限于此,尽管参照前述实施例对本发明进行了详细的说明,本领域的 普通技术人员应当理解:任何熟悉本技术领域的技术人员在本发明揭 露的技术范围内,其依然可以对前述实施例所记载的技术方案进行修 改或可轻易想到变化,或者对其中部分技术特征进行等同替换;而这 些修改、变化或者替换,并不使相应技术方案的本质脱离本发明实施 例技术方案的精神和范围,都应涵盖在本发明的保护范围之内。因此, 本发明的保护范围应所述以权利要求的保护范围为准。
Claims (7)
1.一种聚偏二氟乙烯的增强配混物,其特征在于:包含如下步骤:
S1:在低于35℃的温度下,取长度小于25毫米的短切多组分纤维10-25%与包含羧酸类接枝的官能化的含氟聚合物的基质混合合成聚合物;
S2:加热,将温度保持在60-90℃,将聚合物中的水分散性磺基聚酯去除,形成配混物。
2.根据权利要求1所述的一种聚偏二氟乙烯的增强配混物,其特征在于:所述短切多组分纤维包含至少一种水分散性磺基聚酯和至少一种与所述水分散性磺基聚酯不混溶的水不分散性合成聚合物。
3.根据权利要求2所述的一种聚偏二氟乙烯的增强配混物,其特征在于:所述接枝的含氟聚合物是均聚物,或者具有大于50重量%的偏二氟乙烯的共聚物,或者包含乙烯和四氟乙烯单体单元的共聚物。
4.根据权利要求3所述的一种聚偏二氟乙烯的增强配混物,其特征在于:所述含氟聚合物是热塑性均聚物和共聚物,所述共聚物具有按重量计大于90%重量的含氟单体单元。
5.根据权利要求4所述的一种聚偏二氟乙烯的增强配混物,其特征在于:可用于形成含氟聚合物的含氟单体包括但不限于:偏二氟乙烯、四氟乙烯、三氟乙烯、氯三氟乙烯、六氟丙烯、氟乙烯、六氟异丁烯、全氟丁基乙烯、五氟丙烯、3,3,3-三氟1丙烯、2三氟甲基3,3,3三氟丙烯、氟化乙烯基醚、包括全氟甲基醚、全氟乙基乙烯基醚、全氟丙基乙烯基醚、全氟丁基乙烯基醚、长链全氟化乙烯基醚、氟化间二氧化环戊烯、C4和更高碳的部分氟化或全氟化的α烯烃、C3和更高碳的部分氟化或全氟化的环烯烃。
6.根据权利要求1所述的一种聚偏二氟乙烯的增强配混物,其特征在于:所述羧酸类接枝的含氟聚合物包含马来酸酐作为接枝官能团。
7.根据权利要求1所述的一种聚偏二氟乙烯的增强配混物,其特征在于:所述短切多组分纤维选自下组:碳纤维,玻璃纤维,芳族聚酰胺纤维,聚酰胺纤维,PEKK,PEEK,二氧化硅纤维,碳纳米管,以及它们的混合物。
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CN110891672A (zh) * | 2017-07-14 | 2020-03-17 | 阿科玛股份有限公司 | 基于高强度聚偏二氟乙烯的增强配混物 |
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CN110891672A (zh) * | 2017-07-14 | 2020-03-17 | 阿科玛股份有限公司 | 基于高强度聚偏二氟乙烯的增强配混物 |
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