JP5284280B2 - 向上した低温衝撃性を有するフッ化ビニリデンコポリマー組成物 - Google Patents
向上した低温衝撃性を有するフッ化ビニリデンコポリマー組成物 Download PDFInfo
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- JP5284280B2 JP5284280B2 JP2009547240A JP2009547240A JP5284280B2 JP 5284280 B2 JP5284280 B2 JP 5284280B2 JP 2009547240 A JP2009547240 A JP 2009547240A JP 2009547240 A JP2009547240 A JP 2009547240A JP 5284280 B2 JP5284280 B2 JP 5284280B2
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- Prior art keywords
- vinylidene fluoride
- vinyl ether
- copolymer composition
- reactor
- perfluoroalkyl vinyl
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- -1 perfluoroalkyl ethers Chemical class 0.000 claims abstract description 49
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 6
- 239000004816 latex Substances 0.000 claims description 4
- 229920000126 latex Polymers 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- CSJWOWRPMBXQLD-UHFFFAOYSA-N perfluoromethylvinylether group Chemical group FC(=C(C(F)(F)F)F)OC(=C(F)C(F)(F)F)F CSJWOWRPMBXQLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 abstract description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000003999 initiator Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 238000007792 addition Methods 0.000 description 18
- 239000004094 surface-active agent Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000003607 modifier Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002519 antifouling agent Substances 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 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 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
a)フッ化ビニリデンモノマー単位85〜98モル%と、
b)1種または複数種のパーフルオロアルキルビニルエーテルモノマー単位2〜15モル%と
から本質的になる不均一系コポリマー組成物に関する。
CF2=CF−O−Rf
(式中、−Rfは、−CF3、−CF2CF3、または−CF2CF2CF3から選択される1種または複数種のパーフルオロアルキルである)を有するパーフルオロアルキルビニルエーテルである。従って、パーフルオロアルキル基は、例えばパーフルオロメチルビニルエーテル(PMVE)、パーフルオロエチルビニルエーテル(PEVE)、および/またはパーフルオロプロピルビニル(PPVE)である。好ましいパーフルオロアルキルビニルエーテルはPMVEである。
(a)水性混合物を形成するために、簡便ないずれかの順序で、脱イオン水、界面活性剤、任意に防汚剤、任意に緩衝剤、任意に分子量調整剤を反応器に装入する;
(b)反応器から空気を除去する;
(c)重合を起こすのに十分な熱および攪拌を提供する;
(d)フッ化ビニリデンで反応器を反応圧力にする;
(e)ラジカル開始剤を添加して、重合を開始する;
(f)フッ化ビニリデンを供給して所望の反応圧力を維持することによって、重合を続け、更なる開始剤、熱、および攪拌を必要に応じて用いて、反応の進行を続ける;
(g)計画装入総量の内の50〜90重量%となるように選択される量のフッ化ビニリデンを反応器に供給した後、所望の最終的な選択ポリマー組成物が得られる量でパーフルオロアルキルビニルエーテルモノマーを反応器に供給する;
(h)フッ化ビニリデンの計画装入総量の内の残りを反応器に供給する;
(i)モノマー供給を止めた後に、残りのモノマーを消費するために、供給後期間を任意に設けることができる。この供給後期間は、残りのモノマーの消費を助けるための更なるラジカル開始剤の添加など、いくつかの反応成分の更なる添加を含み得る;
(j)反応器から余分なガスを抜く;
(k)分子量調整剤、緩衝剤、およびラジカル開始剤の添加は、所望の分子量プロファイル、酸性度プロファイル、およびプロセス速度が得られるように、反応器の最初の充填中、反応中、または供給後期間中のいずれかの時点で任意に行うことができる。空気の除去、界面活性剤の添加、防汚剤の添加、熱および攪拌の適用は、使用される装置に対して反応の開始が最適化されるように、重合が開始される前の様々な時点で任意に行うことができる;
(l)反応後、ラテックス状のコポリマー組成物を使用してもよいし、あるいは塩添加、機械的分離、または乾燥などの公知の分離法によって、反応混合物の残りから組成物を任意に単離してもよい;
(m)単離コポリマー組成物を任意に、洗浄などによってさらに精製し、乾燥させて粉末とし、任意にペレットなどの簡便な形状へとさらに加工することができる;
(n)コポリマーを用いてコーティングを形成することができ、あるいは溶融プロセスなどによってシート、フィルム、異形材、または最終製品へと加工することができる。
実施例1〜6は、一般的な重合および単離方法に従った。これらの実施例では、異なる量の酢酸エチル溶液とパーフルオロアルキルビニルエーテルを使用した。使用したパーフルオロアルキルビニルエーテルはPMVEであった。使用された酢酸エチル溶液とPMVEの量は、測定された溶融粘度、融点、および得られた乾燥粉末の組成と共に表Iに示す。
Claims (9)
- a)フッ化ビニリデンモノマー単位85〜98モル%と、
b)次式:
CF2=CF−O−Rf
(式中、−Rfは、
−CF3、
−CF2CF3、および−CF2CF2CF3からなる群から選択される1種または複数種のパーフルオロアルキル基である)
で表わされる1種または複数種のパーフルオロアルキルビニルエーテルモノマー単位2〜15モル%と
から本質的になるコポリマー組成物であって、前記コポリマーが不均一系であり、かつ156℃以上の融点を有する、コポリマー組成物。 - フッ化ビニリデンモノマー単位90〜97モル%およびパーフルオロアルキルビニルエーテルモノマー単位3〜10モル%を含む、請求項1に記載のコポリマー組成物。
- フッ化ビニリデンモノマー単位91〜96モル%およびパーフルオロアルキルビニルエーテルモノマー単位4〜9モル%を含む、請求項2に記載のコポリマー組成物。
- フッ化ビニリデンモノマー単位91〜95モル%およびパーフルオロアルキルビニルエーテルモノマー単位5〜9モル%を含む、請求項3に記載のコポリマー組成物。
- 前記コポリマーが160℃以上の融点を有する、請求項4に記載のコポリマー組成物。
- 前記パーフルオロアルキルビニルエーテルがパーフルオロメチルビニルエーテルである、請求項1に記載のコポリマー組成物。
- ラテックスの形にある、請求項1に記載のコポリマー組成物。
- 乾燥粉末の形にある、請求項1に記載のコポリマー組成物。
- シート、フィルム、異形材、または完成品の形にある、請求項1に記載のコポリマー組成物。
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US11/698,387 US7700700B2 (en) | 2007-01-26 | 2007-01-26 | Vinylidene fluoride copolymer composition with improved low-temperature impact properties |
US11/698,387 | 2007-01-26 | ||
PCT/US2007/086746 WO2008094355A1 (en) | 2007-01-26 | 2007-12-07 | Vinylidene fluoride copolymer composition with improved low-temperature impact properties |
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EP3256528B1 (en) * | 2015-02-09 | 2021-04-07 | Arkema, Inc. | Heterogeneous, co-continuous copolymers of vinylidene fluoride |
JP6751722B2 (ja) | 2015-03-11 | 2020-09-09 | アーケマ・インコーポレイテッド | フッ化ビニリデン含有ポリマーの高耐衝撃性ブレンド物 |
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US3136745A (en) | 1961-06-23 | 1964-06-09 | Du Pont | Elastomeric copolymers of vinylidene fluoride and perfluoroalkyl perfluorovinyl ethers |
US3235537A (en) | 1961-06-23 | 1966-02-15 | Du Pont | Fluorine containing terpolymer of a perfluorovinyl ether, vinylidene fluoride and a monomer of the structure cfx=cfy |
US3929934A (en) * | 1973-11-19 | 1975-12-30 | Du Pont | Novel fluoroelastomers in powder form |
JPS57109810A (en) * | 1980-12-26 | 1982-07-08 | Asahi Glass Co Ltd | Copolymer giving fluorine-containing elastomer with cold and alcohol resistance |
JPS5895753A (ja) * | 1981-12-02 | 1983-06-07 | Daikin Ind Ltd | 加圧定着用カプセル化トナ− |
FR2610325B1 (fr) * | 1987-02-03 | 1989-10-06 | Atochem | Copolymere heterogene de fluorure de vinylidene et de chlorotrifluoroethylene. procede de fabrication du copolymere heterogene |
US5093427A (en) * | 1990-05-10 | 1992-03-03 | Atochem North America, Inc. | Copolymers of vinylidene fluoride and hexafluoropropylene and process for preparing the same |
US6821675B1 (en) * | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
JP2000057847A (ja) * | 1998-08-03 | 2000-02-25 | Teijin Ltd | ポリマー電解質膜及び複合型ポリマー電解質膜 |
IT1307756B1 (it) * | 1999-02-05 | 2001-11-19 | Ausimont Spa | Polimeri elettroliti per batterie ricaricabili al litio. |
MXPA01008840A (es) * | 1999-03-02 | 2002-05-14 | Du Pont | Metodo de polimerizacion de radicales libres para copolimeros fluorados. |
JP2001135353A (ja) * | 1999-11-02 | 2001-05-18 | Nippon Mektron Ltd | リチウムイオン電池用ゲル電解質 |
JP2003527468A (ja) * | 1999-12-29 | 2003-09-16 | ハイドロ−ケベック | 低いTgを有し、ビニリデンフルオライドを主成分とし、かつテトラフルオロエチレンもシロキサン基も含まないフルオロエラストマー |
KR100416471B1 (ko) | 1999-12-30 | 2004-01-31 | 삼성아토피나주식회사 | 폴리머 중합용 신규 메탈로센 담지촉매 |
FR2804438A1 (fr) | 2000-01-31 | 2001-08-03 | Atofina | Procede de preparation d'un polymere fluore par polymerisation radicalaire d'une emulsion aqueuse |
JP4283431B2 (ja) * | 2000-10-31 | 2009-06-24 | 株式会社日立製作所 | 液晶表示装置 |
CA2446014A1 (en) * | 2001-05-02 | 2002-11-07 | 3M Innovative Properties Company | Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers |
FR2842203A1 (fr) | 2002-07-12 | 2004-01-16 | Atofina | Procede de fabrication du polymere du fluorure de vinylidene |
FR2896250B1 (fr) * | 2006-01-13 | 2012-08-17 | Arkema | Agent d'extrusion a base de pvdf |
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