WO2022181827A1 - 含フッ素共重合体 - Google Patents
含フッ素共重合体 Download PDFInfo
- Publication number
- WO2022181827A1 WO2022181827A1 PCT/JP2022/008443 JP2022008443W WO2022181827A1 WO 2022181827 A1 WO2022181827 A1 WO 2022181827A1 JP 2022008443 W JP2022008443 W JP 2022008443W WO 2022181827 A1 WO2022181827 A1 WO 2022181827A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- containing copolymer
- units
- polymerization
- present disclosure
- Prior art date
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 131
- 229920001577 copolymer Polymers 0.000 title claims abstract description 129
- 239000011737 fluorine Substances 0.000 title claims abstract description 128
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 126
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical group FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 36
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 29
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000155 melt Substances 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims description 38
- 238000012546 transfer Methods 0.000 claims description 17
- 239000011247 coating layer Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 235000012438 extruded product Nutrition 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 62
- 238000012360 testing method Methods 0.000 description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 238000000034 method Methods 0.000 description 40
- 239000008188 pellet Substances 0.000 description 35
- -1 polytetrafluoroethylene Polymers 0.000 description 32
- 239000007789 gas Substances 0.000 description 31
- 238000000465 moulding Methods 0.000 description 26
- 239000010410 layer Substances 0.000 description 23
- 230000035699 permeability Effects 0.000 description 23
- 238000001125 extrusion Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 150000002978 peroxides Chemical class 0.000 description 20
- 239000010408 film Substances 0.000 description 19
- 230000000977 initiatory effect Effects 0.000 description 19
- 239000007788 liquid Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 230000006835 compression Effects 0.000 description 15
- 238000007906 compression Methods 0.000 description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000011255 nonaqueous electrolyte Substances 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000012856 packing Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000011162 core material Substances 0.000 description 12
- 238000003682 fluorination reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 230000008054 signal transmission Effects 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000004978 peroxycarbonates Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UJZCJVSSNLSCSR-UHFFFAOYSA-N (15,16,16,17,17,18,18,19,19,20,20-undecachloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,22,22,22-triacontafluorodocosanoyl) 15,16,16,17,17,18,18,19,19,20,20-undecachloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14 Chemical compound FC(F)(F)CC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(F)(Cl)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)CC(F)(F)F UJZCJVSSNLSCSR-UHFFFAOYSA-N 0.000 description 1
- HBGQVKNZGOFLRH-UHFFFAOYSA-N (3,3-dichloro-2,2,4,4,4-pentafluorobutanoyl) 3,3-dichloro-2,2,4,4,4-pentafluorobutaneperoxoate Chemical compound FC(F)(F)C(Cl)(Cl)C(F)(F)C(=O)OOC(=O)C(F)(F)C(Cl)(Cl)C(F)(F)F HBGQVKNZGOFLRH-UHFFFAOYSA-N 0.000 description 1
- QFKDUYDESCLRNT-UHFFFAOYSA-N (4,5,5-trichloro-2,2,3,3,4,6,6,6-octafluorohexanoyl) 4,5,5-trichloro-2,2,3,3,4,6,6,6-octafluorohexaneperoxoate Chemical compound FC(F)(F)C(Cl)(Cl)C(F)(Cl)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(Cl)C(Cl)(Cl)C(F)(F)F QFKDUYDESCLRNT-UHFFFAOYSA-N 0.000 description 1
- HLTAACNVRUAPLX-UHFFFAOYSA-N (6,6,7,7-tetrachloro-2,2,3,3,4,4,5,5,8,8,8-undecafluorooctanoyl) 6,6,7,7-tetrachloro-2,2,3,3,4,4,5,5,8,8,8-undecafluorooctaneperoxoate Chemical compound FC(F)(F)C(Cl)(Cl)C(Cl)(Cl)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)(Cl)C(Cl)(Cl)C(F)(F)F HLTAACNVRUAPLX-UHFFFAOYSA-N 0.000 description 1
- IDSJUBXWDMSMAR-UHFFFAOYSA-N (7,8,8,9,9-pentachloro-2,2,3,3,4,4,5,5,6,6,7,10,10,10-tetradecafluorodecanoyl) 7,8,8,9,9-pentachloro-2,2,3,3,4,4,5,5,6,6,7,10,10,10-tetradecafluorodecaneperoxoate Chemical compound FC(F)(F)C(Cl)(Cl)C(Cl)(Cl)C(F)(Cl)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(F)(F)F IDSJUBXWDMSMAR-UHFFFAOYSA-N 0.000 description 1
- GWTYBAOENKSFAY-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-(1,2,2-trifluoroethenoxy)ethane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)F GWTYBAOENKSFAY-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- LNTDXONIQLFHFG-UHFFFAOYSA-N 1-ethenoxy-2-methylpropan-1-ol Chemical compound CC(C)C(O)OC=C LNTDXONIQLFHFG-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- FLFWDKGWSOCXQK-UHFFFAOYSA-N 1-ethenoxycyclohexan-1-ol Chemical compound C=COC1(O)CCCCC1 FLFWDKGWSOCXQK-UHFFFAOYSA-N 0.000 description 1
- GBOWGKOVMBDPJF-UHFFFAOYSA-N 1-fluoro-3-(trifluoromethyl)benzene Chemical compound FC1=CC=CC(C(F)(F)F)=C1 GBOWGKOVMBDPJF-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
- LWJHSQQHGRQCKO-UHFFFAOYSA-N 1-prop-2-enoxypropane Chemical compound CCCOCC=C LWJHSQQHGRQCKO-UHFFFAOYSA-N 0.000 description 1
- JUTIIYKOQPDNEV-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl 2,2,3,3,4,4,4-heptafluorobutaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)F JUTIIYKOQPDNEV-UHFFFAOYSA-N 0.000 description 1
- QLJQYPFKIVUSEF-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanoyl 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QLJQYPFKIVUSEF-UHFFFAOYSA-N 0.000 description 1
- LFCQGZXAGWRTAL-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoyl 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LFCQGZXAGWRTAL-UHFFFAOYSA-N 0.000 description 1
- YQIZLPIUOAXZKA-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YQIZLPIUOAXZKA-UHFFFAOYSA-N 0.000 description 1
- BECCBTJLCWDIHG-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononanoyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BECCBTJLCWDIHG-UHFFFAOYSA-N 0.000 description 1
- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- GENYBPRYOMJDAG-UHFFFAOYSA-N 3,4-dioctylphthalic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C(C(O)=O)=C1CCCCCCCC GENYBPRYOMJDAG-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- OJPSFJLSZZTSDF-UHFFFAOYSA-N 3-ethoxyprop-1-ene Chemical compound CCOCC=C OJPSFJLSZZTSDF-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 1
- PRQREXSTQVWUGV-UHFFFAOYSA-N 6-ethenoxy-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(=O)OC=C PRQREXSTQVWUGV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- ZHIUCPNDVATEDB-TWTPFVCWSA-N ethenyl (2e,4e)-hexa-2,4-dienoate Chemical compound C\C=C\C=C\C(=O)OC=C ZHIUCPNDVATEDB-TWTPFVCWSA-N 0.000 description 1
- WGXGKXTZIQFQFO-CMDGGOBGSA-N ethenyl (e)-3-phenylprop-2-enoate Chemical compound C=COC(=O)\C=C\C1=CC=CC=C1 WGXGKXTZIQFQFO-CMDGGOBGSA-N 0.000 description 1
- IYNRVIKPUTZSOR-HWKANZROSA-N ethenyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC=C IYNRVIKPUTZSOR-HWKANZROSA-N 0.000 description 1
- KYFYEPDVLXDDOM-UHFFFAOYSA-N ethenyl 1-hydroxycyclohexane-1-carboxylate Chemical compound C=COC(=O)C1(O)CCCCC1 KYFYEPDVLXDDOM-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- XMDWTZUMJSUCGR-UHFFFAOYSA-N ethenyl 2-hydroxy-2-methylpropanoate Chemical compound CC(C)(O)C(=O)OC=C XMDWTZUMJSUCGR-UHFFFAOYSA-N 0.000 description 1
- BLANBUKUVIWWGZ-UHFFFAOYSA-N ethenyl 2-hydroxyacetate Chemical compound OCC(=O)OC=C BLANBUKUVIWWGZ-UHFFFAOYSA-N 0.000 description 1
- KGVSOPFIFAGTSN-UHFFFAOYSA-N ethenyl 2-hydroxybutanoate Chemical compound CCC(O)C(=O)OC=C KGVSOPFIFAGTSN-UHFFFAOYSA-N 0.000 description 1
- KFDVEIXTDOVJKZ-UHFFFAOYSA-N ethenyl 2-hydroxypentanoate Chemical compound CCCC(O)C(=O)OC=C KFDVEIXTDOVJKZ-UHFFFAOYSA-N 0.000 description 1
- MPOGZNTVZCEKSW-UHFFFAOYSA-N ethenyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC=C MPOGZNTVZCEKSW-UHFFFAOYSA-N 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 1
- HUGGPHJJSYXCDJ-UHFFFAOYSA-N ethenyl undec-10-enoate Chemical compound C=CCCCCCCCCC(=O)OC=C HUGGPHJJSYXCDJ-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- VLAGSAGYAIGJSU-UHFFFAOYSA-N hexanoyl hexaneperoxoate Chemical compound CCCCCC(=O)OOC(=O)CCCCC VLAGSAGYAIGJSU-UHFFFAOYSA-N 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical class OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229920006120 non-fluorinated polymer Polymers 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009372 pisciculture Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 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
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D127/00—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
- H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
Definitions
- the present disclosure relates to fluorine-containing copolymers.
- U.S. Pat. No. 5,301,003 discloses (a) tetrafluoroethylene, (b) hexafluoropropylene in an amount of from about 4 to about 12 weight percent based on the weight of the terpolymer, and (c) about 0.5 weight percent based on the weight of the terpolymer.
- Terpolymers containing from to about 3% by weight of perfluoro(ethyl vinyl ether) or perfluoro(n-propyl vinyl ether), in copolymerized form, are described.
- a fluorine-containing copolymer containing tetrafluoroethylene units, hexafluoropropylene units and perfluoro(propyl vinyl ether) units wherein the content of hexafluoropropylene units is On the other hand, it is 4.10 to 5.20 mol%, the content of perfluoro (propyl vinyl ether) units is 0.53 to 0.86 mol% with respect to the total monomer units, and the temperature is 372 ° C.
- a fluorine-containing copolymer having a melt flow rate of 0.7 to 2.5 g/10 minutes is provided.
- the content of hexafluoropropylene units is preferably 4.35 to 4.97 mol % with respect to all monomer units.
- the content of perfluoro(propyl vinyl ether) units is preferably 0.66 to 0.78 mol % with respect to the total monomer units.
- a melt flow rate at 372° C. is preferably 0.7 to 2.0 g/10 minutes.
- the number of functional groups is preferably 50 or less per 10 6 carbon atoms in the main chain.
- an extrusion molded article or a transfer molded article containing the fluorine-containing copolymer there is provided an extrusion molded article or a transfer molded article containing the fluorine-containing copolymer.
- a covered electric wire that includes a covering layer containing the fluorine-containing copolymer.
- a molded article containing the fluorine-containing copolymer wherein the molded article is a sheet or a pipe.
- the fluorine-containing copolymer of the present disclosure contains tetrafluoroethylene (TFE) units, hexafluoropropylene (HFP) units and perfluoro(propyl vinyl ether) (PPVE) units.
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- PPVE perfluoro(propyl vinyl ether)
- Patent Document 1 proposes the above-described terpolymer as a fluorocarbon polymer that overcomes these drawbacks.
- Thick sheets of melt-processable fluororesin are generally manufactured by extruding fluororesin using an extruder.
- the molten fluororesin extruded from the extruder tends to be deformed easily by its own weight until it is cooled and solidified, so when trying to produce a thick sheet, it is difficult to produce a sheet with the desired thickness.
- thick sheets tend to be deformed more easily when a load is continuously applied for a long period of time than thin sheets.
- thick sheets are often used as machine parts, and are required to have high-temperature wear resistance, low water vapor permeability, and durability against repeated loads.
- the fluorine-containing copolymer By adjusting the contents of the HFP units and PPVE units of the fluorine-containing copolymer containing TFE units, HFP units and PPVE units, and the melt flow rate within a very limited range, the fluorine-containing copolymer It has been found that the self-weight deformation in the molten state can be suppressed, and furthermore, the repulsive force and compression set of a molded article obtained from such a fluorine-containing copolymer are improved. Therefore, the fluorocopolymer of the present disclosure is resistant to deformation even in a molten state, and a thick sheet having a uniform thickness can be easily obtained by using the fluorocopolymer of the present disclosure.
- the molded article obtained using the fluorine-containing copolymer of the present disclosure is resistant to deformation even when a load is continuously applied for a long period of time, and has abrasion resistance at 80 ° C., low water vapor permeability, and resistance to repeated loads. It is also very durable.
- the fluorine-containing copolymer of the present disclosure is less deformed under its own weight even in a molten state, even when it is molded into a thick pipe, the obtained pipe has a clean cross section and a uniform thickness. .
- the fluorocopolymer of the present disclosure is a melt-processable fluororesin.
- Melt processability means that the polymer can be melt processed using conventional processing equipment such as an extruder.
- the content of HFP units in the fluorine-containing copolymer is 4.10 to 5.20 mol %, preferably 4.11 mol % or more, more preferably 4.11 mol % or more, based on the total monomer units. 20 mol% or more, more preferably 4.30 mol% or more, particularly preferably 4.35 mol% or more, preferably 5.10 mol% or less, more preferably 5.00 mol% or less, more preferably 4.97 mol % or less. If the content of the HFP units is too high, the molded article obtained by molding the fluorocopolymer tends to deform when a load is continuously applied for a long period of time, and also has low water vapor permeability. become inferior. If the content of HFP units is too low, the molded article obtained by molding the fluorine-containing copolymer will be inferior in wear resistance at 80°C.
- the content of PPVE units in the fluorine-containing copolymer is 0.53 to 0.86 mol %, preferably 0.54 mol % or more, more preferably 0.54 mol % or more, based on the total monomer units. 57 mol % or more, more preferably 0.60 mol % or more, particularly preferably 0.63 mol % or more, most preferably 0.66 mol % or more, preferably 0.84 mol % %, more preferably 0.82 mol % or less, still more preferably 0.80 mol % or less, and particularly preferably 0.78 mol % or less.
- the fluorine-containing copolymer is less likely to deform even in a molten state, and by molding such a fluorine-containing copolymer, a thick sheet with a uniform thickness can be easily produced. can get to
- the molded article obtained using such a fluorine-containing copolymer is resistant to deformation even when a load is continuously applied for a long period of time, and has abrasion resistance at 80°C, low water vapor permeability, and resistance to repeated loads. It is also excellent in durability. If the PPVE unit content is too low, the molded article obtained by molding the fluorine-containing copolymer will be inferior in wear resistance at 80°C.
- the content of TFE units in the fluorine-containing copolymer is preferably 93.94 to 95.37 mol%, more preferably 94.06 mol% or more, and still more preferably, based on the total monomer units. is 94.18 mol% or more, still more preferably 94.23 mol% or more, particularly preferably 94.25 mol% or more, more preferably 95.32 mol% or less, still more preferably It is 95.20 mol % or less, more preferably 95.07 mol % or less, and particularly preferably 94.99 mol % or less. Also, the content of TFE units may be selected so that the total content of HFP units, PPVE units, TFE units and other monomer units is 100 mol %.
- the fluorine-containing copolymer of the present disclosure contains the above three monomer units, even if it is a copolymer containing only the above three monomer units, the above three It may be a copolymer containing monomeric units and other monomeric units.
- Other monomers are not particularly limited as long as they are copolymerizable with TFE, HFP and PPVE, and may be fluoromonomers or fluorine-free monomers.
- Fluorine-free monomers include hydrocarbon-based monomers copolymerizable with TFE, HFP and PPVE.
- hydrocarbon-based monomers include alkenes such as ethylene, propylene, butylene, and isobutylene; alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; vinyl acetate, vinyl propionate, n- Vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl benzoate , vinyl para-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate
- the non-fluorine-containing monomer may also be a functional group-containing hydrocarbon-based monomer copolymerizable with TFE, HFP and PPVE.
- functional group-containing hydrocarbon monomers include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; glycidyl group-containing monomers such as glycidyl vinyl ether and glycidyl allyl ether.
- fluorine-free monomers fluorine-free monomers having an amino group such as aminoalkyl vinyl ether and aminoalkyl allyl ether; fluorine-free monomers having an amide group such as (meth)acrylamide and methylolacrylamide; bromine-containing olefins, iodine-containing olefins, bromine-containing vinyl ethers, iodine-containing vinyl ethers; non-fluorine-containing monomers having a nitrile group;
- the content of other monomer units in the fluorine-containing copolymer of the present disclosure is preferably 0 to 1.43 mol%, more preferably 1.0 mol%, based on the total monomer units. or less, more preferably 0.5 mol % or less, and particularly preferably 0.1 mol % or less.
- the melt flow rate (MFR) of the fluorine-containing copolymer is 0.7 to 2.5 g/10 minutes, preferably 0.8 g/10 minutes or more, more preferably 0.9 g/10 minutes or more. more preferably 1.0 g/10 min or more, preferably 2.4 g/10 min or less, more preferably 2.3 g/10 min or more, still more preferably 2.2 g/10 min or less , particularly preferably 2.1 g/10 minutes or less, and most preferably 2.0 g/10 minutes or less.
- MFR of the fluorine-containing copolymer is within the above range, the fluorine-containing copolymer is less likely to be deformed even in a molten state. can be easily obtained.
- the melt flow rate is measured in accordance with ASTM D-1238 using a melt indexer G-01 (manufactured by Toyo Seiki Seisakusho) at 372°C under a load of 5 kg from a die with an inner diameter of 2 mm and a length of 8 mm. The value is given as the mass of polymer that flows out per 10 minutes (g/10 minutes).
- the MFR can be adjusted by adjusting the type and amount of the polymerization initiator and the type and amount of the chain transfer agent used when polymerizing the monomers.
- the fluorocopolymer of the present disclosure may or may not have a functional group.
- the functional group is a functional group present at the main chain end or side chain end of the fluorine-containing copolymer, and a functional group present in the main chain or side chain.
- the number of functional groups per 10 6 carbon atoms in the main chain of the fluorine-containing copolymer is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and particularly preferably 20. or less, and most preferably less than 15.
- the number of functional groups of the fluorine-containing copolymer is within the above range, it is possible to obtain a molded article from which fluorine ions are less likely to be eluted in a chemical solution such as hydrogen peroxide solution.
- the number of —CF 2 H groups per 10 6 carbon atoms in the main chain of the fluorine-containing copolymer is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less.
- Infrared spectroscopic analysis can be used to identify the types of functional groups and measure the number of functional groups.
- the number of functional groups is measured by the following method.
- the fluorine-containing copolymer is cold-pressed to form a film having a thickness of 0.25 to 0.30 mm.
- This film is analyzed by Fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of the fluorine-containing copolymer, and the difference spectrum from the completely fluorinated base spectrum in which no functional groups are present. From the absorption peak of the specific functional group appearing in this difference spectrum, the number N of functional groups per 1 ⁇ 10 6 carbon atoms in the fluorine-containing copolymer is calculated according to the following formula (A).
- N I ⁇ K/t (A) I: Absorbance K: Correction coefficient t: Film thickness (mm)
- Table 1 shows absorption frequencies, molar extinction coefficients and correction factors for some functional groups. Also, the molar extinction coefficient was determined from the FT-IR measurement data of the low-molecular-weight model compound.
- the absorption frequencies of —CH 2 CF 2 H, —CH 2 COF, —CH 2 COOH, —CH 2 COOCH 3 and —CH 2 CONH 2 are shown in the table, respectively, —CF 2 H, —COF and —COOH free.
- the absorption frequency of -COOH bonded, -COOCH 3 and -CONH 2 is several tens of Kaiser (cm -1 ) lower than that of -CONH 2 .
- the number of functional groups of —COF is determined from the number of functional groups obtained from the absorption peak at an absorption frequency of 1883 cm ⁇ 1 due to —CF 2 COF and from the absorption peak at an absorption frequency of 1840 cm ⁇ 1 due to —CH 2 COF. It is the sum of the number of functional groups.
- the number of -CF 2 H groups can also be obtained from the peak integration value of -CF 2 H groups by performing 19 F-NMR measurement using a nuclear magnetic resonance apparatus at a measurement temperature of (the melting point of the polymer +20) °C. can be done.
- the functional group is a functional group present at the main chain end or side chain end of the fluorine-containing copolymer, and a functional group present in the main chain or side chain.
- the functional group is introduced into the fluorocopolymer by, for example, a chain transfer agent or a polymerization initiator used in producing the fluorocopolymer.
- a chain transfer agent for example, an alcohol is used as a chain transfer agent, or a peroxide having a structure of —CH 2 OH is used as a polymerization initiator, —CH 2 OH is introduced at the main chain end of the fluorine-containing copolymer. .
- the functional group is introduced into the side chain end of the fluorine-containing copolymer.
- a fluorine-containing copolymer having the number of functional groups within the above range can be obtained by subjecting the fluorine-containing copolymer having such functional groups to treatment such as wet heat treatment and fluorination treatment.
- the fluorocopolymer of the present disclosure is preferably subjected to wet heat treatment or fluorination treatment, more preferably fluorination treatment.
- the fluorine-containing copolymer of the present disclosure also preferably has a —CF 3 terminal group.
- the melting point of the fluorine-containing copolymer is preferably 255-285°C, more preferably 263-277°C.
- the fluorine-containing copolymer is more resistant to deformation even in a molten state.
- a fluorine-containing copolymer having a melting point within the above range a thick sheet with a uniform thickness can be obtained more easily, and even when a load is continuously applied for a long period of time, the sheet will be deformed further. It is possible to obtain a molded article which is difficult to be worn, has 80° C. wear resistance, low water vapor permeability, and is more excellent in durability against repeated loads.
- the melting point can be measured using a differential scanning calorimeter [DSC].
- the fluorine-containing copolymer of the present disclosure preferably has a water vapor permeability of 13.5 g ⁇ cm/m 2 or less, more preferably 13.0 g ⁇ cm/m 2 or less. Since the water vapor transmission rate is within the above range, when the fluorine-containing copolymer of the present disclosure is used to obtain molded articles such as sheets, tubes, pipes, joints, flowmeter bodies, bottles, nuts, etc., the outside air It is possible to sufficiently suppress the permeation of water such as water vapor inside the molded body.
- the fluorine-containing copolymer of the present disclosure when used to obtain a molded product such as a gasket or packing and is applied to a non-aqueous electrolyte battery, it is possible to prevent water vapor from permeating from the outside into the non-aqueous electrolyte battery. can be suppressed, and deterioration and shortening of the battery performance of the non-aqueous electrolyte battery can be suppressed.
- the amount of eluted fluorine ions detected in an immersion test in hydrogen peroxide water is preferably 4.0 ppm or less, more preferably 3.0 ppm or less, on a mass basis. , more preferably 2.8 ppm or less.
- a molded body is obtained using the fluorocopolymer of the present disclosure, and a piping member used for transporting the chemical liquid, and a flow meter frame including a flow path for the chemical liquid in the flow meter.
- the immersion test in hydrogen peroxide water is performed by using a fluorine-containing copolymer to prepare a test piece having a weight equivalent to 10 molded articles (15 mm ⁇ 15 mm ⁇ 0.2 mm). and 15 g of a 3% by mass aqueous hydrogen peroxide solution are placed in a constant temperature bath at 95° C. and allowed to stand for 20 hours.
- the fluorine-containing copolymer of the present disclosure can be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
- conditions such as temperature and pressure, polymerization initiator, chain transfer agent, solvent and other additives can be appropriately set according to the desired composition and amount of the fluorine-containing copolymer. .
- an oil-soluble radical polymerization initiator or a water-soluble radical initiator can be used as the polymerization initiator.
- Oil-soluble radical polymerization initiators may be known oil-soluble peroxides, for example, Dialkyl peroxycarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate; Peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate; Dialkyl peroxides such as di-t-butyl peroxide; Di[fluoro (or fluorochloro) acyl] peroxides; etc. are typical examples.
- Dialkyl peroxycarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate
- Peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate
- Dialkyl peroxides such as di-
- Di[fluoro(or fluorochloro)acyl] peroxides include diacyl represented by [(RfCOO)-] 2 (Rf is a perfluoroalkyl group, ⁇ -hydroperfluoroalkyl group or fluorochloroalkyl group) peroxides.
- Di[fluoro(or fluorochloro)acyl] peroxides include, for example, di( ⁇ -hydro-dodecafluorohexanoyl) peroxide, di( ⁇ -hydro-tetradecafluoroheptanoyl) peroxide, di( ⁇ -hydro-hexadecafluorononanoyl)peroxide, di(perfluorobutyryl)peroxide, di(perfluoropareryl)peroxide, di(perfluorohexanoyl)peroxide, di(perfluoroheptanoyl)peroxide oxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di( ⁇ -chloro-hexafluorobutyryl) peroxide, di( ⁇ -chloro-decafluorohexanoyl) peroxide, Di( ⁇ -chloro-tetrade
- the water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts, potassium salts, sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, etc. , t-butyl permaleate, t-butyl hydroperoxide and the like.
- a reducing agent such as sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.
- chain transfer agents examples include hydrocarbons such as ethane, isopentane, n-hexane and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetic esters such as ethyl acetate and butyl acetate; , ethanol, 2,2,2-trifluoroethanol and other alcohols; methyl mercaptan and other mercaptans; carbon tetrachloride, chloroform, methylene chloride, methyl chloride and other halogenated hydrocarbons; 3-fluorobenzotrifluoride and the like mentioned.
- the amount to be added may vary depending on the magnitude of the chain transfer constant of the compound used, but it is usually used in the range of 0.01 to 20 parts by weight per 100 parts by weight of the solvent.
- the molecular weight of the resulting fluorine-containing copolymer becomes too high, resulting in a desired melt flow rate.
- chain transfer agents can be used to control the molecular weight.
- the solvent examples include water, a mixed solvent of water and alcohol, and the like.
- the monomer used for the polymerization of the fluorine-containing copolymer of the present disclosure can also be used as a solvent.
- a fluorinated solvent may be used in addition to water.
- Hydrochlorofluoroalkanes such as CH 3 CClF 2 , CH 3 CCl 2 F, CF 3 CF 2 CCl 2 H, CF 2 ClCF 2 CFHCl; CF 2 ClCFClCF 2 CF 3 , CF 3 CFClCFClCF 3 , etc. chlorofluoroalkanes ; perfluoroalkanes such as perfluorocyclobutane , CF3CF2CF2CF3 , CF3CF2CF2CF2CF3 , CF3CF2CF2CF2CF2CF3 , etc. _ Among them, perfluoroalkanes are preferred.
- the amount of fluorine-based solvent to be used is preferably 10 to 100 parts by mass per 100 parts by mass of the solvent, from the viewpoint of suspendability and economy.
- the polymerization temperature is not particularly limited, and may be 0 to 100°C.
- the polymerization initiator may be reduced from 0 to It is preferred to employ a relatively low polymerization temperature, such as in the range of 35°C.
- the polymerization pressure is appropriately determined according to other polymerization conditions such as the type of solvent used, the amount of solvent, the vapor pressure, and the polymerization temperature, but usually it may be 0 to 9.8 MPaG.
- the polymerization pressure is preferably 0.1 to 5 MPaG, more preferably 0.5 to 2 MPaG, still more preferably 0.5 to 1.5 MPaG. Moreover, when the polymerization pressure is 1.5 MPaG or more, the production efficiency can be improved.
- Additives in polymerization include, for example, suspension stabilizers.
- the suspension stabilizer is not particularly limited as long as it is a conventionally known one, and methyl cellulose, polyvinyl alcohol and the like can be used.
- a suspension stabilizer is used, the suspended particles generated by the polymerization reaction are stably dispersed in the aqueous medium. Suspended particles are less likely to adhere to Therefore, since a reactor that can withstand high pressure can be used, polymerization can be performed under high pressure, and production efficiency can be improved.
- suspension stabilizer when polymerization is carried out without using a suspension stabilizer, if a SUS reaction tank that has not been subjected to an anti-adhesion treatment is used, suspended particles may adhere, resulting in a decrease in production efficiency.
- concentration of the suspension stabilizer in the aqueous medium can be appropriately adjusted depending on the conditions.
- the dry fluoropolymer may be recovered by coagulating the fluorine-containing copolymer contained in the aqueous dispersion, washing, and drying. Moreover, when the fluorine-containing copolymer is obtained as a slurry by the polymerization reaction, the slurry may be taken out from the reaction vessel, washed and dried to recover the dried fluoropolymer. By drying, the fluorine-containing copolymer can be recovered in the form of powder.
- the fluorine-containing copolymer obtained by polymerization may be molded into pellets.
- a molding method for molding into pellets is not particularly limited, and conventionally known methods can be used. For example, a method of melt extruding a fluorine-containing copolymer using a single-screw extruder, twin-screw extruder, or tandem extruder, cutting it into a predetermined length, and molding it into a pellet can be used.
- the extrusion temperature for melt extrusion must be changed according to the melt viscosity of the fluorine-containing copolymer and the production method, and is preferably from the melting point of the fluorine-containing copolymer +20°C to the melting point of the fluorine-containing copolymer +140°C.
- the method for cutting the fluorine-containing copolymer is not particularly limited, and conventionally known methods such as a strand cut method, a hot cut method, an underwater cut method, and a sheet cut method can be employed.
- the obtained pellets may be heated to remove volatile matter in the pellets (deaeration treatment).
- the obtained pellets may be treated by contacting them with warm water of 30-200°C, steam of 100-200°C, or hot air of 40-200°C.
- a fluorine-containing copolymer obtained by polymerization may be heated to a temperature of 100° C. or higher in the presence of air and water (wet heat treatment).
- wet heat treatment methods include a method in which an extruder is used to melt and extrude the fluorine-containing copolymer obtained by polymerization while supplying air and water.
- the thermally unstable functional groups such as —COF and —COOH of the fluorocopolymer can be converted to relatively thermally stable —CF 2 H, and the fluorocopolymer
- the conversion reaction to —CF 2 H can be promoted.
- contamination with alkali metal salts should be avoided.
- a fluorine-containing copolymer obtained by polymerization may be subjected to a fluorination treatment.
- the fluorination treatment can be carried out by contacting the unfluorinated fluorocopolymer with a fluorine-containing compound.
- thermally Functional groups such as —CF 2 H, which are relatively stable to
- the fluorine-containing compound is not particularly limited, but includes fluorine radical sources that generate fluorine radicals under fluorination treatment conditions.
- fluorine radical source include F 2 gas, CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, halogen fluoride (eg IF 5 , ClF 3 ), and the like.
- the fluorine radical source such as F 2 gas may have a concentration of 100%, but from the viewpoint of safety, it is preferable to mix it with an inert gas and dilute it to 5 to 50% by mass before use. It is more preferable to dilute to 30% by mass before use.
- the inert gas include nitrogen gas, helium gas, argon gas, etc. Nitrogen gas is preferable from an economical point of view.
- Conditions for the fluorination treatment are not particularly limited, and the melted fluorine-containing copolymer may be brought into contact with the fluorine-containing compound. It can be carried out at a temperature of 220°C, more preferably from 100 to 200°C.
- the fluorination treatment is generally carried out for 1 to 30 hours, preferably 5 to 25 hours.
- the fluorination treatment is preferably carried out by contacting a fluorine-containing copolymer that has not been fluorinated with fluorine gas ( F2 gas).
- a composition may be obtained by mixing the fluorine-containing copolymer of the present disclosure with other components, if necessary.
- Other components include fillers, plasticizers, processing aids, release agents, pigments, flame retardants, lubricants, light stabilizers, weather stabilizers, conductive agents, antistatic agents, ultraviolet absorbers, antioxidants, Foaming agents, fragrances, oils, softening agents, dehydrofluorination agents and the like can be mentioned.
- fillers include silica, kaolin, clay, organic clay, talc, mica, alumina, calcium carbonate, calcium terephthalate, titanium oxide, calcium phosphate, calcium fluoride, lithium fluoride, crosslinked polystyrene, potassium titanate, Examples include carbon, boron nitride, carbon nanotubes, glass fibers, and the like.
- the conductive agent include carbon black and the like.
- plasticizers include dioctylphthalic acid and pentaerythritol.
- processing aids include carnauba wax, sulfone compounds, low-molecular-weight polyethylene, fluorine-based aids, and the like.
- dehydrofluorination agents include organic oniums and amidines.
- polymers other than the fluorine-containing copolymers described above may be used as the other components.
- Other polymers include fluororesins, fluororubbers, and non-fluorinated polymers other than the above fluorocopolymers.
- Examples of the method for producing the composition include a method of dry mixing the fluorocopolymer and other components, or a method of premixing the fluorocopolymer and other components in a mixer, followed by kneading and melting. A method of melt-kneading with an extruder or the like can be mentioned.
- the fluorine-containing copolymer of the present disclosure or the composition described above can be used as a processing aid, molding material, etc., but is preferably used as a molding material.
- Aqueous dispersions, solutions, suspensions, and copolymer/solvent systems of the fluorocopolymers of the present disclosure are also available, which can be applied as coatings, encapsulated, impregnated, flowed into films. It can be used for spreading.
- the fluorine-containing copolymer of the present disclosure has the properties described above, it is preferably used as the molding material.
- a molded article may be obtained by molding the fluorine-containing copolymer of the present disclosure or the above composition.
- the method for molding the fluorine-containing copolymer or composition is not particularly limited, and injection molding, extrusion molding, compression molding, blow molding, transfer molding, roto molding, roto lining molding, and the like can be used. mentioned.
- extrusion molding, compression molding, or transfer molding is preferable, and extrusion molding or transfer molding is more preferable, and extrusion molding is even more preferable, because a molded product can be produced with high productivity.
- the molded body is preferably an extrusion molded body, a compression molded body, an injection molded body or a transfer molded body, and is more preferably an extrusion molded body or a transfer molded body because it can be produced with high productivity. More preferably, it is an extrudate.
- a beautiful molded article can be obtained by molding the fluorine-containing copolymer of the present disclosure by an extrusion molding method or a transfer molding method.
- Molded articles containing the fluorocopolymer of the present disclosure include, for example, nuts, bolts, joints, films, bottles, gaskets, wire coatings, tubes, hoses, pipes, valves, sheets, seals, packings, tanks, and rollers. , vessels, cocks, connectors, filter housings, filter cages, flow meters, pumps, wafer carriers, wafer boxes, and the like.
- the fluorine-containing copolymer of the present disclosure, the above composition, or the above molding can be used, for example, in the following applications.
- Films for food packaging, lining materials for fluid transfer lines used in food manufacturing processes, packings, sealing materials, and fluid transfer members for food manufacturing equipment such as sheets
- Drug stoppers for drugs, packaging films, lining materials for fluid transfer lines used in the process of manufacturing drugs, packings, sealing materials, and chemical liquid transfer members such as sheets
- Inner lining members for chemical tanks and piping in chemical plants and semiconductor factories O (square) rings, tubes, packings, valve core materials, hoses, sealing materials, etc. used in automobile fuel systems and peripheral devices; fuel transfer members such as hoses, sealing materials, etc.
- Coating and ink components such as coating rolls, hoses, tubes, and ink containers for coating equipment; Tubes for food and drink or tubes such as food and drink hoses, hoses, belts, packings, food and drink transfer members such as joints, food packaging materials, glass cooking equipment; Parts for transporting waste liquid such as tubes and hoses for transporting waste liquid; Parts for transporting high-temperature liquids, such as tubes and hoses for transporting high-temperature liquids; Steam piping members such as steam piping tubes and hoses; Anti-corrosion tape for piping such as tape to be wrapped around piping on ship decks; Various coating materials such as wire coating materials, optical fiber coating materials, transparent surface coating materials and back coating materials provided on the light incident side surface of photovoltaic elements of solar cells; Sliding members such as diaphragms of diaphragm pumps and various packings; Agricultural films, weather-resistant covers for various roofing materials and side walls; Interior materials used in the construction field, coating materials for glasses such
- fuel transfer members used in the fuel system of automobiles include fuel hoses, filler hoses, and evaporation hoses.
- the above-mentioned fuel transfer member can also be used as a fuel transfer member for sour gasoline-resistant fuel, alcohol-resistant fuel, and fuel containing gasoline additives such as methyl tert-butyl ether and amine-resistant fuel.
- the above drug stoppers and packaging films for drugs have excellent chemical resistance against acids and the like.
- an anticorrosive tape to be wound around chemical plant pipes can also be mentioned.
- Examples of the above molded bodies also include automobile radiator tanks, chemical liquid tanks, bellows, spacers, rollers, gasoline tanks, containers for transporting waste liquids, containers for transporting high-temperature liquids, fisheries and fish farming tanks, and the like.
- Examples of the molded article include automobile bumpers, door trims, instrument panels, food processing equipment, cooking equipment, water- and oil-repellent glass, lighting-related equipment, display panels and housings for OA equipment, illuminated signboards, displays, and liquid crystals.
- Members used for displays, mobile phones, printed circuit boards, electrical and electronic parts, miscellaneous goods, trash cans, bathtubs, unit baths, ventilation fans, lighting frames and the like are also included.
- the molded article containing the fluorocopolymer of the present disclosure is resistant to deformation even when a load is continuously applied for a long period of time, and has excellent wear resistance at 80°C, low water vapor permeability, and durability against repeated loads. Since it is excellent, it can be suitably used for nuts, bolts, joints, packings, valves, cocks, connectors, filter housings, filter cages, flowmeters, pumps, and the like. Among others, it can be suitably used as a piping member (especially valves and joints) used for transporting chemical liquids, and as a flowmeter frame provided with a chemical liquid flow path in a flowmeter.
- the piping member and the flow meter body of the present disclosure are resistant to deformation even when a load is continuously applied for a long period of time, and are excellent in 80° C. abrasion resistance, low water vapor permeability, and durability against repeated loads. Therefore, the piping member and the flow meter body of the present disclosure are less likely to be damaged even if stress is repeatedly applied according to the start, stop, and change in flow rate of the chemical solution.
- Molded articles containing the fluorocopolymer of the present disclosure are excellent in sealability, 80° C. wear resistance, low water vapor permeability, and durability against repeated loads. can be suitably used as a member to be compressed.
- the compressible member of the present disclosure may be a gasket or packing.
- the gasket or packing of the present disclosure has excellent sealing properties, 80° C. wear resistance, low water vapor permeability, and durability against repeated loads. Since the member to be compressed of the present disclosure is excellent in low water vapor permeability and sealing properties, it can be suitably used as a piping member for transferring a chemical liquid that should not be mixed with water such as water vapor in the outside air.
- the size and shape of the member to be compressed of the present disclosure may be appropriately set according to the application, and are not particularly limited.
- the shape of the compressible member of the present disclosure may be annular, for example.
- the member to be compressed of the present disclosure may have a shape such as a circle, an oval, or a rectangle with rounded corners in a plan view, and may have a through hole in the center thereof.
- the member to be compressed of the present disclosure is preferably used as a member for configuring a non-aqueous electrolyte battery.
- the member to be compressed of the present disclosure has excellent sealing properties, 80 ° C. abrasion resistance, low water vapor permeability, and excellent durability against repeated loads, so the non-aqueous electrolyte in the non-aqueous electrolyte battery It is particularly suitable as a member used in a state of being in contact with. That is, the member to be compressed of the present disclosure may have a liquid contact surface with the non-aqueous electrolyte in the non-aqueous electrolyte battery.
- the compressed member of the present disclosure is less permeable to water vapor. Therefore, by using the member to be compressed of the present disclosure, it is possible to suppress permeation of water vapor from the outside into the secondary battery. As a result, by using the member to be compressed of the present disclosure, it is possible to suppress the deterioration of the battery performance and the shortening of the life of the non-aqueous electrolyte battery.
- the water vapor permeability of the member to be compressed of the present disclosure is preferably 13.5 g cm/m 2 or less, more preferably 13 .0 g ⁇ cm/m 2 or less.
- the water vapor permeability of the member to be compressed can be measured at a temperature of 95° C. for 30 days.
- the non-aqueous electrolyte battery is not particularly limited as long as it is a battery with a non-aqueous electrolyte, and examples thereof include lithium ion secondary batteries and lithium ion capacitors. Further, examples of members constituting the non-aqueous electrolyte battery include a sealing member and an insulating member.
- the non-aqueous electrolyte is not particularly limited, but includes propylene carbonate, ethylene carbonate, butylene carbonate, ⁇ -butyl lactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, dimethyl carbonate, and diethyl carbonate. , ethyl methyl carbonate and the like can be used.
- the nonaqueous electrolyte battery may further include an electrolyte.
- the electrolyte is not particularly limited, but LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCl, LiBr, CH 3 SO 3 Li, CF 3 SO 3 Li, cesium carbonate, or the like can be used.
- the member to be compressed of the present disclosure can be suitably used as, for example, a sealing member such as a sealing gasket and sealing packing, and an insulating member such as an insulating gasket and insulating packing.
- a sealing member is a member used to prevent leakage of liquid or gas or intrusion of liquid or gas from the outside.
- An insulating member is a member used to insulate electricity.
- Compressed members of the present disclosure may be members used for both sealing and insulating purposes.
- the member to be compressed of the present disclosure has excellent sealing properties, and is also excellent in 80° C. wear resistance, low water vapor permeability, and durability against repeated loads. It can be suitably used as an insulating member for aqueous electrolyte batteries.
- the member to be compressed of the present disclosure contains the fluorine-containing copolymer, it has excellent insulating properties. Therefore, when the compressible member of the present disclosure is used as an insulating member, it adheres tightly to two or more conductive members to prevent short circuits over time.
- the fluorine-containing copolymer of the present disclosure can be suitably used as a material for forming wire coatings.
- a covered electric wire includes a core wire and a coating layer provided around the core wire and containing the fluorine-containing copolymer of the present disclosure.
- the coating layer can be an extruded product obtained by melt extruding the fluorine-containing copolymer of the present disclosure on the core wire.
- the coated electric wire is suitable for LAN cables (Ethernet Cable), high frequency transmission cables, flat cables, heat resistant cables, etc., and particularly suitable for transmission cables such as LAN cables (Eathnet Cable) and high frequency transmission cables.
- the core wire for example, a metal conductor material such as copper or aluminum can be used.
- the core wire preferably has a diameter of 0.02 to 3 mm.
- the diameter of the cord is more preferably 0.04 mm or more, still more preferably 0.05 mm or more, and particularly preferably 0.1 mm or more.
- the diameter of the cord is more preferably 2 mm or less.
- core wires include AWG (American Wire Gauge)-46 (solid copper wire with a diameter of 40 micrometers), AWG-26 (solid copper wire with a diameter of 404 micrometers), AWG-24 (diameter 510 micrometer solid copper wire), AWG-22 (635 micrometer diameter solid copper wire), etc. may be used.
- AWG American Wire Gauge
- AWG-46 solid copper wire with a diameter of 40 micrometers
- AWG-26 solid copper wire with a diameter of 404 micrometers
- AWG-24 diameter 510 micrometer solid copper wire
- AWG-22 (635 micrometer diameter solid copper wire), etc.
- the thickness of the coating layer is preferably 0.1 to 3.0 mm. It is also preferable that the thickness of the coating layer is 2.0 mm or less.
- a coaxial cable is an example of a high-frequency transmission cable.
- a coaxial cable generally has a structure in which an inner conductor, an insulating coating layer, an outer conductor layer and a protective coating layer are laminated in order from the core to the outer periphery.
- a molded article containing the fluorocopolymer of the present disclosure can be suitably used as an insulating coating layer containing the fluorocopolymer.
- the thickness of each layer in the above structure is not particularly limited, but usually the inner conductor has a diameter of about 0.1 to 3 mm, the insulating coating layer has a thickness of about 0.3 to 3 mm, and the outer conductor layer has a thickness of about 0.5-10 mm, the protective coating layer is about 0.5-2 mm thick.
- the coating layer may contain air bubbles, and it is preferable that the air bubbles are uniformly distributed in the coating layer.
- the average bubble diameter of the bubbles is not limited, for example, it is preferably 60 ⁇ m or less, more preferably 45 ⁇ m or less, even more preferably 35 ⁇ m or less, and even more preferably 30 ⁇ m or less. It is preferably 25 ⁇ m or less, particularly preferably 23 ⁇ m or less, and most preferably 23 ⁇ m or less. Also, the average bubble diameter is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. The average bubble diameter can be obtained by taking an electron microscope image of the cross section of the electric wire, calculating the diameter of each bubble by image processing, and averaging the diameters.
- the coating layer may have an expansion rate of 20% or more. It is more preferably 30% or more, still more preferably 33% or more, and even more preferably 35% or more.
- the upper limit is not particularly limited, it is, for example, 80%.
- the upper limit of the expansion rate may be 60%.
- the foaming rate is a value obtained by ((specific gravity of wire coating material ⁇ specific gravity of coating layer)/specific gravity of wire coating material) ⁇ 100. The foaming rate can be appropriately adjusted depending on the application, for example, by adjusting the amount of gas inserted into the extruder, which will be described later, or by selecting the type of gas to be dissolved.
- the covered electric wire may have another layer between the core wire and the covering layer, and may have another layer (outer layer) around the covering layer.
- the electric wire of the present disclosure has a two-layer structure (skin-foam) in which a non-foaming layer is inserted between the core wire and the covering layer, or a two-layer structure in which the outer layer is covered with a non-foaming layer. (foam-skin), or a three-layer structure (skin-foam-skin) in which the outer layer of skin-foam is covered with a non-foamed layer.
- the non-foamed layer is not particularly limited, and includes TFE/HFP copolymers, TFE/PAVE copolymers, TFE/ethylene copolymers, vinylidene fluoride polymers, polyolefin resins such as polyethylene [PE], polychlorinated It may be a resin layer made of a resin such as vinyl [PVC].
- a covered electric wire can be produced, for example, by heating a fluorine-containing copolymer using an extruder and extruding the melted fluorine-containing copolymer onto a core wire to form a coating layer.
- the fluorocopolymer is heated and a gas is introduced into the fluorocopolymer in a molten state to form the coating layer containing air bubbles.
- a gas such as chlorodifluoromethane, nitrogen, carbon dioxide, or a mixture of the above gases can be used.
- the gas may be introduced as a pressurized gas into the heated fluorocopolymer, or may be generated by incorporating a chemical blowing agent into the fluorocopolymer. The gas dissolves in the molten fluorine-containing copolymer.
- the fluorine-containing copolymer of the present disclosure can be suitably used as a material for high-frequency signal transmission products.
- the product for high-frequency signal transmission is not particularly limited as long as it is a product used for high-frequency signal transmission. Molded bodies such as high-frequency vacuum tube bases and antenna covers, (3) coated electric wires such as coaxial cables and LAN cables, and the like.
- the above products for high-frequency signal transmission can be suitably used in equipment that uses microwaves, particularly microwaves of 3 to 30 GHz, such as satellite communication equipment and mobile phone base stations.
- the fluorine-containing copolymer of the present disclosure can be suitably used as an insulator because of its low dielectric loss tangent.
- a printed wiring board is preferable in terms of obtaining good electrical characteristics.
- the printed wiring board include, but are not particularly limited to, printed wiring boards for electronic circuits such as mobile phones, various computers, and communication devices.
- an antenna cover is preferable in terms of low dielectric loss.
- the fluorocopolymer of the present disclosure is resistant to deformation even in a molten state, and a thick sheet with a uniform thickness can be easily obtained. Since it is resistant to deformation even in the case of deformation, and has excellent wear resistance at 80° C., low water vapor permeability, and durability against repeated loads, it can be suitably used as a film or sheet.
- the film of the present disclosure is useful as a release film.
- the release film can be produced by molding the fluorine-containing copolymer of the present disclosure by melt extrusion molding, calendar molding, press molding, casting molding, or the like. From the viewpoint of obtaining a uniform thin film, the release film can be produced by melt extrusion molding.
- the film of the present disclosure can be applied to the surface of rolls used in OA equipment.
- the fluorine-containing copolymer of the present disclosure is molded into a required shape by extrusion molding, compression molding, press molding, etc., and is molded into a sheet, film, or tube, and is used for OA equipment rolls, OA equipment belts, and the like.
- thick sheets and large pipes can be produced by melt extrusion molding.
- the fluorine-containing copolymer of the present disclosure is difficult to deform even in a molten state, it can be easily molded into a beautiful thick pipe by an extrusion molding method. Furthermore, the resulting molded article is resistant to deformation even when a load is applied continuously for a long period of time, and is excellent in 80° C. wear resistance, low water vapor permeability, and durability against repeated loads. Therefore, the fluorocopolymer of the present disclosure can be suitably used for tubes or pipes.
- the pipe containing the fluorine-containing copolymer of the present disclosure can be manufactured with high productivity even when the diameter is large or when the thickness is large, and the pipe has a beautiful shape. It is resistant to deformation even when a load is continuously applied for a long period of time, and has excellent wear resistance at 80°C, low water vapor permeability, and durability against repeated loads.
- each monomer unit of the fluorine-containing copolymer is measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured
- the number of —CF 2 H groups in the fluorine-containing copolymer is measured by 19 F-NMR using a nuclear magnetic resonance apparatus AVANCE-300 (manufactured by Bruker Biospin) at a temperature of (the melting point of the polymer +20)°C. , was obtained from the peak integration value of the —CF 2 H group.
- N I ⁇ K/t (A) I: Absorbance K: Correction coefficient t: Film thickness (mm)
- Table 2 shows the absorption frequencies, molar extinction coefficients, and correction coefficients for the functional groups in the examples. Also, the molar extinction coefficient was determined from the FT-IR measurement data of the low-molecular-weight model compound.
- MFR Melt flow rate
- melting point The melting point of the fluorine-containing copolymer was measured using a differential scanning calorimeter (trade name: X-DSC7000, manufactured by Hitachi High-Tech Science Co., Ltd.) at a heating rate of 10°C/min from 200°C to 350°C for the first time. followed by cooling from 350° C. to 200° C. at a cooling rate of 10° C./min; The melting point was determined from the peak of the melting curve that occurred during the heating process.
- Example 1 40.25 kg of deionized water and 0.291 kg of methanol were put into an autoclave with a volume of 174 L and equipped with a stirrer, and the inside of the autoclave was sufficiently replaced with vacuum nitrogen. After that, the inside of the autoclave was evacuated, and 40.25 kg of HFP and 1.19 kg of PPVE were put into the vacuumed autoclave, and the autoclave was heated to 25.5°C. Subsequently, TFE was added until the internal pressure of the autoclave reached 0.924 MPa, and then 1.25 kg of 8 mass% di( ⁇ -hydroperfluorohexanoyl) peroxide solution (hereinafter abbreviated as DHP) was added to the autoclave.
- DHP di( ⁇ -hydroperfluorohexanoyl) peroxide solution
- the internal pressure of the autoclave at the start of polymerization was set to 0.874 MPa, and the set pressure was maintained by continuously adding TFE. After 1.5 hours from the initiation of polymerization, 0.291 kg of methanol was added. After 2 hours and 4 hours from the start of polymerization, 1.25 kg of DHP was added and the internal pressure was lowered by 0.002 MPa. After 6 hours, 0.96 kg was added and the internal pressure was lowered by 0.002 MPa. Thereafter, 0.25 kg of DHP was added every 2 hours until the reaction was completed, and the internal pressure was lowered by 0.002 MPa each time.
- the resulting powder was melt extruded at 370°C with a screw extruder (trade name: PCM46, manufactured by Ikegai Co., Ltd.) to obtain copolymer pellets.
- a screw extruder (trade name: PCM46, manufactured by Ikegai Co., Ltd.) to obtain copolymer pellets.
- various physical properties were measured by the methods described above. Table 3 shows the results.
- Example 2 The amount of methanol charged before the start of polymerization was changed to 0.124 kg, the amount of methanol charged separately after the start of polymerization was changed to 0.124 kg, and the amount of PPVE charged before the start of polymerization was changed to 1.0 kg. 06 kg, the amount of PPVE to be separately added after the start of polymerization was changed to 0.21 kg, and the set pressure inside the autoclave before and after the start of polymerization was changed to 0.906 MPa. to obtain copolymer pellets. Using the obtained pellets, the HFP content and PPVE content were measured by the methods described above. Table 3 shows the results.
- the obtained pellets were degassed in an electric furnace at 200°C for 8 hours, then placed in a vacuum vibration reactor VVD-30 (manufactured by Okawara Seisakusho Co., Ltd.) and heated to 200°C. After evacuation, F2 gas diluted to 20 % by volume with N2 gas was introduced to atmospheric pressure. After 0.5 hours from the introduction of the F2 gas, the chamber was once evacuated, and the F2 gas was introduced again. Further, after 0.5 hours, the chamber was evacuated again and F 2 gas was introduced again. Thereafter, the F 2 gas introduction and evacuation operations were continued once an hour, and the reaction was carried out at a temperature of 200° C. for 8 hours. After completion of the reaction, the interior of the reactor was sufficiently replaced with N 2 gas to complete the fluorination reaction and obtain pellets. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Example 3 The amount of methanol charged before the initiation of polymerization was changed to 0.030 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.030 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.030 kg.
- the obtained pellets were fluorinated in the same manner as in Example 2. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Comparative example 1 The amount of methanol charged before the initiation of polymerization was changed to 0.327 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.327 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.327 kg.
- Comparative example 2 The amount of methanol charged before the initiation of polymerization was changed to 0.257 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.257 kg, and the amount of PPVE charged before the initiation of polymerization was changed to 1.5 kg.
- Comparative example 3 The amount of methanol charged before the start of polymerization was changed to 0.664 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.664 kg, and the amount of PPVE charged before the start of polymerization was changed to 1.664 kg.
- Comparative example 4 The amount of methanol charged before the initiation of polymerization was changed to 0.012 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.012 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.012 kg.
- Comparative example 5 945 g of deionized water was charged into an autoclave with a volume of 4 L and equipped with a stirrer, and the inside of the autoclave was sufficiently replaced with vacuum nitrogen. After that, the inside of the autoclave was evacuated, and 945 g of HFP and 25.0 g of PPVE were put into the vacuumed autoclave, and the autoclave was heated to 25.5°C. Subsequently, TFE was added until the internal pressure of the autoclave reached 0.892 MPa, and then 29.4 g of 8 mass% di( ⁇ -hydroperfluorohexanoyl) peroxide solution (hereinafter abbreviated as DHP) was added to the autoclave. to initiate polymerization.
- DHP di( ⁇ -hydroperfluorohexanoyl) peroxide solution
- the internal pressure of the autoclave at the start of polymerization was set to 0.892 MPa, and the set pressure was maintained by continuously adding TFE. After 2 hours and 4 hours from the initiation of polymerization, 29.4 g of DHP was added and the internal pressure was lowered by 0.002 MPa, and after 6 hours, 22.6 g was added and the internal pressure was lowered by 0.002 MPa. Thereafter, 1.1 g of DHP was added every 2 hours until the reaction was completed, and the internal pressure was lowered by 0.002 MPa each time.
- the obtained powder was placed in a portable reactor TVS type 1 (manufactured by Pressure Glass Industry Co., Ltd.) and heated to 200°C. After evacuation, F2 gas diluted to 20 % by volume with N2 gas was introduced to atmospheric pressure. After 0.5 hours from the introduction of the F2 gas, the chamber was once evacuated, and the F2 gas was introduced again. Further, after 0.5 hours, the chamber was evacuated again and F 2 gas was introduced again. Thereafter, the F 2 gas introduction and evacuation operations were continued once an hour, and the reaction was carried out at a temperature of 200° C. for 8 hours. After completion of the reaction, the inside of the reactor was sufficiently replaced with N 2 gas to complete the fluorination reaction and obtain powder. Using the obtained powder, various physical properties were measured by the methods described above. Table 3 shows the results.
- the description “ ⁇ 9” in Table 3 means that the number of —CF 2 H groups is less than nine.
- the weight of the test piece was measured after 1000 rotations, and the weight of the test piece was measured after an additional 4000 rotations of the same test piece.
- Storage modulus (E') It was determined by performing dynamic viscoelasticity measurement using DVA-220 (manufactured by IT Keisoku Co., Ltd.). As a sample test piece, a heat press molded sheet with a length of 25 mm, a width of 5 mm, and a thickness of 0.2 mm was used, and the temperature was raised at a rate of 2° C./min and the frequency was 10 Hz. , 65° C. storage modulus (MPa) was read.
- the amount of restoration was measured according to the method described in ASTM D395 or JIS K6262:2013.
- compression set compression set
- test piece having an outer diameter of 13 mm and a height of 6 mm was produced in the same manner as the molding method described in the measurement of the amount of restoration.
- the prepared test piece was compressed to a compressive deformation rate of 50% (that is, a test piece with a height of 6 mm was compressed to a height of 3 mm) at room temperature using a compression device. While the compressed test piece was fixed to the compression device, it was allowed to stand in an electric furnace and left at 65° C. for 72 hours. The compression device was removed from the electric furnace, and after cooling to room temperature, the test piece was removed.
- Compression set (%) (t 0 - t 2 )/(t 0 - t 1 ) x 100 t 0 : original thickness of test piece (mm) t 1 : spacer thickness (mm) t 2 : thickness of test piece removed from compression device (mm)
- Compression set (%) (t 0 - t 2 )/(t 0 - t 1 ) x 100 t 0 : original thickness of test piece (mm) t 1 : spacer thickness (mm) t 2 : thickness of test piece removed from compression device (mm)
- a compact having a small compression set at 65° C. is less likely to deform even when a load is continuously applied for a long period of time.
- the tensile strength was measured after 60,000 cycles using a fatigue tester MMT-250NV-10 manufactured by Shimadzu Corporation.
- a sheet with a thickness of about 2.4 mm was produced using a pellet and heat press molding machine, and a dumbbell-shaped sample (thickness 2.4 mm, width 5.0 mm, measurement length 22 mm) was prepared using ASTM D1708 micro dumbbells. made.
- a sample was attached to a measuring jig, and the measuring jig with the sample attached was placed in a constant temperature bath at 110°C. With a stroke of 0.2 mm and a frequency of 100 Hz, uniaxial tension was repeatedly applied, and the tensile strength (tensile strength when the stroke was +0.2 mm, unit: N) was measured.
- a sheet with high tensile strength after 60,000 cycles maintains high tensile strength even after loading 60,000 times, and has excellent durability (110°C) against repeated loads.
- Bottom area increase rate (%) ⁇ bottom area of test piece after heating (mm 2 ) ⁇ bottom area of test piece before heating (mm 2 ) ⁇ /bottom area of test piece before heating (mm 2 ) ⁇ 100 It means that the lower the base area increase rate, the less likely the compact is to deform due to its own weight when melted.
- a fluorine-containing copolymer that gives a molded article with a low base area increase rate can be molded in a molten state even when the fluorine-containing copolymer is molded by an extrusion molding method to produce a thick sheet or a large pipe. It is excellent in that the body is difficult to deform and a molded body having a desired shape can be obtained after cooling and solidification.
- the extrusion molding of the fluorine-containing copolymer was continued until the fluorine-containing copolymer could be stably extruded from the molding machine. Subsequently, by extruding the fluorine-containing copolymer, a sheet having a length of 3 m or more and a thickness of 1.00 mm (width of 70 mm) was produced. A portion of 2 to 3 m from the edge of the obtained sheet was cut to prepare a test piece (length 1 m, width 70 mm) for measuring variation in thickness. The thickness was measured at a total of three points, namely, the central point in the width direction of the edge of the produced sheet and two points separated from the central point in the width direction by 25 mm.
- a total of 9 points, 3 center points arranged at intervals of 25 cm from the center point in the width direction of the edge of the sheet toward the other end and 2 points 25 mm apart in the width direction from each center point thickness was measured. If the number of measured values outside the range of ⁇ 10% of 1.00 mm is 1 or less out of the total 12 measured values, the number of measured values outside the range of ⁇ 10% of 1.00 mm is indicated as O. x is 2 or more.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Insulated Conductors (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
パーフルオロ(プロピルビニルエーテル)単位の含有量が、全単量体単位に対して、0.66~0.78モル%であることが好ましい。
372℃におけるメルトフローレートが、0.7~2.0g/10分であることが好ましい。
官能基数が、主鎖炭素数106個あたり、50個以下であることが好ましい。
I:吸光度
K:補正係数
t:フィルムの厚さ(mm)
ジノルマルプロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジsec-ブチルパーオキシジカーボネートなどのジアルキルパーオキシカーボネート類;
t-ブチルパーオキシイソブチレート、t-ブチルパーオキシピバレートなどのパーオキシエステル類;
ジt-ブチルパーオキサイドなどのジアルキルパーオキサイド類;
ジ[フルオロ(またはフルオロクロロ)アシル]パーオキサイド類;
などが代表的なものとしてあげられる。
食品包装用フィルム、食品製造工程で使用する流体移送ラインのライニング材、パッキン、シール材、シート等の食品製造装置用流体移送部材;
薬品用の薬栓、包装フィルム、薬品製造工程で使用される流体移送ラインのライニング材、パッキン、シール材、シート等の薬液移送部材;
化学プラントや半導体工場の薬液タンクや配管の内面ライニング部材;
自動車の燃料系統並びに周辺装置に用いられるO(角)リング・チューブ・パッキン、バルブ芯材、ホース、シール材等、自動車のAT装置に用いられるホース、シール材等の燃料移送部材;
自動車のエンジン並びに周辺装置に用いられるキャブレターのフランジガスケット、シャフトシール、バルブステムシール、シール材、ホース等、自動車のブレーキホース、エアコンホース、ラジエーターホース、電線被覆材等のその他の自動車部材;
半導体製造装置のO(角)リング、チューブ、パッキン、バルブ芯材、ホース、シール材、ロール、ガスケット、ダイヤフラム、継手等の半導体装置用薬液移送部材;
塗装設備用の塗装ロール、ホース、チューブ、インク用容器等の塗装・インク用部材;
飲食物用のチューブ又は飲食物用ホース等のチューブ、ホース、ベルト、パッキン、継手等の飲食物移送部材、食品包装材、ガラス調理機器;
廃液輸送用のチューブ、ホース等の廃液輸送用部材;
高温液体輸送用のチューブ、ホース等の高温液体輸送用部材;
スチーム配管用のチューブ、ホース等のスチーム配管用部材;
船舶のデッキ等の配管に巻き付けるテープ等の配管用防食テープ;
電線被覆材、光ファイバー被覆材、太陽電池の光起電素子の光入射側表面に設ける透明な表面被覆材および裏面剤等の各種被覆材;
ダイヤフラムポンプのダイヤフラムや各種パッキン類等の摺動部材;
農業用フィルム、各種屋根材・側壁等の耐侯性カバー;
建築分野で使用される内装材、不燃性防火安全ガラス等のガラス類の被覆材;
家電分野等で使用されるラミネート鋼板等のライニング材;
含フッ素共重合体の各単量体単位の含有量は、NMR分析装置(たとえば、ブルカーバイオスピン社製、AVANCE300 高温プローブ)、または、赤外吸収測定装置(パーキンエルマー社製、Spectrum One)を用いて測定した。
含フッ素共重合体の-CF2H基の数は、核磁気共鳴装置AVANCE-300(ブルカーバイオスピン社製)を用い、測定温度を(ポリマーの融点+20)℃として19F-NMR測定を行い、-CF2H基のピーク積分値から求めた。
実施例および比較例で得られた乾燥粉体もしくはペレットを、コールドプレスにより成形して、厚さ0.25~0.3mmのフィルムを作製した。このフィルムをフーリエ変換赤外分光分析装置〔FT-IR(Spectrum One、パーキンエルマー社製)〕により40回スキャンし、分析して赤外吸収スペクトルを得た。得られた赤外吸収スペクトルを、既知のフィルムの赤外吸収スペクトルと比較して末端基の種類を決定した。また、得られた赤外吸収スペクトルと、既知のフィルムの赤外吸収スペクトルとの差スペクトルに現れる特定の官能基の吸収ピークから、下記式(A)に従って試料における炭素原子1×106個あたりの官能基数Nを算出した。
I:吸光度
K:補正係数
t:フィルムの厚さ(mm)
含フッ素共重合体のMFRは、ASTM D-1238に準拠して、メルトインデクサーG-01(東洋精機製作所製)を用い、372℃、5kg荷重下で、内径2mm、長さ8mmのダイから10分間あたりに流出するポリマーの質量(g/10分)を測定することにより、求めた。
含フッ素共重合体の融点は、示差走査熱量計(商品名:X-DSC7000、日立ハイテクサイエンス社製)を用いて、昇温速度10℃/分で200℃から350℃までの1度目の昇温を行い、続けて、冷却速度10℃/分で350℃から200℃まで冷却し、再度、昇温速度10℃/分で200℃から350℃までの2度目の昇温を行い、2度目の昇温過程で生ずる溶融曲線ピークから融点を求めた。
容積174Lの攪拌機付きオートクレーブに脱イオン水40.25kgとメタノール0.291kgを投入し、オートクレーブ内を十分に真空窒素置換した。その後、オートクレーブ内を真空脱気し、真空状態となったオートクレーブ内にHFP40.25kgとPPVE1.19kg投入し、オートクレーブを25.5℃に加温した。続けて、オートクレーブの内部圧力が0.924MPaになるまでTFEを投入し、次に8質量%のジ(ω-ヒドロパーフルオロヘキサノイル)パーオキサイド溶液(以下DHPと略す)1.25kgをオートクレーブ内に投入して重合を開始した。重合開始時点のオートクレーブの内部圧力を0.874MPaに設定し、TFEを連続追加することで設定圧力を保つようにした。重合開始から1.5時間後にメタノール0.291kgを追加投入した。重合開始から2時間後、4時間後、にDHP1.25kgを追加投入するとともに内部圧力を0.002MPa下げ、6時間後に0.96kgを投入するとともに内部圧力を0.002MPa下げた。以降、反応が終了するまで2時間ごとにDHP0.25kgを追加投入し、その都度内部圧力を0.002MPa下げた。
重合開始前に投入するメタノールの量を0.124kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.124kgに変更し、重合開始前に投入するPPVEの量を1.06kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.21kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.906MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.030kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.030kgに変更し、重合開始前に投入するPPVEの量を0.90kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.19kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.892MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.327kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.327kgに変更し、重合開始前に投入するPPVEの量を0.56kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.11kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.906MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.257kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.257kgに変更し、重合開始前に投入するPPVEの量を1.12kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.23kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.892MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.664kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.664kgに変更し、重合開始前に投入するPPVEの量を1.35kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.17kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.994MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.012kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.012kgに変更し、重合開始前に投入するPPVEの量を0.93kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.22kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.855MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
容積4Lの攪拌機付きオートクレーブに脱イオン水945gを投入し、オートクレーブ内を十分に真空窒素置換した。その後、オートクレーブ内を真空脱気し、真空状態となったオートクレーブ内にHFP945gとPPVE25.0g投入し、オートクレーブを25.5℃に加温した。続けて、オートクレーブの内部圧力が0.892MPaになるまでTFEを投入し、次に8質量%のジ(ω-ヒドロパーフルオロヘキサノイル)パーオキサイド溶液(以下DHPと略す)29.4gをオートクレーブ内に投入して重合を開始した。重合開始時点のオートクレーブの内部圧力を0.892MPaに設定し、TFEを連続追加することで設定圧力を保つようにした。重合開始から2時間後、4時間後、にDHP29.4gを追加投入するとともに内部圧力を0.002MPa下げ、6時間後に22.6gを投入するとともに内部圧力を0.002MPa下げた。以降、反応が終了するまで2時間ごとにDHP1.1gを追加投入し、の都度内部圧力を0.002MPa下げた。
ペレットおよびヒートプレス成形機を用いて、厚さ約0.2mmのシート状試験片を作製し、これから10cm×10cmの試験片を切り出した。テーバー摩耗試験機(No.101 特型テーバー式アブレーションテスター、安田精機製作所社製)の試験台に作製した試験片を固定し、試験片表面温度80℃、荷重500g、摩耗輪CS-10(研磨紙#240で20回転研磨したもの)、回転速度60rpmの条件で、テーバー摩耗試験機を用いて摩耗試験を行った。1000回転後の試験片重量を計量し、同じ試験片でさらに4000回転試験後に試験片重量を計量した。次式により、摩耗量を求めた。
摩耗量(mg)=M1-M2
M1:1000回転後の試験片重量(mg)
M2:4000回転後の試験片重量(mg)
ペレットおよびヒートプレス成形機を用いて、厚さ約0.2mmのシート状試験片を作製した。試験カップ(透過面積12.56cm2)内に水を18g入れ、シート状試験片で覆い、PTFEガスケットを挟んで締め付け、密閉した。シート状試験片と水が接するようにして、温度95℃で30日間保持した後取出し、室温で2時間放置後に質量減少量を測定した。次式により、水蒸気透過度(g・cm/m2)を測定した。
水蒸気透過度(g・cm/m2)=質量減少量(g)×シート状試験片の厚さ(cm)/透過面積(m2)
DVA-220(アイティー計測制御社製)を用いた動的粘弾性測定を行い求めた。サンプル試験片として、長さ25mm、幅5mm、厚み0.2mmのヒートプレス成形シートを用いて、昇温速度2℃/分、周波数10Hz条件下で、30℃~250℃の範囲で測定を行い、65℃の貯蔵弾性率(MPa)を読み取った。
復元量の測定は、ASTM D395またはJIS K6262:2013に記載の方法に準じた。
復元量(mm)=t2-t1
t1:スペーサの高さ(mm)
t2:圧縮装置から取り外した試験片の高さ(mm)
上記の試験においては、t1=3mmである。
65℃での復元量測定の結果と65℃における貯蔵弾性率測定の結果から、次式により65℃反発力を求めた。
65℃反発力(MPa)=(t2-t1)/t1×E’
t1:スペーサの高さ(mm)
t2:圧縮装置から取り外した試験片の高さ(mm)
E’:65℃での貯蔵弾性率(MPa)
65℃における反発力が大きい成形体は、長期間、継続して荷重が負荷された場合でも変形しにくい。
これらの試験および測定は、ASTM D395またはJIS K6262に記載の方法に準じた。復元量の測定において説明した成形方法と同様にして、外径13mm、高さ6mmの試験片を作製した。作製した試験片を、圧縮装置を用いて、常温で、圧縮変形率50%まで圧縮(つまり、高さ6mmの試験片を、高さ3mmまで圧縮)した。圧縮した試験片を圧縮装置に固定したまま、電気炉内に静置し、65℃で72時間放置した。電気炉から圧縮装置を取り出し、室温まで冷却後、試験片を取り外した。回収した試験片を室温で30分放置した後、回収した試験片の高さを測定し、次式により、圧縮永久歪み率を求めた。
圧縮永久歪み(%)=(t0-t2)/(t0-t1)×100
t0:試験片の元の厚さ(mm)
t1:スペーサの厚さ(mm)
t2:圧縮装置から取り外した試験片の厚さ(mm)
65℃における圧縮永久歪みが小さい成形体は、長期間、継続して荷重が負荷された場合でも変形しにくい。
島津製作所社製疲労試験機MMT-250NV-10を用いて6万回サイクル後引張強度を測定した。ペレットおよびヒートプレス成形機を用いて、厚さ約2.4mmのシートを作製し、ASTM D1708マイクロダンベル用いて、ダンベル形状(厚み2.4mm、幅5.0mm、測定部長さ22mm)のサンプルを作製した。サンプルを測定治具に装着し、サンプルを装着した状態で測定治具を110℃の恒温槽中に設置した。ストローク0.2mm、周波数100Hzで、一軸方向への引張りを繰り返し、引張り毎の引張強度(ストロークが+0.2mmの時の引張強度、単位:N)を測定した。
ペレットおよびヒートプレス成形機を用いて、直径13mm、高さ約6.5mmの成形体を作製した。得られた成形体を切削して、高さ6.3mmの試験片を作製した。作製した試験片をSUS製シャーレに入れ、電気炉にて330℃で30分間加熱後、試験片を入れたシャーレごと水冷した。取り出した試験片のシャーレに接していた面(底面)の直径をノギスで計測し、次式により、底面積増加率を算出した。
底面積増加率(%)={加熱後試験片底面積(mm2)―加熱前試験片底面積(mm2)}/加熱前試験片底面積(mm2)×100
底面積増加率が低いほど、成形体が溶融時に自重により変形しにくいことを意味する。底面積増加率が低い成形体を与える含フッ素共重合体は、押出成形法によって含フッ素共重合体を成形して、厚いシートや大型のパイプを作製する場合であっても、溶融状態の成形体が変形しにくく、冷却固化した後に所望の形状の成形体が得られる点で優れている。
φ14mm押出機(井元製作所製)およびTダイを用いて、ペレットを成形し、シートを作製した。押出成形条件は以下の通りである。
a)巻き取り速度:0.1m/分
b)ロール温度:120℃
c)シート幅:70mm
d)厚み:1.00mm
e)押出条件:
・シリンダー軸径=14mm,L/D=20の単軸押出成形機
押出機の設定温度:バレル部C-1(330℃)、バレル部C-2(350℃)、バレル部C-3(360℃)、Tダイ部(365℃)
φ30mm押出機(田辺プラスチックス機械製)を用いて、ペレットを押出成形し、外径10.0mm、肉厚1.0mmのパイプを得た。押出成形条件は以下の通りである。
a)ダイ内径:25mm
b)マンドレル外径:13mm
c)サイジングダイ内径:10.5mm
d)引取り速度:0.4m/分
e)外径:10.0mm
f)肉厚:1.0mm
g)押出条件:
・シリンダー軸径=30mm,L/D=22の単軸押出成形機
押出機の設定温度:バレル部C-1(350℃)、バレル部C-2(370℃)、バレル部C-3(380℃)、ヘッド部H-1(390℃)、ダイ部D-1(390℃)、ダイ部D-2(390℃)
得られたパイプを観察し、以下の基準により評価した。パイプの外観は、目視により確認した。
〇:外観が良好である
×:断面が円形になっておらず、扁平していたり偏肉が観られるなど、外観が不良である
ペレットおよびヒートプレス成形機を用いて、厚さ約0.2mmのシートを作製し、15mm四方の試験片を作製した。50mLポリプロピレン製ボトルに、試験片10枚と3質量%過酸化水素水溶液15gを入れ、電気炉にて95℃で20時間加熱後、室温まで冷却した。過酸化水素水溶液から試験片を取り出し、残った過酸化水素水溶液にTISAB溶液(10)(関東化学社製)を添加し、得られた過酸化水素水溶液中のフッ素イオン濃度を、フッ素イオンメーターにて測定した。得られた測定値から、下記式にしたがって、シート重量当たりのフッ素イオン濃度(溶出フッ素イオン濃度)を算出した。
溶出フッ素イオン濃度(質量ppm)=測定値(ppm)×過酸化水素水溶液量(g)/試験片重量(g)
Claims (9)
- テトラフルオロエチレン単位、ヘキサフルオロプロピレン単位およびパーフルオロ(プロピルビニルエーテル)単位を含有する含フッ素共重合体であって、
ヘキサフルオロプロピレン単位の含有量が、全単量体単位に対して、4.10~5.20モル%であり、
パーフルオロ(プロピルビニルエーテル)単位の含有量が、全単量体単位に対して、0.53~0.86モル%であり、
372℃におけるメルトフローレートが、0.7~2.5g/10分である
含フッ素共重合体。 - ヘキサフルオロプロピレン単位の含有量が、全単量体単位に対して、4.35~4.97モル%である請求項1に記載の含フッ素共重合体。
- パーフルオロ(プロピルビニルエーテル)単位の含有量が、全単量体単位に対して、0.66~0.78モル%である請求項1または2に記載の含フッ素共重合体。
- 372℃におけるメルトフローレートが、0.7~2.0g/10分である請求項1~3のいずれかに記載の含フッ素共重合体。
- 官能基数が、主鎖炭素数106個あたり、50個以下である請求項1~4のいずれかに記載の含フッ素共重合体。
- 請求項1~5のいずれかに記載の含フッ素共重合体を含有する押出成形体。
- 請求項1~5のいずれかに記載の含フッ素共重合体を含有するトランスファー成形体。
- 請求項1~5のいずれかに記載の含フッ素共重合体を含有する被覆層を備える被覆電線。
- 請求項1~5のいずれかに記載の含フッ素共重合体を含有する成形体であって、前記成形体が、シートまたはパイプである成形体。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280015024.7A CN116848159A (zh) | 2021-02-26 | 2022-02-28 | 含氟共聚物 |
US18/451,227 US20230399430A1 (en) | 2021-02-26 | 2023-08-17 | Fluorine-containing copolymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021031104 | 2021-02-26 | ||
JP2021-031104 | 2021-02-26 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/451,227 Continuation US20230399430A1 (en) | 2021-02-26 | 2023-08-17 | Fluorine-containing copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022181827A1 true WO2022181827A1 (ja) | 2022-09-01 |
Family
ID=83047518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/008443 WO2022181827A1 (ja) | 2021-02-26 | 2022-02-28 | 含フッ素共重合体 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20230399430A1 (ja) |
JP (1) | JP7193765B2 (ja) |
CN (1) | CN116848159A (ja) |
WO (1) | WO2022181827A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005049661A1 (ja) * | 2003-11-20 | 2005-06-02 | Daikin Industries, Ltd. | 含フッ素重合体製造方法及び含フッ素重合体物 |
JP2014028953A (ja) * | 2012-07-05 | 2014-02-13 | Daikin Ind Ltd | 改質フッ素樹脂混合物、フッ素樹脂成形品、及び、フッ素樹脂成形品の製造方法 |
WO2015104974A1 (ja) * | 2014-01-08 | 2015-07-16 | ダイキン工業株式会社 | 耐熱電線 |
JP2017503052A (ja) * | 2013-12-20 | 2017-01-26 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | 配向フルオロポリマーフィルム |
-
2022
- 2022-02-28 JP JP2022029701A patent/JP7193765B2/ja active Active
- 2022-02-28 WO PCT/JP2022/008443 patent/WO2022181827A1/ja active Application Filing
- 2022-02-28 CN CN202280015024.7A patent/CN116848159A/zh active Pending
-
2023
- 2023-08-17 US US18/451,227 patent/US20230399430A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005049661A1 (ja) * | 2003-11-20 | 2005-06-02 | Daikin Industries, Ltd. | 含フッ素重合体製造方法及び含フッ素重合体物 |
JP2014028953A (ja) * | 2012-07-05 | 2014-02-13 | Daikin Ind Ltd | 改質フッ素樹脂混合物、フッ素樹脂成形品、及び、フッ素樹脂成形品の製造方法 |
JP2017503052A (ja) * | 2013-12-20 | 2017-01-26 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | 配向フルオロポリマーフィルム |
WO2015104974A1 (ja) * | 2014-01-08 | 2015-07-16 | ダイキン工業株式会社 | 耐熱電線 |
Also Published As
Publication number | Publication date |
---|---|
JP7193765B2 (ja) | 2022-12-21 |
US20230399430A1 (en) | 2023-12-14 |
JP2022132211A (ja) | 2022-09-07 |
CN116848159A (zh) | 2023-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7112013B1 (ja) | 含フッ素共重合体 | |
JP7121327B1 (ja) | 含フッ素共重合体 | |
JP7193768B2 (ja) | 含フッ素共重合体 | |
JP7112014B1 (ja) | 含フッ素共重合体 | |
JP7219411B2 (ja) | 含フッ素共重合体 | |
JP7265210B2 (ja) | 含フッ素共重合体 | |
JP7277842B2 (ja) | 含フッ素共重合体 | |
JP7277843B2 (ja) | 含フッ素共重合体 | |
JP7280539B2 (ja) | 含フッ素共重合体 | |
JP7193767B2 (ja) | 含フッ素共重合体 | |
JP7108223B1 (ja) | 含フッ素共重合体 | |
JP7193765B2 (ja) | 含フッ素共重合体 | |
JP7193764B2 (ja) | 含フッ素共重合体 | |
JP7177378B2 (ja) | 含フッ素共重合体 | |
JP7265209B2 (ja) | 含フッ素共重合体 | |
JP7174312B2 (ja) | 含フッ素共重合体 | |
WO2023190901A1 (ja) | 含フッ素共重合体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22759860 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280015024.7 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 28/11/2023). |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22759860 Country of ref document: EP Kind code of ref document: A1 |