WO2010113951A1 - 含フッ素エラストマー混合物、その製造方法、パーオキサイド加硫用組成物、及び、成形品 - Google Patents
含フッ素エラストマー混合物、その製造方法、パーオキサイド加硫用組成物、及び、成形品 Download PDFInfo
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- WO2010113951A1 WO2010113951A1 PCT/JP2010/055709 JP2010055709W WO2010113951A1 WO 2010113951 A1 WO2010113951 A1 WO 2010113951A1 JP 2010055709 W JP2010055709 W JP 2010055709W WO 2010113951 A1 WO2010113951 A1 WO 2010113951A1
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- WIPO (PCT)
- Prior art keywords
- fluorine
- containing elastomer
- mol
- units
- peroxide
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 202
- 239000000806 elastomer Substances 0.000 title claims abstract description 192
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000011737 fluorine Substances 0.000 title claims abstract description 190
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 190
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 46
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 19
- -1 perfluoro Chemical group 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000010060 peroxide vulcanization Methods 0.000 claims description 10
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 abstract description 50
- 230000035699 permeability Effects 0.000 abstract description 42
- 238000004073 vulcanization Methods 0.000 description 33
- 229920000642 polymer Polymers 0.000 description 26
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920001973 fluoroelastomer Polymers 0.000 description 10
- 239000011630 iodine Substances 0.000 description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002497 iodine compounds Chemical class 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 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
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 description 2
- SYXTYIFRUXOUQP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy butaneperoxoate Chemical compound CCCC(=O)OOOC(C)(C)C SYXTYIFRUXOUQP-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- GBBZLMLLFVFKJM-UHFFFAOYSA-N 1,2-diiodoethane Chemical compound ICCI GBBZLMLLFVFKJM-UHFFFAOYSA-N 0.000 description 1
- HZMRWVMITKPWFK-UHFFFAOYSA-N 1,3,5-tris(2,3,3-trifluoroprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound FC(F)=C(F)CN1C(=O)N(CC(F)=C(F)F)C(=O)N(CC(F)=C(F)F)C1=O HZMRWVMITKPWFK-UHFFFAOYSA-N 0.000 description 1
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VFTWMPNBHNNMAV-UHFFFAOYSA-N 2-tert-butylperoxy-1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C(OOC(C)(C)C)=C1 VFTWMPNBHNNMAV-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- PDFSXHZXNZCKNF-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodeca-1,9-diene Chemical compound C=CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C PDFSXHZXNZCKNF-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- HZTNYDWTDTYXQC-UHFFFAOYSA-N bis(prop-2-ynyl) benzene-1,4-dicarboxylate Chemical compound C#CCOC(=O)C1=CC=C(C(=O)OCC#C)C=C1 HZTNYDWTDTYXQC-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000003139 buffering effect Effects 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
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical class CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 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
- 239000010453 quartz Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- PNWOTXLVRDKNJA-UHFFFAOYSA-N tert-butylperoxybenzene Chemical compound CC(C)(C)OOC1=CC=CC=C1 PNWOTXLVRDKNJA-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a fluorine-containing elastomer mixture, a production method thereof, a composition for peroxide vulcanization, and a molded article.
- Cold-resistant fluororubber which is a copolymer of perfluoroalkyl vinyl ether (PAVE) copolymer based on vinylidene fluoride (VdF), exhibits excellent cold resistance even under low temperature conditions of -25 ° C or lower.
- VdF / hexafluoropropylene (HFP) copolymer and VdF / HFP / tetrafluoroethylene (TFE) copolymer the low fuel permeability required in the above is low and has low cold resistance and low fuel permeability. A balance is desired.
- thermoplastic elastomer obtained by block polymerization of a fluororesin component on a fluorine-containing elastomer is excellent in low permeability of automobile fuel. This is considered because the resin component in the polymer suppresses the permeation of fuel.
- the molded product obtained from this elastomer needs to increase the amount of the resin component in order to achieve low permeability, so that the hardness is increased or the cold resistance of the fluorine-containing elastomer is deteriorated. At the expense of Therefore, it cannot be a material having both low fuel permeability and cold resistance, which are the targets of the present application.
- Patent Document 1 TFE and PAVE, perfluoromethyl vinyl ether (PMVE), are copolymerized in the presence of an iodine and / or bromine-containing compound, and this reaction is continued without releasing unreacted monomers.
- a method for producing a fluorinated copolymer in which TFE and VdF are supplied to the system to continue the polymerization reaction is disclosed.
- the production method in Patent Document 1 can produce a copolymer in high yield and increase productivity, but has not yet solved the problem of achieving both cold resistance and low fuel permeability.
- the present invention relates to a fluorine-containing elastomer mixture that gives a molded product having low hardness and excellent fuel low permeability while maintaining the cold resistance of the cold-resistant fluororubber, a composition for peroxide vulcanization containing the fluorine-containing elastomer mixture, Another object is to provide a molded article obtained from the peroxide vulcanizing composition.
- the present invention relates to (A) a copolymer (a1) consisting of only 50 to 85 mol% vinylidene fluoride units and 15 to 50 mol% perfluoro (alkyl vinyl ether) units, or 45 to 85 mol% fluorine.
- This is a copolymer (a2) consisting only of vinylidene fluoride units, 1 to 30 mol% tetrafluoroethylene units and 14 to 30 mol% perfluoro (alkyl vinyl ether) units, and is capable of peroxide vulcanization having iodine atoms.
- the fluorine-containing elastomer (B) is a copolymer (b1) consisting of 45 to 85 mol% tetrafluoroethylene units and 15 to 55 mol% perfluoro (alkyl vinyl ether) units, 15 to 85 mol% tetra A copolymer (b2) comprising only fluoroethylene units, 1 to 30 mol% ethylene units and 14 to 55 mol% perfluoro (alkyl vinyl ether) units, and 25 to 85 mol% vinylidene fluoride units, 0 It is preferably at least one copolymer selected from the group consisting of a copolymer (b3) comprising only ⁇ 40 mol% tetrafluoroethylene units and 15 to 40 mol% hexafluoropropylene units.
- the mass ratio (A) / (B) of the fluorine-containing elastomer (A) to the fluorine-containing elastomer (B) is preferably 60/40 to 95/5.
- the present invention is also a peroxide vulcanizing composition containing the fluorine-containing elastomer mixture (i), the polyfunctional unsaturated compound (ii), and the peroxide (iii).
- the present invention is also a molded article obtained by molding the peroxide vulcanizing composition.
- the present invention is also a method for producing the above-mentioned fluorine-containing elastomer mixture, which comprises the step of co-coagulating an aqueous dispersion containing the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B). It is also a method.
- the fluorine-containing elastomer mixture of the present invention is used, a molded product having both cold resistance and low fuel permeability can be obtained.
- an operation for exchanging the polymerization monomer was necessary, but the fluorine-containing elastomer mixture of the present invention can be produced without such complicated steps, so it is extremely productive. Excellent in properties.
- the present invention relates to (A) a copolymer (a1) comprising only 50 to 85 mol% of vinylidene fluoride [VdF] units and 15 to 50 mol% of perfluoro (alkyl vinyl ether) [PAVE] units, or 45 A copolymer (a2) comprising only -85 mol% vinylidene fluoride units, 1-30 mol% tetrafluoroethylene [TFE] units, and 14-30 mol% perfluoro (alkyl vinyl ether) units; A fluorine-containing elastomer containing an atom-containing peroxide vulcanizable elastomer and (B) a fluorine-containing elastomer capable of vulcanizing a peroxide having a fluorine content of 70.0% by mass or more and having an iodine atom Relates to the mixture.
- the fluorine-containing elastomer (A) may be a copolymer (a1) and a
- the fluorine-containing elastomer mixture of the present invention provides a molded product having low hardness and excellent fuel low permeability while maintaining the cold resistance of the cold resistant fluororubber.
- the fluorine-containing elastomer that gives a molded article having excellent cold resistance, low fuel permeability and low hardness includes a raw material monomer of the fluorine-containing elastomer (A) and a raw material monomer of the fluorine-containing elastomer (B).
- A raw material monomer of the fluorine-containing elastomer
- B raw material monomer of the fluorine-containing elastomer
- a block copolymer obtained by block copolymerization with a monomer is also conceivable, the production of the block copolymer requires repeated block polymerization by one-pot synthesis, and requires replacement work of raw material monomers. Since the fluorine-containing elastomer mixture of the present invention does not require such replacement work and can be easily manufactured, productivity
- the fluorine-containing elastomer mixture of the present invention is a fluorine-containing elastomer mixture containing two types of elastomers, a fluorine-containing elastomer (A) and a fluorine-containing elastomer (B), for example, a fluorine-containing elastomer mixture which is a vulcanizing composition When a molded product is formed using, its hardness is kept low and the compression set is good.
- the form of the fluorine-containing elastomer mixture is not particularly limited as long as it contains the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B).
- a mixed powder containing a powder of the fluorine-containing elastomer (A) and a powder of the fluorine-containing elastomer (B) may be used, or an aqueous dispersion containing the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B) may be used.
- the above-mentioned fluorine-containing elastomer mixture usually does not have a melting point derived from the fluorine-containing elastomers (A) and (B).
- the presence / absence of the melting point is, for example, a mixed powder containing the powders of the fluorine-containing elastomers (A) and (B), and the temperature rising speed is 10 ° C./min in the temperature range of 60 to 400 ° C. by differential scanning calorimetry (DSC). It is possible to confirm whether or not the peak derived from the fluorine-containing elastomer (A) and (B) can be measured within the range by measuring the heat balance of the second scan.
- the mass ratio (A) / (B) between the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B) is preferably 60/40 to 95/5.
- the content ratio (A) / (B) is more preferably 65/35 to 90/10 in terms of mass ratio, and 65/35 to 80 / 20 is more preferable.
- Rf means a C 3-10 perfluoroether group containing 1 to 2 ether
- the perfluoro (alkyl vinyl ether) unit of the copolymers (a1) and (a2) may be a perfluoro (methyl vinyl ether) unit, a perfluoro (ethyl vinyl ether) unit, or a perfluoro (propyl vinyl ether) unit. More preferred is a perfluoro (methyl vinyl ether) unit.
- PAVE in a fluorine-containing elastomer (A) may be 1 type, and may be used 2 or more types.
- the fluorine-containing elastomer (A) is a copolymer (a1)
- the fluorine-containing elastomer (A) contains 50 to 85 mol% of vinylidene fluoride units and 15 to 50 mol% of perfluoro (alkyl vinyl ether). Since it consists only of units, it has good cold resistance and flexibility. More preferably, the copolymer (a1) is composed of only 55 to 80 mol% of vinylidene fluoride units and 20 to 45 mol% of perfluoro (alkyl vinyl ether) units.
- the fluorine-containing elastomer (A) is a copolymer (a2)
- the fluorine-containing elastomer (A) contains 45 to 85 mol% of vinylidene fluoride units and 1 to 30 mol% of tetrafluoroethylene units. And 14 to 30 mol% of perfluoro (alkyl vinyl ether) units, the cold resistance and flexibility are good.
- the copolymer (a2) comprises only 50 to 80 mol% vinylidene fluoride units, 5 to 25 mol% tetrafluoroethylene units and 15 to 28 mol% perfluoro (alkyl vinyl ether) units. It is.
- the number average molecular weight (Mn) of the fluorine-containing elastomer (A) depends on the amount of the fluorine-containing elastomer (B), but the molding processability of the resulting fluorine-containing elastomer mixture is good. From the viewpoint of improving the dispersibility of B), 20,000 or more is preferable, and 30,000 or more is more preferable. Moreover, 300,000 or less is preferable and 200,000 or less is more preferable.
- the Mooney viscosity at 100 ° C. of the fluorine-containing elastomer (A) is preferably 2 or more, and more preferably 5 or more, from the viewpoint that the moldability of the fluorine-containing elastomer mixture obtained in the same manner as the molecular weight is good. Moreover, 200 or less is preferable and 150 or less is more preferable.
- the fluorine content of the fluorine-containing elastomer (A) is preferably 63.5% by mass or more, more preferably 64.0% by mass or more, and 64.5% by mass or more from the viewpoint of good low fuel permeability. Is more preferable.
- the fluorine content of the fluorine-containing elastomer (A) is preferably 68.0% by mass or less, more preferably 67.5% by mass or less, and 67.0% by mass or less from the viewpoint of good cold resistance. Further preferred.
- the fluorine-containing elastomer (A) has an iodine atom.
- the fluorine-containing elastomer (A) having an iodine atom is a known iodine transfer polymerization method from the point that the molecular weight distribution of the obtained polymer is narrow and the molecular weight can be easily controlled, and an iodine atom can be introduced into the terminal. It is preferable to manufacture using.
- emulsification in an aqueous medium in the presence of a radical initiator while stirring the monomer constituting the elastomer under pressure in the presence of an iodine compound, preferably a diiodine compound, in the absence of oxygen examples include polymerization, suspension polymerization, and solution polymerization.
- iodine compound used include, for example, RI n (wherein n is an integer of 1 to 2 and R is a saturated or unsaturated fluorohydrocarbon group having 1 to 8 carbon atoms or a chlorofluorohydrocarbon). Group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom).
- q is preferably an integer of 1 or more).
- An iodine atom is introduced into the fluorine-containing elastomer obtained by using such an iodine compound (see, for example, JP-A-53-125491 and JP-A-63-30409).
- the fluorine-containing elastomer (A) is preferably produced by a known polymerization method such as an emulsion polymerization method, a suspension polymerization method, or a solution polymerization method using an iodine transfer polymerization method. What is necessary is just to determine suitably polymerization conditions, such as temperature at the time of superposition
- a wide range of emulsifiers can be used for the emulsion polymerization. From the viewpoint of suppressing chain transfer reaction to the emulsifier molecules that occur during the polymerization, a carboxylic acid having a fluorocarbon chain or a fluoropolyether chain is used. Salts are desirable. It is also desirable to use a reactive emulsifier.
- the radical polymerization initiator is not particularly limited, and known organic and inorganic peroxides can be used.
- oil-soluble organic peroxides include diisopropyl peroxycarbonates such as diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, disec-butyl peroxydicarbonate, t-butyl peroxybutyrate, Examples thereof include peroxyesters such as t-butyl peroxypivalate, and dialkyl peroxides such as di-t-butyl peroxide.
- the inorganic peroxide includes a carboxyl group or a group capable of generating a carboxyl group (for example, acid fluoride, acid chloride, CF 2 OH, etc., all of which generate a carboxyl group in the presence of water).
- a carboxyl group or a group capable of generating a carboxyl group for example, acid fluoride, acid chloride, CF 2 OH, etc., all of which generate a carboxyl group in the presence of water.
- Can be present at the end of the elastomer and specific examples include ammonium persulfate (APS), potassium persulfate (KPS), and the like.
- pH adjuster in the polymerization system examples include electrolyte substances having buffering ability such as phosphate, carbonate, borate, sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like.
- Examples of the molecular weight regulator include the iodine compounds mentioned above.
- Examples of a method for isolating the polymerization product from the polymerization reaction mixture include a method in which a metal salt such as magnesium chloride, calcium chloride, sodium chloride, magnesium sulfate, barium sulfate is added and coagulated.
- a metal salt such as magnesium chloride, calcium chloride, sodium chloride, magnesium sulfate, barium sulfate is added and coagulated.
- the fluorine-containing elastomer (B) is a fluorine-containing elastomer having a fluorine content of 70.0% by mass or more and capable of peroxide vulcanization having iodine atoms. Since the fluorine-containing elastomer (B) has a high fluorine content of 70.0% by mass or more, it has excellent fuel low permeability. Then, the fluorine-containing elastomer (B) is finely dispersed in the fluorine-containing elastomer (A) forming the matrix to form microdomains. Therefore, when used as a mixture with the fluorine-containing elastomer (A) in a vulcanizing composition or the like, it is considered that a bypass effect is exhibited when the fuel permeates and low permeability can be realized.
- the cross-linked product is a polymer having a low fuel permeability superior to that of the fluorine-containing elastomer (A). Furthermore, it is preferably a polymer that has low compatibility with the fluorine-containing elastomer (A) and that undergoes phase separation. “Phase-separated” means that when both the fluorine-containing elastomers (A) and (B) are allowed to coexist, for example, glass transition temperatures due to the respective polymers are observed.
- Examples of such fluorine-containing rubber-containing elastomers (B) include fluorine-containing elastomers based on VdF, fluorine-containing elastomers based on TFE, and fluorine-containing elastomers based on ethylene (Et).
- B1 a copolymer comprising only TFE units and PAVE units
- B2 a copolymer comprising only TFE units, Et units and PAVE units
- the polymer itself is preferable in that it is excellent in low fuel low permeability.
- a copolymer (b1) having only a TFE unit and a PAVE unit having a lower affinity (not containing VdF) and the fluorine-containing elastomer (A) is more preferable.
- the perfluoro (alkyl vinyl ether) unit of the copolymers (b1) and (b2) is a perfluoro (methyl vinyl ether) unit, a perfluoro (ethyl vinyl ether) unit or a perfluoro (propyl vinyl ether) unit. Is more preferable, and a perfluoro (methyl vinyl ether) unit is more preferable.
- the copolymer (b1) is a copolymer composed of only 45 to 85 mol% of tetrafluoroethylene units and 15 to 55 mol% of perfluoro (alkyl vinyl ether) units, and has flexibility and low fuel permeability. Is good. From the viewpoint of better flexibility and low fuel permeability, the copolymer should be composed of only 50 to 85 mol% tetrafluoroethylene units and 15 to 50 mol% perfluoro (alkyl vinyl ether) units. It is more preferable that the copolymer be composed of only 55 to 80 mol% of tetrafluoroethylene units and 20 to 45 mol% of perfluoro (alkyl vinyl ether) units.
- the copolymer (b2) is a copolymer consisting only of 15 to 85 mol% tetrafluoroethylene units, 1 to 30 mol% ethylene units and 14 to 55 mol% perfluoro (alkyl vinyl ether) units. Good flexibility, low fuel permeability. 20 to 70 mol% tetrafluoroethylene units, 5 to 25 mol% ethylene units and 20 to 55 mol% perfluoro (alkyl vinyl ether) units from the viewpoint of better flexibility and low fuel permeability It is preferable that it is a copolymer consisting of only.
- the copolymer (b3) is a copolymer consisting only of 25 to 85 mol% vinylidene fluoride units, 0 to 40 mol% tetrafluoroethylene units and 15 to 40 mol% hexafluoropropylene units, Good flexibility and low fuel permeability. Only 30 to 70 mol% vinylidene fluoride units, 10 to 40 mol% tetrafluoroethylene units, and 15 to 35 mol% hexafluoropropylene units are more flexible and have low fuel permeability.
- the number average molecular weight (Mn) of the fluorine-containing elastomer (B) is preferably 20,000 to 300,000 from the viewpoint of fluidity that can be finely dispersed in the fluorine-containing elastomer (A). More preferably, it is 25,000 to 250,000, and still more preferably 30,000 to 200,000.
- the Mooney viscosity at 100 ° C. of the fluorine-containing elastomer (B) is preferably 2 or more and more preferably 5 or more from the viewpoint of good moldability. Further, the Mooney viscosity at 100 ° C. of the fluorine-containing elastomer mixture is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less, from the viewpoint that molding processability is also good.
- the fluorine content of the fluorine-containing elastomer (B) is 70.0% by mass or more, the fuel has low fuel permeability.
- the fluorine content of the fluorine-containing elastomer (B) is preferably 71.0% by mass or more. In view of better cold resistance and flexibility, the content is preferably 74.0% by mass or less, and more preferably 73.5% by mass or less.
- the fluorine-containing elastomer (B) is a perfluoropolymer elastomer.
- the manufacturing method of the said fluorine-containing elastomer (B) is not specifically limited, It can obtain by a general polymerization method.
- the method mentioned in the method for producing the fluorine-containing elastomer (A) can be used, and it is preferable to use an iodine transfer polymerization method.
- the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B) are not compatible with each other, and two glass transition temperatures are observed when they are not compatible with each other.
- the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B) are compatible with each other, the low fuel permeability is improved, but the glass transition temperature is significantly increased, and the target cold resistance may not be obtained. is there.
- the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B) are not compatible with each other, the cold resistance, which is a characteristic of the cold-resistant fluororubber of the fluorine-containing elastomer (A) serving as a matrix, is further improved. Further, the low fuel permeability is improved by the microscopic dispersion of the low-permeability fluorine-containing elastomer (B).
- the fluorine-containing elastomer mixture of the present invention has improved low fuel permeability by containing the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B), the molded product obtained by crosslinking is It has low fuel permeability and low hardness.
- the flexibility inherent to the elastomer is impaired. From the mixture of the present invention, it is possible to obtain a molded article having low fuel permeability and maintaining low hardness that can function as a rubber.
- the glass transition temperature of the fluorine-containing elastomer (A) is preferably lower than the glass transition temperature of the fluorine-containing elastomer (B) from the viewpoint of good cold resistance, and specifically, ⁇ 33 ° C.
- the temperature is preferably -20 ° C, more preferably -32 ° C to -24 ° C.
- the glass transition temperature of the fluorine-containing elastomer (B) is preferably higher than the glass transition temperature of the fluorine-containing elastomer (A) from the viewpoint of good low fuel permeability.
- -20 ° C to 10 ° C is preferable, and -15 ° C to 5 ° C is more preferable.
- the glass transition temperatures of the fluorine-containing elastomers (A) and (B) are measured by a differential scanning calorimetry (DSC) apparatus.
- the fluorine-containing elastomer (A) or the fluorine-containing elastomer (B) may be measured individually or in the form of a mixture.
- the heat balance of the second scan was measured at a temperature increase rate of 10 ° C./min in the temperature range of ⁇ 50 ° C. to 150 ° C. and detected. It can be determined by the midpoint method using two inflection points.
- the fluorine-containing elastomers (A) and (B) preferably have an iodine atom content of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, and 0.1 to 5%. More preferably, it is% by weight.
- the iodine content was measured by mixing 5 mg of Na 2 SO 3 with 12 mg of sample (fluorinated elastomer), and mixing Na 2 CO 3 and K 2 CO 3 in a 1: 1 ratio (weight ratio) with 20 ml of pure water. It is possible to measure using an Shimadzu 20A ion chromatograph after 30 mg of the absorbing solution dissolved in a quartz combustion flask, burned in oxygen and allowed to stand for 30 minutes. As the calibration curve, a KI standard solution, one containing 0.5 ppm of iodine ions or one containing 1.0 ppm can be used.
- the binding position of the iodine atom may be the end of the main chain or the side chain of the fluorine-containing elastomer, and of course may be both.
- the iodine terminal or bromine terminal serves as a crosslinking point (crosslinking site), and a crosslinked fluorine-containing elastomer having a high crosslinking density can be obtained, and peroxide crosslinking can be performed more easily. become.
- a molded product having a TR10 of ⁇ 30 ° C. or lower can be obtained.
- a molded article having a fuel permeability coefficient of 75 g ⁇ cm / cm 2 ⁇ s ⁇ cmHg or less can be obtained.
- the fluorine-containing elastomer mixture of the present invention can be produced by various methods. For example, when the fluorine-containing elastomer mixture is a mixed powder, the fluorine-containing elastomer (A) powder and the fluorine-containing elastomer (B) powder And a method of obtaining a co-coagulated powder by co-coagulating an aqueous dispersion containing the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B). .
- Examples thereof include a method of adding the fluorine-containing elastomer (A) to the aqueous dispersion of the fluorine-containing elastomer (B).
- the method for producing the fluorine-containing elastomer includes an aqueous dispersion containing the fluorine-containing elastomer (A) and the fluorine-containing elastomer (B). It is preferable to include a co-coagulation step for co-coagulating the liquid.
- Examples of the co-coagulation method include: (i) a method of coagulating after mixing an aqueous dispersion of the fluorine-containing elastomer (A) and an aqueous dispersion of the fluorine-containing elastomer (B); A method of coagulating after adding the fluoroelastomer (A) powder to the aqueous dispersion of the fluoroelastomer (B), (iii) aqueous dispersion of the fluoroelastomer (A) with the powder of the fluoroelastomer (B) The method of coagulating after adding to a liquid is mentioned.
- the method (i) is preferable in that each elastomer is particularly easily dispersed uniformly.
- the co-coagulation is preferably carried out by adding an acid such as nitric acid, hydrochloric acid, or sulfuric acid; and metal salt such as magnesium chloride, calcium chloride, sodium chloride, aluminum sulfate, magnesium sulfate, or barium sulfate.
- an acid such as nitric acid, hydrochloric acid, or sulfuric acid
- metal salt such as magnesium chloride, calcium chloride, sodium chloride, aluminum sulfate, magnesium sulfate, or barium sulfate.
- the manufacturing method of the said fluorine-containing elastomer mixture is what manufactures at least any one of the said fluorine-containing elastomer (A) and (B) by the method containing the iodine transfer polymerization method mentioned above.
- the process for producing the fluorine-containing elastomer mixture of the present invention is performed by RI n (wherein n is an integer of 1 to 2 and R is a saturated or unsaturated fluorohydrocarbon group having 1 to 8 carbon atoms or chlorofluoro Radical polymerization is carried out in the presence of an iodine-containing compound represented by a hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms and may contain an oxygen atom), and the fluorine-containing elastomer (A) And a step of polymerizing at least one of (B).
- This invention is also the composition for peroxide vulcanization
- the polyfunctional unsaturated compound (ii) may be a compound having reaction activity with respect to peroxy radicals and polymer radicals.
- Examples thereof include polyfunctional compounds having a functional group such as CF-.
- triallyl cyanurate triallyl isocyanurate (TAIC), trimethallyl isocyanurate, TAIC prepolymer, triacryl formal, triallyl trimellitate, N, N′-n-phenylenebismaleimide , Dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1 , 3,5-triazine-2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallyl phosphor Amide, N, N, N ′, N′-tetraallylte
- the content of the polyfunctional unsaturated compound is 0.5 with respect to the total amount of the fluorine-containing elastomers (A) and (B) from the viewpoint that the compression set and strength properties of the vulcanizate are good. % By mass or more is preferable, and 1.0% by mass or more is more preferable. Further, the content of the polyfunctional unsaturated compound is preferably 6.0% by mass or less with respect to the total amount of the fluorine-containing elastomers (A) and (B), from the viewpoint of preventing mold contamination. The mass% or less is more preferable.
- the peroxide (iii) is generally preferably one that easily generates a peroxy radical in the presence of heat or a redox system.
- the content of the peroxide is preferably 0.5% by mass or more with respect to a total of 100% by mass of the fluorine-containing elastomers (A) and (B) from the viewpoint that a sufficient vulcanization rate is obtained.
- the mass% or more is more preferable.
- the content of the peroxide is preferably 10.0% by mass or less with respect to a total of 100% by mass of the fluorine-containing elastomers (A) and (B), from the viewpoint that sufficient vulcanization characteristics can be obtained. 0.0 mass% or less is more preferable.
- peroxide vulcanizing composition usual additives, for example, fillers, processing aids, plasticizers, colorants and the like, which are blended into the vulcanizable elastomer composition, can be blended as necessary. Further, one or more conventional vulcanizing agents and vulcanization accelerators different from those described above may be blended. Moreover, you may mix and use another type of elastomer in the range which does not impair the effect of this invention.
- the peroxide vulcanizing composition may contain a general filler.
- Common fillers include organic fillers made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyoxybenzoate, polytetrafluoroethylene powder; aluminum oxide, silicon oxide, yttrium oxide, titanium oxide, etc.
- layered minerals represented by montmorillonite are useful for improving the low fuel permeability.
- the composition for peroxide vulcanization can be prepared by mixing the above-described components using an ordinary rubber processing machine, for example, an open roll, a Banbury mixer, a kneader or the like. In addition, it can be prepared by a method using a closed mixer or a method of co-coagulation from emulsion mixing.
- the conditions for vulcanizing the peroxide vulcanizing composition are not particularly limited, and can be performed under the vulcanizing conditions of a normal fluorine-containing elastomer composition.
- the peroxide vulcanizing composition is placed in a mold and kept under pressure at 120 to 250 ° C. (preferably 160 to 220 ° C., more preferably 180 to 220 ° C.) for 1 to 120 minutes.
- Vulcanization followed by oven vulcanization by holding in a furnace at 160-300 ° C (preferably 180-250 ° C, more preferably 180-200 ° C) for 0-48 hours (preferably 4-24 hours)
- a vulcanized product can be obtained.
- This invention is also a molded article obtained by shape
- Specific examples of the molded product include, but are not limited to, the following molded products.
- Sealing material In the automobile field, it can be used for gaskets, shaft seals, valve stem seals, various sealing materials used for engines and peripheral devices, and various sealing materials for AT devices. Examples of the sealing material used in the fuel system and peripheral devices include O (square) -rings, packings, and diaphragms.
- the molded product is more preferably an automobile part that comes into contact with fuel. That is, the present invention also relates to an automobile part that contacts the fuel and is molded using the peroxide vulcanizing composition. Specific examples of automobile parts that come into contact with fuel include, but are not limited to, molded articles in the automobile field described above.
- the fluorine content of the fluorine-containing elastomer mixture is determined from the composition ratio of each polymer calculated from the raw rubber specific gravity value.
- the fluorine content of each polymer is determined by calculation from the polymer composition measured by 19 F-NMR.
- Tg Glass transition temperature
- Tb tensile breaking strength
- Eb tensile breaking elongation
- VdF / TFE / PMVE 68/12/20 mol%
- Reference example 2 A stainless steel autoclave with an internal volume of 6 liters is charged with 3000 g of pure water and 30 g of C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 and 0.27 g of (NH 4 ) 2 CO 3 as emulsifiers.
- the system was thoroughly replaced with nitrogen gas, degassed, and the internal temperature was raised to 50 ° C. while stirring at 600 rpm, and initial preparation of tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE) was performed.
- APS ammonium persulfate
- the fluorine content was 73.0% by mass, and the glass transition temperature measured by DSC was ⁇ 5 ° C.
- Example 1 610 g of the dispersion obtained in Reference Example 1 (polymer content 170 g) and 190 g of the dispersion obtained in Reference Example 2 (polymer content 30 g) were mixed at room temperature, and then co-coagulated with aluminum sulfate. After thoroughly washing with pure water, it was dried with hot air at 80 ° C. for 8 hours and at 120 ° C. for 12 hours to obtain 200 g of a polymer (mixed elastomer powder).
- the raw rubber specific gravity value of the mixed elastomer powder was 1.833 g / cm 3 .
- the content of the TFE / PMVE copolymer elastomer in the following Table 1 is a value obtained from the raw rubber specific gravity value.
- Carbon black (Thermax N990, manufactured by Cancarb) is 20% by mass, TAIC is 3% by mass, and dialkyl peroxide (Perhexa 25B, manufactured by NOF Corporation) is 1 with respect to 100% by mass of the mixed elastomer powder.
- the mixture was kneaded at a ratio of 5% by mass to obtain a vulcanizing composition.
- the physical properties of the obtained vulcanizing composition after press vulcanization under standard vulcanization conditions and further oven vulcanization are as shown in Table 1 below, and it has cold resistance, low fuel permeability and flexibility. An excellent molded product was obtained.
- Example 2 After mixing 510 g of the dispersion obtained in Reference Example 1 (polymer content 140 g) and 380 g of the dispersion obtained in Reference Example 2 (polymer content 60 g) at room temperature, co-coagulation using aluminum sulfate was performed. After thoroughly washing with pure water, it was dried with hot air at 80 ° C. for 8 hours and at 120 ° C. for 12 hours to obtain 200 g of a polymer (mixed elastomer powder).
- a mixed elastomer powder was obtained in the same manner as in Example 1, and a vulcanizing composition was obtained in the same manner as in Example 1.
- the physical properties of the vulcanizing composition were measured.
- the physical properties of the resulting vulcanizing composition after press vulcanization under standard vulcanization conditions and further oven vulcanization are as shown in Table 1 below, and are molded articles with excellent cold resistance and low fuel permeability. was gotten.
- the raw rubber specific gravity value of the mixed elastomer powder in Example 2 was 1.874 g / cm 3 .
- Comparative Example 1 Based on 100% by mass of the elastomer powder obtained in Reference Example 1, 20% by mass of carbon black (Thermax N990, manufactured by Cancarb), 3% by mass of TAIC, dialkyl peroxide (Perhexa 25B, NOF) was kneaded at a ratio of 1.5% by mass to obtain a vulcanizing composition.
- the physical properties of the obtained vulcanizing composition after press vulcanization under standard vulcanization conditions and further oven vulcanization are shown in Table 1 below.
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Abstract
Description
ここで、単量体単位とは、単量体に由来する繰り返し単位を意味する。
なお、含フッ素エラストマー(A)におけるPAVEは、1種でもよいし、2種以上用いてもよい。
水性分散液の場合、含フッ素エラストマー(A)の水性分散液と含フッ素エラストマー(B)の水性分散液を混合する方法、含フッ素エラストマー(A)の水性分散液に含フッ素エラストマー(B)を添加する方法、含フッ素エラストマー(B)の水性分散液に含フッ素エラストマー(A)を添加する方法等が挙げられる。
上記共凝析の方法としては、特に各エラストマーが均一に分散し易い点で、上記(i)の方法が好ましい。
自動車分野では、エンジンならびに周辺装置に用いるガスケット、シャフトシール、バルブステムシール、各種シール材や、AT装置の各種シール材に用いることができる。燃料系統ならびに周辺装置に用いるシール材としては、O(角)-リング、パッキン、ダイアフラムなどがあげられる。具体的には、エンジンヘッドガスケット、メタルガスケット、オイルパンガスケット、クランクシャフトシール、カムシャフトシール、バルブステムシール、マニホールドパッキン、酸素センサー用シール、インジェクターO-リング、インジェクターパッキン、燃料ポンプO-リング、ダイアフラム、クランクシャフトシール、ギアボックスシール、パワーピストンパッキン、シリンダーライナーのシール、バルブステムのシール、自動変速機のフロントポンプシール、リアーアクスルピニオンシール、ユニバーサルジョイントのガスケット、スピードメーターのピニオンシール、フートブレーキのピストンカップ、トルク伝達のO-リング、オイルシール、排ガス再燃焼装置のシール、ベアリングシール、キャブレターのセンサー用ダイアフラム等として用いることができる。
また、上記成形品は、中でも、燃料に接触する自動車部品であることがより好ましい。すなわち、本発明は、上記パーオキサイド加硫用組成物を用いて成形された、燃料に接触する自動車部品にも関する。燃料に接触する自動車部品の具体例としては、上記した自動車分野における成形品が挙げられるが、これらに限定されるものではない。
JIS K6268に準拠して東洋精機社製の自動比重計型式D-1を用いて測定する。
生ゴム比重値から計算により求める。
含フッ素エラストマー混合物のフッ素含有率は、生ゴム比重値から計算された各ポリマーの組成比から求める。
各ポリマーのフッ素含有率は、19F-NMRにて測定されたポリマー組成から計算によって求める。
METTLER TOLEDO社製のDSCにて測定し、10mgのポリマーを-50~150℃の温度範囲で昇温スピード10℃/分、セカンドスキャンの条件で熱収支を測定し、検知された2つの変極点から、中点法により求める。
ASTM-D1646およびJIS K6300に準拠して測定する。
測定機器 :ALPHA TECHNOLOGIES社製のMV2000E型
ローター回転数:2rpm
測定温度 :100℃
各組成物をつぎの標準加硫条件で1次プレス加硫および2次オーブン加硫して、厚さ2mmのシートとし、JIS-K6251に準じて測定する。
(標準加硫条件)
混練方法 :ロール練り
プレス加硫 :160℃で10分
オーブン加硫:180℃で4時間
各組成物を標準加硫条件で1次プレス加硫および2次オーブン加硫して、厚さ2mmのシートとし、JIS-K6251に準じて測定する。
各組成物を標準加硫条件で1次プレス加硫および2次オーブン加硫して、厚さ2mmのシートとし、JIS-K6253に準じて測定する。
ASTM D1329に準拠してUeshima社製のTR試験機にて測定する。
各組成物を下記標準加硫条件で1次プレス加硫および2次オーブン加硫して、厚さ0.5mmのシートとし、ASTM E96に準拠したカップ法にてCE20を用いて40℃で燃料透過係数を測定する。燃料透過係数が小さいほど燃料低透過性において優れる。
混練方法 :ロール練り
プレス加硫 :160℃で10分
オーブン加硫:180℃で4時間
内容積30リットルのステンレススチール製オートクレーブに、純水15kg、乳化剤としてC7F15COONH4を30.0g、リン酸水素ニナトリウムを1.3g仕込み、系内を窒素ガスで充分に置換し脱気したのち、150rpmで攪拌しながら、80℃に昇温し、VdF、TFEおよびPMVEをVdF/TFE/PMVE=64/8/28モル%で、内圧が0.80MPa・Gになるように仕込んだ。ついで、過硫酸アンモニウム(APS)の42.5mg/mlの濃度の水溶液20m1を窒素圧で圧入して反応を開始した。重合の進行により内圧が、0.75MPa・Gまで降下した時点で、I(CF2CF2)2Iを24.9g窒素圧にて圧入した。ついで圧力が0.85MPa・Gになるように、VdF、TFEおよびPMVEの混合ガス(VdF/TFE/PMVE=68/12/20モル%)をそれぞれ圧入した。以後、VdF、TFEおよびPMVEの混合ガス(VdF/TFE/PMVE=68/12/20モル%)を圧入し、0.75~0.85MPa・Gの間で、昇圧、降圧を繰り返した。また3時間毎にAPSを追加し、重合終了までに、840mg追加した。
内容積6リットルのステンレススチール製オートクレーブに、純水3000gおよび乳化剤としてC3F7OCF(CF3)CF2OCF(CF3)COONH4を30g、(NH4)2CO3を0.27g仕込み、系内を窒素ガスで充分に置換し、脱気したのち、600rpmで撹拌しながら、内温を50℃に昇温し、テトラフルオロエチレン(TFE)とパーフルオロメチルビニルエーテル(PMVE)の初期仕込み混合ガス(TFE/PMVE=25.6/74.4モル%比)を内圧が0.83MPa・Gになるように仕込んだ。ついで、過硫酸アンモニウム(APS)0.558gを純水10gに溶解させた溶液を窒素圧で圧入して反応を開始した。
分析の結果、この重合体のモノマー単位組成は、TFE/PMVE=63.3/36.7モル%であり、ムーニー粘度は74であった。フッ素含有率は73.0質量%であり、DSCにて測定したガラス転移温度は-5℃であった。
参考例1で得られた分散液610g(ポリマー含有量170g)と参考例2で得られた分散液190g(ポリマー含有量30g)を室温で混合した後、硫酸アルミニウムを用いて共凝析し、純水で充分に洗浄した後、80℃で8時間、120℃で12時間熱風乾燥させ、200gのポリマー(混合エラストマー粉末)を得た。
当該混合エラストマー粉末の生ゴム比重値は1.833g/cm3であった。なお、下記表1中のTFE/PMVE共重合体エラストマーの含有量は、生ゴム比重値から求めた値である。
参考例1で得られた分散液510g(ポリマー含有量140g)と参考例2で得られた分散液380g(ポリマー含有量60g)を室温で混合した後、硫酸アルミニウムを用いて共凝析し、純水で充分に洗浄した後、80℃で8時間、120℃で12時間熱風乾燥させ、200gのポリマー(混合エラストマー粉末)を得た。
得られた加硫用組成物を標準加硫条件でプレス加硫して、さらにオーブン加硫を行った後の物性は下記表1のとおりであり、耐寒性、燃料低透過性に優れる成形品が得られた。実施例2における混合エラストマー粉末の生ゴム比重値は1.874g/cm3であった。
参考例1で得られたエラストマー粉末100質量%に対し、ミキシングロールにてカーボンブラック(サーマックスN990、Cancarb社製)を20質量%、TAICを3質量%、ジアルキルパーオキサイド(パーヘキサ25B、日油社製)を1.5質量%の比率で混練りし、加硫用組成物を得た。得られた加硫用組成物を標準加硫条件でプレス加硫して、さらにオーブン加硫を行った後の物性は下記表1のとおりである。
Claims (6)
- (A)50~85モル%のフッ化ビニリデン単位及び15~50モル%のパーフルオロ(アルキルビニルエーテル)単位のみからなる共重合体(a1)、又は、45~85モル%のフッ化ビニリデン単位、1~30モル%のテトラフルオロエチレン単位及び14~30モル%のパーフルオロ(アルキルビニルエーテル)単位のみからなる共重合体(a2)であり、ヨウ素原子を有するパーオキサイド加硫可能な含フッ素エラストマーと、
(B)フッ素含有率が70.0質量%以上であり、ヨウ素原子を有するパーオキサイド加硫可能な含フッ素エラストマーと、
を含むことを特徴とする含フッ素エラストマー混合物。 - 含フッ素エラストマー(B)は、
45~85モル%のテトラフルオロエチレン単位及び15~55モル%のパーフルオロ(アルキルビニルエーテル)単位のみからなる共重合体(b1)、
15~85モル%のテトラフルオロエチレン単位、1~30モル%のエチレン単位及び14~55モル%のパーフルオロ(アルキルビニルエーテル)単位のみからなる共重合体(b2)、及び、
25~85モル%のフッ化ビニリデン単位、0~40モル%のテトラフルオロエチレン単位及び15~40モル%のヘキサフルオロプロピレン単位のみからなる共重合体(b3)からなる群より選ばれる少なくとも1種の共重合体である
請求項1記載の含フッ素エラストマー混合物。 - 含フッ素エラストマー(A)と含フッ素エラストマー(B)との質量比(A)/(B)が60/40~95/5である
請求項1又は2に記載の含フッ素エラストマー混合物。 - 請求項1~3のいずれかに記載の含フッ素エラストマー混合物(i)、多官能性不飽和化合物(ii)およびパーオキサイド(iii)を含む
ことを特徴とするパーオキサイド加硫用組成物。 - 請求項4記載のパーオキサイド加硫用組成物を成形して得られる
ことを特徴とする成形品。 - 請求項1~3のいずれかに記載の含フッ素エラストマー混合物を製造する方法であって、含フッ素エラストマー(A)及び含フッ素エラストマー(B)を含む水性分散液を共凝析する工程を含む
ことを特徴とする含フッ素エラストマー混合物の製造方法。
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JP (1) | JP5413455B2 (ja) |
CN (1) | CN102365326B (ja) |
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CN103755856A (zh) * | 2013-12-16 | 2014-04-30 | 江苏梅兰化工有限公司 | 一种用于过氧化物硫化氟弹性体的生产方法 |
JP2015013972A (ja) * | 2013-07-08 | 2015-01-22 | Nok株式会社 | フッ素ゴム系シール材用組成物およびフッ素ゴム系シール材 |
US20150094428A1 (en) * | 2013-09-30 | 2015-04-02 | Honeywell International Inc. | Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization |
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JP5465175B2 (ja) * | 2007-08-29 | 2014-04-09 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | (パー)フルオロエラストマー組成物 |
JP5998588B2 (ja) * | 2012-04-02 | 2016-09-28 | ユニマテック株式会社 | 含フッ素エラストマーブレンド物およびその組成物 |
EP3006473A4 (en) * | 2013-05-27 | 2016-11-23 | Daikin Ind Ltd | PROCESS FOR PRODUCING FLUORINATED POLYMERS |
CN103342772B (zh) * | 2013-07-12 | 2015-08-05 | 中昊晨光化工研究院有限公司 | 一种可用过氧化物硫化的含氟弹性体的制备方法 |
EP3124542A4 (en) * | 2014-03-25 | 2017-11-15 | Asahi Glass Company, Limited | Fluororubber molded article |
US20200299467A1 (en) * | 2016-03-24 | 2020-09-24 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomer composition |
JP6369511B2 (ja) * | 2016-08-30 | 2018-08-08 | ダイキン工業株式会社 | 改質成形品の製造方法、成形品、ダイヤフラム及びダイヤフラムバルブ |
CN113692351B (zh) * | 2019-04-04 | 2023-06-13 | Agc株式会社 | 层叠体的制造方法及层叠体 |
JP2023507103A (ja) * | 2019-12-17 | 2023-02-21 | 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 | 超低温弾性フルオロポリマー組成物及びそれを調製するためのプロセス |
EP4276144A4 (en) * | 2021-01-07 | 2024-08-28 | Nok Corp | FLUOROR RUBBER COMPOSITION AND SEALING ELEMENT |
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JP2000212363A (ja) * | 1999-01-21 | 2000-08-02 | Mitsubishi Cable Ind Ltd | 耐アミン性ゴムシ―ル材 |
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US9394394B2 (en) * | 2013-09-30 | 2016-07-19 | Honeywell International Inc. | Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization |
CN103755856A (zh) * | 2013-12-16 | 2014-04-30 | 江苏梅兰化工有限公司 | 一种用于过氧化物硫化氟弹性体的生产方法 |
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CN102365326B (zh) | 2015-04-22 |
JPWO2010113951A1 (ja) | 2012-10-11 |
US20120029152A1 (en) | 2012-02-02 |
CN102365326A (zh) | 2012-02-29 |
US8450423B2 (en) | 2013-05-28 |
JP5413455B2 (ja) | 2014-02-12 |
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