JP5790423B2 - Fluorine-containing polyether compound and process for producing the same - Google Patents
Fluorine-containing polyether compound and process for producing the same Download PDFInfo
- Publication number
- JP5790423B2 JP5790423B2 JP2011245128A JP2011245128A JP5790423B2 JP 5790423 B2 JP5790423 B2 JP 5790423B2 JP 2011245128 A JP2011245128 A JP 2011245128A JP 2011245128 A JP2011245128 A JP 2011245128A JP 5790423 B2 JP5790423 B2 JP 5790423B2
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- JP
- Japan
- Prior art keywords
- fluorine
- compound
- polyether compound
- containing polyether
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000001875 compounds Chemical class 0.000 title claims description 54
- 229910052731 fluorine Inorganic materials 0.000 title claims description 36
- 239000011737 fluorine Substances 0.000 title claims description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 35
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 28
- 229920000570 polyether Polymers 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 24
- -1 dicarboxylic acid fluoride compound Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 150000001448 anilines Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 150000001451 organic peroxides Chemical class 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- JOQDDLBOAIKFQX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I JOQDDLBOAIKFQX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- AEKNNFQRMWYGTR-UHFFFAOYSA-N 2-iodo-N-methyl-N-phenylacetamide Chemical compound ICC(=O)N(C)C1=CC=CC=C1 AEKNNFQRMWYGTR-UHFFFAOYSA-N 0.000 description 2
- YXNAWCUIZOCJNG-UHFFFAOYSA-N 2-iodo-n-phenylacetamide Chemical compound ICC(=O)NC1=CC=CC=C1 YXNAWCUIZOCJNG-UHFFFAOYSA-N 0.000 description 2
- WPHUUIODWRNJLO-UHFFFAOYSA-N 2-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1S(Cl)(=O)=O WPHUUIODWRNJLO-UHFFFAOYSA-N 0.000 description 2
- IZVRDZGBMDYYQT-UHFFFAOYSA-N 4-iodo-n-methylaniline Chemical compound CNC1=CC=C(I)C=C1 IZVRDZGBMDYYQT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YOHCESILUZUPTL-UHFFFAOYSA-N N-(4-iodophenyl)-N-methyl-2-nitrobenzenesulfonamide Chemical compound CN(c1ccc(I)cc1)S(=O)(=O)c1ccccc1[N+]([O-])=O YOHCESILUZUPTL-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 2
- ZTAPIPKJZHGVJV-UHFFFAOYSA-N n-(4-iodophenyl)-2-nitrobenzenesulfonamide Chemical compound [O-][N+](=O)C1=CC=CC=C1S(=O)(=O)NC1=CC=C(I)C=C1 ZTAPIPKJZHGVJV-UHFFFAOYSA-N 0.000 description 2
- SIULLDWIXYYVCU-UHFFFAOYSA-N n-(4-iodophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(I)C=C1 SIULLDWIXYYVCU-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 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
- QBEWJJSQJWLVAI-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-icosafluoro-1,10-diiododecane Chemical compound FC(F)(I)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)I QBEWJJSQJWLVAI-UHFFFAOYSA-N 0.000 description 1
- SRDQTCUHAMDAMG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1,8-diiodooctane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I SRDQTCUHAMDAMG-UHFFFAOYSA-N 0.000 description 1
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- 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
- SSFSNKZUKDBPIT-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=C(S(Cl)(=O)=O)C([N+]([O-])=O)=C1 SSFSNKZUKDBPIT-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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- YLDILLQKQASWBA-UHFFFAOYSA-N 2-bromo-n-methyl-n-phenylacetamide Chemical compound BrCC(=O)N(C)C1=CC=CC=C1 YLDILLQKQASWBA-UHFFFAOYSA-N 0.000 description 1
- DCPLOIFDMMEBQZ-UHFFFAOYSA-N 2-bromo-n-phenylacetamide Chemical compound BrCC(=O)NC1=CC=CC=C1 DCPLOIFDMMEBQZ-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-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
- SNWPATXDOVKHSC-UHFFFAOYSA-N CNC1=CC=C(C=C1)C(C(C(C(C(C(F)(F)I)(F)F)(F)F)(F)F)(F)F)(F)F Chemical compound CNC1=CC=C(C=C1)C(C(C(C(C(C(F)(F)I)(F)F)(F)F)(F)F)(F)F)(F)F SNWPATXDOVKHSC-UHFFFAOYSA-N 0.000 description 1
- PFJFNQUFMTYCHB-UHFFFAOYSA-N C[SiH2]N[SiH3] Chemical compound C[SiH2]N[SiH3] PFJFNQUFMTYCHB-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- 150000005690 diesters Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- XXHOHJTVFUJJMT-UHFFFAOYSA-N n-(3-bromophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(Br)=C1 XXHOHJTVFUJJMT-UHFFFAOYSA-N 0.000 description 1
- MSLICLMCQYQNPK-UHFFFAOYSA-N n-(4-bromophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Br)C=C1 MSLICLMCQYQNPK-UHFFFAOYSA-N 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 239000007966 viscous suspension Substances 0.000 description 1
Landscapes
- Polyethers (AREA)
Description
本発明は、含フッ素ポリエーテル化合物およびその製造法に関する。さらに詳しくは、高分子主鎖両末端に架橋性反応部位を有する含フッ素ポリエーテル化合物およびその製造法に関する。 The present invention relates to a fluorine-containing polyether compound and a method for producing the same. More specifically, the present invention relates to a fluorine-containing polyether compound having a crosslinkable reaction site at both ends of a polymer main chain and a method for producing the same.
分子末端に官能基を有する含フッ素ポリエーテル化合物としては、例えば一般式
で表わされる化合物が知られている(特許文献1参照)。
As the fluorine-containing polyether compound having a functional group at the molecular end, for example, a general formula
Is known (see Patent Document 1).
また、上記化合物の主鎖構造をオリゴマー化した、より一般的な化合物として、一般式
で表わされる化合物が知られている(特許文献2参照)。
In addition, as a more general compound obtained by oligomerizing the main chain structure of the above compound, a general formula
Is known (see Patent Document 2).
これらの一般式で表わされる化合物群は、分子内にSi-H基を複数個有する含フッ素オルガノ水素シロキサン化合物および白金化合物触媒により硬化し、非常に優れた特性(耐薬品性、耐熱性、低温特性)を有するエラストマー性成形物を与え得るとされ、特に-50℃程度の低温条件下でも柔軟性を失わずに、使用に耐え得るとされる。また、これらを主成分とする硬化性組成物は、抜群の成形加工性を有し、RIM成形も可能とさせる。しかしながら、この硬化物は、分子内架橋構造にシロキサン結合を有するため、フッ化水素などの酸性物質が存在する条件下で使用されると、化学的劣化によりそれの機械的な強度が低下するなどの好ましくない結果を与えることもある。 The compounds represented by these general formulas are cured by a fluorine-containing organohydrogensiloxane compound having a plurality of Si-H groups in the molecule and a platinum compound catalyst, and have excellent properties (chemical resistance, heat resistance, low temperature) It is said that an elastomeric molded product having characteristics) can be provided, and in particular, it can be used without loss of flexibility even under a low temperature condition of about -50 ° C. Moreover, the curable composition which has these as a main component has outstanding moldability, and also enables RIM molding. However, since this cured product has a siloxane bond in its intramolecular cross-linked structure, its mechanical strength decreases due to chemical degradation when used under conditions where acidic substances such as hydrogen fluoride are present. May give undesirable results.
本発明者は先に、Si-H結合を有する含フッ素オルガノ水素シロキサン化合物を必要としないで硬化可能であり、その上耐熱性、低温特性および成形加工性に優れ、しかも酸性条件下での使用に耐え得る硬化物を与える含フッ素ポリエーテル化合物として、一般式
(ここで、R1は水素原子、炭素数1〜3のアルキル基またはフェニル基であり、Xはヨウ素原子または臭素原子であり、Xのフェニル基上の置換位置はNR1結合置換基に対してm-またはp-位であり、lおよびmはそれぞれ独立に10以上の整数であって、l+mは30〜130である)で表わされる含フッ素ポリエーテル化合物を提案している(特許文献3参照)。
The present inventor previously can cure without the need for a fluorine-containing organohydrogensiloxane compound having a Si—H bond, and is excellent in heat resistance, low temperature characteristics and moldability, and used under acidic conditions. As a fluorine-containing polyether compound that gives a cured product that can withstand
(Wherein R 1 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, X is an iodine atom or a bromine atom, and the substitution position of X on the phenyl group is relative to the NR 1 -bonded substituent. And m- or p-position, l and m are each independently an integer of 10 or more, and l + m is 30 to 130). Reference 3).
この含フッ素ポリエーテル化合物は、ボロン酸エステル化合物により硬化し、エラストマー性成形物を与えることができるが、より一般的な架橋方法である過酸化物架橋には不適である。 This fluorine-containing polyether compound can be cured with a boronic acid ester compound to give an elastomeric molded product, but is not suitable for peroxide crosslinking, which is a more general crosslinking method.
本発明の目的は、主鎖として
を有する含フッ素ポリエーテル化合物の高分子主鎖両末端に有機過酸化物またはアゾ化合物により架橋可能な反応部位を形成させた新規化合物およびその製造法を提供することにある。
The purpose of the present invention is to
It is an object of the present invention to provide a novel compound in which reactive sites capable of cross-linking with an organic peroxide or an azo compound are formed at both ends of a polymer main chain of a fluorine-containing polyether compound having the above and a method for producing the same.
本発明によって、一般式
(ここで、R1は水素原子または炭素数1〜3のアルキル基であり、lおよびmはそれぞれ独立に10以上の整数であって、l+mは30〜200であり、nは4〜10の整数である)で表わされる含フッ素ポリエーテル化合物が提供される。
According to the invention, the general formula
(Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, l and m are each independently an integer of 10 or more, l + m is 30 to 200, and n is 4 to 4) And a fluorine-containing polyether compound represented by the following formula:
かかる含フッ素ポリエーテル化合物は、一般式
(ここで、lおよびmはそれぞれ独立に10以上の整数であって、l+mは30〜200である)で表わされる含フッ素ジカルボン酸フルオリド化合物に、一般式
(ここで、R1は水素原子または炭素数1〜3のアルキル基であり、R2は水素原子またはトリメチルシリル基であって、nは4〜10の整数である)で表わされるω-ヨードパーフルオロアルキル置換アニリン誘導体を、好ましくはピリジンまたは3級アミン化合物の存在下で、反応させることによって製造される。
Such fluorine-containing polyether compounds have the general formula
(Wherein l and m are each independently an integer of 10 or more, and l + m is 30 to 200), a fluorine-containing dicarboxylic acid fluoride compound represented by the general formula
(Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2 is a hydrogen atom or a trimethylsilyl group, and n is an integer of 4 to 10). Prepared by reacting a fluoroalkyl-substituted aniline derivative, preferably in the presence of pyridine or a tertiary amine compound.
本発明に係る含フッ素ポリエーテル化合物は、高分子主鎖両末端に反応部位としてω-ヨードパーフルオロアルキル基を有しているので、有機過酸化物またはアゾ化合物による架橋を可能とし、架橋によりエラストマー性成形物を与えることができる。かかる組成物を硬化して得られる成形物は、低温特性、耐薬品性などにすぐれているため、自動車燃料供給系シール材、オイルシール材、航空機燃料系および油圧系シール材、半導体製造装置シール材等の各種用途に好適に使用される。 Since the fluorine-containing polyether compound according to the present invention has ω-iodoperfluoroalkyl groups as reaction sites at both ends of the polymer main chain, crosslinking with an organic peroxide or azo compound is possible. Elastomeric moldings can be provided. Molded products obtained by curing such compositions are excellent in low-temperature characteristics, chemical resistance, etc., so that they are excellent in automobile fuel supply system seal materials, oil seal materials, aircraft fuel systems and hydraulic system seal materials, and semiconductor manufacturing equipment seals. It is suitably used for various applications such as materials.
本発明の含フッ素ポリエーテル化合物
において、lおよびmはそれぞれ独立に10以上の整数であって、l+mは30〜200の整数である。特に、エラストマー性高分子材料の主原料として用いる場合には、硬化後十分な機械的強度を有する成形物を得るために、l+mは50〜150であることが好ましい。R1は水素原子または炭素数1〜3のアルキル基であり、分子間水素結合の形成を避けるためには炭素数1〜3のアルキル基が好ましく、特に製造のし易さの点からはメチル基であることが好ましい。
Fluorinated polyether compound of the present invention
In the formula, l and m are each independently an integer of 10 or more, and l + m is an integer of 30 to 200. In particular, when used as a main raw material for an elastomeric polymer material, l + m is preferably 50 to 150 in order to obtain a molded product having sufficient mechanical strength after curing. R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable in order to avoid the formation of intermolecular hydrogen bonds, and methyl is particularly preferred from the viewpoint of ease of production. It is preferably a group.
本発明の含フッ素ポリエーテル化合物は、例えば以下のような一連の工程を経て製造することができる。
注) HFPO:ヘキサフルオロプロペンオキシド
HFP:ヘキサフルオロプロペン
The fluorine-containing polyether compound of the present invention can be produced, for example, through the following series of steps.
Note) HFPO: Hexafluoropropene oxide
HFP: Hexafluoropropene
第二工程の含フッ素ジカルボン酸フルオリド化合物〔II〕とω-ヨードパーフルオロアルキル置換アニリン誘導体〔III〕との反応において、R1は水素原子または炭素数1〜3のアルキル基であり、R2は水素原子またはトリメチルシリル基である。また、ω-ヨードパーフルオロアルキル基 I(CF2)n-のベンゼン環上の置換位置は、アミノ基(-NR1-)に対してo-、m-またはp-位である。 In the reaction of the fluorine-containing dicarboxylic acid fluoride compound [II] and the ω-iodoperfluoroalkyl-substituted aniline derivative [III] in the second step, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 Is a hydrogen atom or a trimethylsilyl group. In addition, the substitution position on the benzene ring of the ω-iodoperfluoroalkyl group I (CF 2 ) n- is the o-, m-, or p-position with respect to the amino group (-NR 1- ).
ω-ヨードパーフルオロアルキル置換アニリン誘導体〔III〕の具体例としては、2-(6-ドデカフルオロヘキシル)アニリン、2-(8-ヘキサデカフルオロオクチル)アニリン、3-(6-ドデカフルオロヘキシル)アニリン、3-(8-ヘキサデカフルオロオクチル)アニリン、4-(6-ドデカフルオロヘキシル)アニリン、4-(8-ヘキサデカフルオロオクチル)アニリン、2-(6-ドデカフルオロヘキシル)-N-メチルアニリン、2-(8-ヘキサデカフルオロオクチル)-N-メチルアニリン、3-(6-ドデカフルオロヘキシル)-N-メチルアニリン、3-(8-ヘキサデカフルオロオクチル)-N-メチルアニリン、4-(6-ドデカフルオロヘキシル)-N-メチルアニリン、4-(8-ヘキサデカフルオロオクチル)-N-メチルアニリンまたはこれらのN-トリメチルシリル誘導体等が挙げられる。 Specific examples of the ω-iodoperfluoroalkyl-substituted aniline derivative [III] include 2- (6-dodecafluorohexyl) aniline, 2- (8-hexadecafluorooctyl) aniline, and 3- (6-dodecafluorohexyl). Aniline, 3- (8-hexadecafluorooctyl) aniline, 4- (6-dodecafluorohexyl) aniline, 4- (8-hexadecafluorooctyl) aniline, 2- (6-dodecafluorohexyl) -N-methyl Aniline, 2- (8-hexadecafluorooctyl) -N-methylaniline, 3- (6-dodecafluorohexyl) -N-methylaniline, 3- (8-hexadecafluorooctyl) -N-methylaniline, 4 Examples include-(6-dodecafluorohexyl) -N-methylaniline, 4- (8-hexadecafluorooctyl) -N-methylaniline, and N-trimethylsilyl derivatives thereof.
ω-ヨードパーフルオロアルキル置換アニリン誘導体〔III〕は、一般式
(ここで、R1は水素原子または炭素数1〜3のアルキル基であり、Xはヨウ素原子または臭素原子である)で表わされる、ハロゲン基がヨウ素基または臭素基であるハロゲノアセトアニリドまたは炭素数1〜3のアルキル基で置換されたそのN-モノアルキル置換体と一般式
で表わされる、炭素数4〜10のパーフルオロアルキレン基を有するω,ω′-ジヨードパーフルオロアルカン化合物とを、銅触媒の存在下でカップリング反応(U11mann反応)させて得られた、一般式
で表わされる化合物を加水分解することによって、ω-ヨードパーフルオロアルキル置換アニリン誘導体〔III;R2=H〕を得ることができる。
The ω-iodoperfluoroalkyl-substituted aniline derivative [III] has the general formula
(Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is an iodine atom or a bromine atom), a halogenoacetanilide or a carbon number in which the halogen group is an iodine group or a bromine group Its N-monoalkyl substituents substituted with 1 to 3 alkyl groups and the general formula
A ω, ω′-diiodoperfluoroalkane compound having a C 4-10 perfluoroalkylene group represented by the general formula, obtained by a coupling reaction (U11mann reaction) in the presence of a copper catalyst, formula
Is hydrolyzed, an ω-iodoperfluoroalkyl-substituted aniline derivative [III; R 2 = H] can be obtained.
ハロゲノアセトアニリド化合物〔IV〕としては、2-ヨードアセトアニリド、2-ヨード-N-メチルアセトアニリド、3-ヨードアセトアニリド、3-ヨード-N-メチルアセトアニリド、4-ヨードアセトアニリド、4-ヨード-N-メチルアセトアニリド、2-ブロモアセトアニリド、2-ブロモ-N-メチルアセトアニリド、3-ブロモアセトアニリド、3-ブロモ-N-メチルアセトアニリド、4-ブロモアセトアニリド、4-ブロモ-N-メチルアセトアニリド等が挙げられる。反応性の面からは、2-ヨードアセトアニリド、2-ヨード-N-メチルアセトアニリド、3-ヨードアセトアニリド、3-ヨード-N-メチルアセトアニリド、4-ヨードアセトアニリド、4-ヨード-N-メチルアセトアニリドが好ましい。 Examples of the halogenoacetanilide compound [IV] include 2-iodoacetanilide, 2-iodo-N-methylacetanilide, 3-iodoacetanilide, 3-iodo-N-methylacetanilide, 4-iodoacetanilide, 4-iodo-N-methylacetanilide 2-bromoacetanilide, 2-bromo-N-methylacetanilide, 3-bromoacetanilide, 3-bromo-N-methylacetanilide, 4-bromoacetanilide, 4-bromo-N-methylacetanilide and the like. From the viewpoint of reactivity, 2-iodoacetanilide, 2-iodo-N-methylacetanilide, 3-iodoacetanilide, 3-iodo-N-methylacetanilide, 4-iodoacetanilide, 4-iodo-N-methylacetanilide are preferable. .
ハロゲノアセトアニリド化合物〔IV〕との反応に用いられるω,ω′-ジヨードパーフルオロアルカン化合物〔V〕としては、1,4-ジヨードオクタフルオロブタン、1,6-ジヨードドデカフルオロヘキサン、1,8-ジヨードヘキサデカフルオロオクタン、1,10-ジヨードイコサフルオロデカン等が挙げられる。ω,ω′-ジヨードパーフルオロアルカン化合物〔V〕は、ハロゲノアセトアニリド化合物〔IV〕に対して1.0〜3.0モル当量用いられる。特に、カップリング反応生成物〔VI〕の収率面から、1.5〜3.0モル当量用いるのが好ましい。 As the ω, ω′-diiodoperfluoroalkane compound [V] used in the reaction with the halogenoacetanilide compound [IV], 1,4-diiodooctafluorobutane, 1,6-diiodododecafluorohexane, 1 1,8-diiodohexadecafluorooctane, 1,10-diiodoicosafluorodecane, and the like. The ω, ω′-diiodoperfluoroalkane compound [V] is used in an amount of 1.0 to 3.0 molar equivalents relative to the halogenoacetanilide compound [IV]. In particular, it is preferable to use 1.5 to 3.0 molar equivalents from the viewpoint of the yield of the coupling reaction product [VI].
この反応に際しては、市販の銅粉、EDTA・2Na水溶液によって活性化された銅粉、硫酸銅と亜鉛粉末から生成したGattermann銅等の銅触媒を用いることができる。銅触媒は、ハロゲノアセトアニリド化合物〔IV〕に対して、1.5〜2.5モル当量用いられる。1.5モル当量以下では、ハロゲノアセトアニリド化合物〔IV〕の反応率が低下し、結果的にカップリング反応生成物〔VI〕の収率が低下する。一方、2.5モル当量以上では、意図しない反応による副生成物の生成により、カップリング反応生成物〔VI〕の収率が低下する。 In this reaction, a copper catalyst such as commercially available copper powder, copper powder activated with an EDTA · 2Na aqueous solution, or Gattermann copper produced from copper sulfate and zinc powder can be used. The copper catalyst is used in an amount of 1.5 to 2.5 molar equivalents relative to the halogenoacetanilide compound [IV]. When the amount is 1.5 molar equivalents or less, the reaction rate of the halogenoacetanilide compound [IV] decreases, and as a result, the yield of the coupling reaction product [VI] decreases. On the other hand, at 2.5 molar equivalents or more, the yield of the coupling reaction product [VI] decreases due to the formation of by-products due to unintended reactions.
ハロゲノアセトアニリド化合物〔IV〕とω,ω′-ジヨードパーフルオロアルカン化合物〔V〕とのカップリング反応は、非プロトン性極性溶媒中で行われる。用いられる非プロトン性極性溶媒としては、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジエチルアセトアミド、N-メチル-2-ピロリドン、ジメチルスルホキシド、ジグライム等、スルホラン等が挙げられ、特にジメチルスルホキシドが好ましい。反応は約50℃〜200℃、好ましくは約80〜150℃で行われる。なお、このカップリング反応は、銅触媒に加えて、2,2′-ビピリジルのような触媒の存在下で行っても良い。 The coupling reaction between the halogenoacetanilide compound [IV] and the ω, ω′-diiodoperfluoroalkane compound [V] is carried out in an aprotic polar solvent. Aprotic polar solvents used include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, diglyme , Sulfolane and the like, and dimethyl sulfoxide is particularly preferable. The reaction is carried out at about 50 to 200 ° C, preferably about 80 to 150 ° C. The coupling reaction may be performed in the presence of a catalyst such as 2,2′-bipyridyl in addition to the copper catalyst.
ハロゲノアセトアニリド化合物〔IV〕は、一般式
で表わされるハロゲノアニリン化合物を、氷酢酸または無水酢酸によりアセチル化することによって容易に得ることができる。
The halogenoacetanilide compound [IV] has the general formula
Can be easily obtained by acetylation with glacial acetic acid or acetic anhydride.
N-モノアルキルハロゲノアニリン化合物(R1:炭素数1〜3のアルキル基の場合)は、ハロゲノアニリン化合物を、N-モノアルキル化することによって得られる。モノアルキル化は、ヨウ化アルキル、ジアルキル硫酸等のアルキル化剤により行うことができる。ただし、この反応では生成物がモノアルキル体、ジアルキル体および未反応の原料の混合物となるので、蒸留、液体クロマトグラフィー等によって、反応混合物からモノアルキル体を分離する操作が必要になる。この分離操作において、モノアルキル体をアセチル化した後分離操作を行い、次いで加水分解して、モノアルキル体を単離することもできる。 An N-monoalkylhalogenoaniline compound (R 1 : in the case of an alkyl group having 1 to 3 carbon atoms) is obtained by N-monoalkylating a halogenoaniline compound. Monoalkylation can be carried out with an alkylating agent such as alkyl iodide or dialkyl sulfuric acid. However, in this reaction, the product becomes a mixture of a monoalkyl body, a dialkyl body and an unreacted raw material, and thus an operation for separating the monoalkyl body from the reaction mixture by distillation, liquid chromatography or the like is required. In this separation operation, the monoalkyl body can be isolated by acetylating the monoalkyl body and then performing the separation operation, followed by hydrolysis.
N-モノアルキルアニリン化合物を製造するに際しては、選択的なN-アルキル化反応を用いることが収率面でより好ましい。例えば、非特許文献1または2に記載されているスルホンアミドを経由する方法が挙げられる。具体的には、ハロゲノアニリン化合物(R1:水素原子の場合)を、2-ニトロベンゼンスルホニルクロリドまたは2,4-ジニトロベンゼンスルホニルクロリドによりスルホンアミド化した後、ハロゲン化アルキルによりN-モノアルキル化する。次いで、塩基性条件下でチオフェノールまたはメルカプト酢酸を作用させることにより、N-モノアルキルハロゲノアニリン化合物を得ることができる。 In producing the N-monoalkylaniline compound, it is more preferable in terms of yield to use a selective N-alkylation reaction. Examples thereof include a method via a sulfonamide described in Non-Patent Document 1 or 2. Specifically, a halogenoaniline compound (R 1 : in the case of a hydrogen atom) is sulfonamidated with 2-nitrobenzenesulfonyl chloride or 2,4-dinitrobenzenesulfonyl chloride, and then N-monoalkylated with an alkyl halide. . Next, an N-monoalkylhalogenoaniline compound can be obtained by reacting thiophenol or mercaptoacetic acid under basic conditions.
また、ω-ヨードパーフルオロアルキル置換アニリン誘導体〔III〕のR2基はN-トリメチルシリル基であってもよく、かかるトリメチルシリル誘導体は、該アニリン誘導体〔III;R2=H〕にトリメチルシリルクロリドまたはヘキサメチルジシラザンを反応させることにより、容易に得ることができる。 The R 2 group of the ω-iodoperfluoroalkyl-substituted aniline derivative [III] may be an N-trimethylsilyl group, and the trimethylsilyl derivative is added to the aniline derivative [III; R 2 = H] by trimethylsilyl chloride or hexa It can be easily obtained by reacting methyldisilazane.
本発明の含フッ素ポリエーテル化合物〔I〕は、含フッ素ジカルボン酸フルオリド〔II〕をω-ヨードパーフルオロアルキル置換アニリン誘導体〔III〕と反応させることにより得ることができる。 The fluorine-containing polyether compound [I] of the present invention can be obtained by reacting a fluorine-containing dicarboxylic acid fluoride [II] with an ω-iodoperfluoroalkyl-substituted aniline derivative [III].
含フッ素ジカルボン酸フルオリド〔II〕とω-ヨードパーフルオロアルキル置換アニリン誘導体〔III〕との反応は、ピリジン等の活性水素を有しない塩基性含窒素複素環式化合物またはトリエチルアミン等の3級アミン化合物の存在下で、ハイドロクロロフルオロカーボン、ハイドロフルオロカーボン、ハイドロフルオロエーテル等の含フッ素溶媒、またはこれらの含フッ素溶媒と非プロトン性非フッ素系溶媒との混合溶媒中で、-50〜150℃、好ましくは0〜100℃の反応温度で行われる。含フッ素溶媒の具体例としては、HCFC-225、HFE-449(住友3M製品HFE7100)、HFE-569(住友3M製品HFE-7200)、1,3-ビス(トリフルオロメチル)ベンゼン等が挙げられる。非プロトン性非フッ素系溶媒としては、例えばジエチルエーテル、ジイソプロピルエーテル、シクロペンチルメチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒が挙げられる。アニリン化合物〔III〕の溶解性を考慮すると、含フッ素溶媒と非プロトン性非フッ素系溶媒の混合溶媒を用いるのがより好ましい。 Reaction of fluorine-containing dicarboxylic acid fluoride [II] with ω-iodoperfluoroalkyl-substituted aniline derivative [III] is a basic nitrogen-containing heterocyclic compound having no active hydrogen such as pyridine or a tertiary amine compound such as triethylamine. -50 to 150 ° C., preferably in a fluorinated solvent such as hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroether, or a mixed solvent of these fluorinated solvent and aprotic non-fluorinated solvent in the presence of It is carried out at a reaction temperature of 0-100 ° C. Specific examples of the fluorine-containing solvent include HCFC-225, HFE-449 (Sumitomo 3M product HFE7100), HFE-569 (Sumitomo 3M product HFE-7200), 1,3-bis (trifluoromethyl) benzene, and the like. . Examples of the aprotic non-fluorine solvent include ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran and dioxane. Considering the solubility of the aniline compound [III], it is more preferable to use a mixed solvent of a fluorinated solvent and an aprotic non-fluorinated solvent.
本発明の含フッ素ポリエーテル化合物の具体例として、
等が例示される。
As a specific example of the fluorine-containing polyether compound of the present invention,
Etc. are exemplified.
本発明に係る含フッ素ポリエーテル化合物は、有機過酸化物またはアゾ化合物によって架橋せしめることができる。架橋に際しては、多官能性不飽和化合物を併用することが好ましい。 The fluorine-containing polyether compound according to the present invention can be crosslinked with an organic peroxide or an azo compound. In crosslinking, it is preferable to use a polyfunctional unsaturated compound in combination.
有機過酸化物としては、例えば2,5-ジメチル-2,5-ジ(第3ブチルパーオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(第3ブチルパーオキシ)ヘキシン-3、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、ベンゾイルパーオキシド、ジ第3ブチルパーオキシド、第3ブチルクミルパーオキシド、ジクミルパーオキシド、第3ブチルパーオキシベンゼン、1,1-ビス(第3ブチルパーオキシ)-3,5,5-トリメチルシクロヘキサン、2,5-ジメチルヘキサン-2,5-ジヒドロキシパーオキシド等が、含フッ素ポリエーテル化合物100重量部当り約0.1〜10重量部、好ましくは約0.5〜5重量部の割合で用いられる。 Examples of the organic peroxide include 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, tert-butyl peroxybenzene, 1, 1-bis (tertiary butyl peroxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxy peroxide, etc. is about 0.1 to 10 per 100 parts by weight of the fluorinated polyether compound. Part by weight, preferably about 0.5 to 5 parts by weight is used.
架橋に際しては、有機過酸化物の代りにアゾ化合物を用いることもできる。アゾ化合物としては、例えば2,2′-アゾビス(イソブチロニトリル)、2,2′-アゾビス(2,4-ジメチルバレロニトリル)等が、含フッ素ポリエーテル化合物100重量部当り約0.5〜5重量部の割合で用いられる。 In crosslinking, an azo compound can be used in place of the organic peroxide. As the azo compound, for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are about 0.5 to 5 per 100 parts by weight of the fluorinated polyether compound. Used in parts by weight.
また、多官能性不飽和化合物としては、例えばトリアリルイソシアヌレート、トリアリルシアヌレート、トリアクリルホルマール、トリアリルトリメリテート等が、含フッ素ポリエーテル化合物100重量部に対し約1〜20重量部、好ましくは約5〜15重量部の割合で用いられる。 In addition, as the polyfunctional unsaturated compound, for example, triallyl isocyanurate, triallyl cyanurate, triacryl formal, triallyl trimellitate and the like are about 1 to 20 parts by weight with respect to 100 parts by weight of the fluorine-containing polyether compound. , Preferably about 5 to 15 parts by weight.
含フッ素ポリエーテル化合物の硬化は、これに有機過酸化物またはアゾ化合物、好ましくは有機過酸化物またはアゾ化合物と多官能性不飽和化合物の両者を加え、さらに必要に応じてカーボンブラック、シリカ等の補強剤または充填剤その他を加え、約100〜180℃で約5〜30分間圧縮成形し、必要に応じて約150〜250℃で約5〜24時間程度オーブン加硫することにより行われる。なお、成形は、RIM成形によっても可能である。 Curing of the fluorine-containing polyether compound is performed by adding an organic peroxide or an azo compound, preferably both an organic peroxide or an azo compound and a polyfunctional unsaturated compound, and further, if necessary, carbon black, silica, etc. The above-mentioned reinforcing agent or filler is added, compression molding is performed at about 100 to 180 ° C. for about 5 to 30 minutes, and if necessary, oven vulcanization is performed at about 150 to 250 ° C. for about 5 to 24 hours. The molding can also be performed by RIM molding.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
参考例1
含フッ素ジカルボン酸フルオリド化合物の調製
攪拌装置、温度センサ、ガス導入口およびドライアイス/エタノール冷却凝縮器を備えた、内容量1Lのガラス製反応容器を低温恒温槽に設置し、ジアルコキシド化合物 CsOCF2CF(CF3)OCF2CF2OCF(CF3)CF2OCs を32ミリモルを含むテトラグライム溶液60gを仕込んだ。内温を-33〜-30℃に調整した後、ガス導入口よりヘキサフルオロプロペンを40g仕込んだ。次に、ヘキサフルオロプロペンオキシドを10g/hr、ヘキサフルオロプロペンを4g/hrの供給速度で反応容器内に仕込んだ。46時間経過後、ガスの供給を停止し(ヘキサフルオロプロペンオキシド総仕込量546g)、さらに1時間-33〜-30℃に内温を保った。減圧下でヘキサフルオロプロペンを反応系内より除去した後、室温までゆっくり昇温した。さらに100℃まで昇温し、減圧下でヘキサフルオロプロペンオリゴマーを反応混合物より除去した。このようにして、フッ化セシウム、テトラグライムおよび含フッ素ジカルボン酸フルオリドからなる混合物を淡黄色粘稠な懸濁液として600g得た。これを精製せずに、次の工程に用いた。
Reference example 1
Preparation of fluorinated dicarboxylic acid fluoride compounds
A 1 L glass reaction vessel equipped with a stirrer, temperature sensor, gas inlet, and dry ice / ethanol cooled condenser was placed in a low-temperature thermostatic chamber, and dialkoxide compound CsOCF 2 CF (CF 3 ) OCF 2 CF 60 g of a tetraglyme solution containing 32 mmol of 2 OCF (CF 3 ) CF 2 OCs was charged. After adjusting the internal temperature to -33 to -30 ° C, 40 g of hexafluoropropene was charged from the gas inlet. Next, hexafluoropropene oxide was charged into the reaction vessel at a feed rate of 10 g / hr and hexafluoropropene at 4 g / hr. After 46 hours, the gas supply was stopped (total amount of hexafluoropropene oxide charged: 546 g), and the internal temperature was kept at -33 to -30 ° C for 1 hour. After removing hexafluoropropene from the reaction system under reduced pressure, the temperature was slowly raised to room temperature. The temperature was further raised to 100 ° C., and the hexafluoropropene oligomer was removed from the reaction mixture under reduced pressure. Thus, 600 g of a mixture composed of cesium fluoride, tetraglyme and fluorine-containing dicarboxylic acid fluoride was obtained as a pale yellow viscous suspension. This was used in the next step without purification.
また、上記混合物の一部をメタノールによりジエステル体〔A〕とした後、19F-NMRによりヘキサフルオロプロペンオキシド数平均重合度および二官能性比(ヘキサフルオロプロペンオキシドオリゴマー〔B〕とのモル分率)を求めた。
ヘキサフルオロプロペンオキシドオリゴマー:
s=Fa(-131ppm)ピーク積分値
t=Fb(-133ppm)ピーク積分値
u=Fc(-146ppm)ピーク積分値
注) ケミカルシフトはCFCl3基準
二官能性比=(t/s-0.5)/(t/s+0.5)=0.79
ヘキサフルオロプロペンオキシド数平均重合度=4u/(2t+s)=80
Further, after a part of the above mixture was converted into a diester form [A] with methanol, the number average polymerization degree of hexafluoropropene oxide and the bifunctional ratio (mole fraction with hexafluoropropene oxide oligomer [B] were determined by 19 F-NMR. Rate).
Hexafluoropropene oxide oligomer:
s = F a (-131ppm) peak integrated value
t = F b (-133ppm) peak integrated value
u = F c (-146ppm) peak integral value
Note) Chemical shift is based on CFCl 3 Bifunctional ratio = (t / s-0.5) / (t / s + 0.5) = 0.79
Hexafluoropropene oxide number average degree of polymerization = 4u / (2t + s) = 80
参考例2
(1) 4-ヨードアニリン36.9g(169ミリモル)、2-ニトロベンゼンスルホニルクロリド43.0g(194ミリモル)およびピリジン(228ミリモル)を、300mlのクロロホルム中、室温条件下で3時間反応させた。得られた反応溶液に400mlのジクロロメタンを加え、これらの混合物よりなる有機相を水で数回洗浄した。水洗された有機相を硫酸マグネシウムで脱水した後溶媒を留去し、茶色の固体としてN-(4-ヨードフェニル)-2-ニトロベンゼンスルホンアミドを58.6g得た(収率85%)。
(2) N-(4-ヨードフェニル)-2-ニトロベンゼンスルホンアミド58.6g(145ミリモル)、ヨードメタン25.7g(181ミリモル)および炭酸カリウム100g(725ミリモル)を、300mlのN,N′-ジメチルホルムアミド〔DMF〕中、室温条件下で4時間反応させた。得られた反応溶液に600mlの水を加えた後、水-DMF混合物相についてジクロロメタンで抽出した。ジクロロメタン相を水で数回洗浄し、硫酸マグネシウムで脱水した後溶媒を留去し、黄色の固体としてN-(4-ヨードフェニル)-N-メチル-2-ニトロベンゼンスルホンアミドを56.3g得た(収率93%)。
(3) N-(4-ヨードフェニル)-N-メチル-2-ニトロベンゼンスルホンアミド10g(24ミリモル)、メルカプト酢酸4.4g(48ミリモル)および水酸化リチウム・一水和物4.0g(96ミリモル)を、80mlのN,N′-ジメチルホルムアミド中、室温条件下で3時間反応させた。得られた反応溶液に300mlの水を加えた後、水-DMF混合物相についてジクロロメタン抽出を行った。ジクロロメタン相を3重量%の炭酸カリウム水溶液で数回洗浄し、硫酸マグネシウムで脱水した後溶媒を留去し、茶褐色の液体として4-ヨード-N-メチルアニリンを5.3g得た(収率95%)。
(4) 4-ヨード-N-メチルアニリン7.7g(33ミリモル)、無水酢酸3.9g(38ミリモル)およびピリジン3.0g(38ミリモル)を、室温条件下で1時間反応させた後、反応混合物に水50mlを加え、クロロホルムで生成物を抽出した。反応後通常の後処理を行い、黄色固体8.6gを得た。この黄色固体について、ジエチルエーテル:エタノール=5:1(v/v)混合溶媒を用いて再結晶を行い、黄色の固体として4-ヨード-N-メチルアセトアニリド7.6g(収率84%)を得た。
(5) 4-ヨード-N-メチルアセトアニリド1.80g(6.55ミリモル)、1,6-ジヨードドデカフルオロヘキサン7.26g(13.1ミリモル)、銅粉0.83g(13.1ミリモル)および2,2′-ビピリジル132mg(0.85ミリモル)を、90mlのジメチルスルホキシド中、窒素雰囲気下で、120℃で9時間反応させた。反応終了後、水300mlおよびジクロロメタン200mlを加え、不溶物をろ別した後有機相を分取した。分取した有機相を水で洗浄し、硫酸マグネシウムで乾燥、次いでジクロロメタンを留去して、反応混合物を得た。反応混合物について、ジエチルエーテル:ヘキサン=2:1(v/v)混合液を流出液とするカラムクロマトグラフィー(ワコーゲルC-300)による分離操作を行い、目的とする4-(6-ヨードドデカフルオロヘキシル)-N-メチルアセトアニリドを1.84g得た(収率49%)。これをジエチルエーテル:n-ヘキサン=1:1(v/v)混合液で再結晶し、無色の固体として精製物1.58gを得た(収率42%)。
(6) 上記手法に従い計2回合成した4-(6-ヨードドデカフルオロヘキシル)-N-メチルアセトアニリド2.70gを、濃塩酸30mlおよびメタノール60mlの混合液中、90℃で5時間反応させた。反応終了後、飽和炭酸水素ナトリウム水溶液を加えて中和した後、ジエチルエーテルで抽出操作を行った。抽出液を硫酸マグネシウムで脱水した後溶媒を留去し、黄色の油状物を2.45g得た。この油状物について、ジクロロメタン:ヘキサン=1:2(v/v)を流出液とするカラムクロマトグラフィー(ワコーゲルC-300)による分離操作を行い、目的とする4-(6-ヨードドデカフルオロヘキシル)-N-メチルアニリンを無色の固体として1.82g得た(収率73%)。
融点:42〜44℃
1H-NMR(CDCl3、300MHz)δ(TMS基準):
2.87ppm (singlet、3H、Nb 3)
4.05ppm (brs、1H、Ha)
6.61ppm (doublet、2Hc、Hc)
7.36ppm (doublet、2Hd、Hd)
19F-NMR(CDCl3、300MHz)δ(CFCl3基準):
-59.7ppm (s、2F、Ff)
-110.3ppm (s、2F、Fa)
-114.1ppm (s、2F、Fe))
-122.1ppm (s、2F、Fb)
-122.4ppm (s、2F、Fc)
-123.1ppm (s、2F、Fd)
IR(neat)γ:
3,420cm-1
1,610cm-1
1,150cm-1
Reference example 2
(1) 36.9 g (169 mmol) of 4-iodoaniline, 43.0 g (194 mmol) of 2-nitrobenzenesulfonyl chloride and pyridine (228 mmol) were reacted in 300 ml of chloroform at room temperature for 3 hours. 400 ml of dichloromethane was added to the resulting reaction solution, and the organic phase composed of these mixtures was washed several times with water. The organic phase washed with water was dehydrated with magnesium sulfate, and then the solvent was distilled off to obtain 58.6 g of N- (4-iodophenyl) -2-nitrobenzenesulfonamide as a brown solid (yield 85%).
(2) 58.6 g (145 mmol) of N- (4-iodophenyl) -2-nitrobenzenesulfonamide, 25.7 g (181 mmol) of iodomethane and 100 g (725 mmol) of potassium carbonate were added to 300 ml of N, N′-dimethylformamide. The reaction was carried out in [DMF] at room temperature for 4 hours. After adding 600 ml of water to the resulting reaction solution, the water-DMF mixture phase was extracted with dichloromethane. The dichloromethane phase was washed several times with water, dehydrated with magnesium sulfate, and then the solvent was distilled off to obtain 56.3 g of N- (4-iodophenyl) -N-methyl-2-nitrobenzenesulfonamide as a yellow solid ( Yield 93%).
(3) 10 g (24 mmol) of N- (4-iodophenyl) -N-methyl-2-nitrobenzenesulfonamide, 4.4 g (48 mmol) of mercaptoacetic acid and 4.0 g (96 mmol) of lithium hydroxide monohydrate Was reacted in 80 ml of N, N′-dimethylformamide at room temperature for 3 hours. After adding 300 ml of water to the resulting reaction solution, the water-DMF mixture phase was extracted with dichloromethane. The dichloromethane phase was washed several times with 3% by weight aqueous potassium carbonate solution and dehydrated with magnesium sulfate, and then the solvent was distilled off to obtain 5.3 g of 4-iodo-N-methylaniline as a brown liquid (yield 95%). ).
(4) 7.7 g (33 mmol) of 4-iodo-N-methylaniline, 3.9 g (38 mmol) of acetic anhydride and 3.0 g (38 mmol) of pyridine were reacted at room temperature for 1 hour, and then the reaction mixture was mixed. 50 ml of water was added and the product was extracted with chloroform. After the reaction, usual post-treatment was performed to obtain 8.6 g of a yellow solid. The yellow solid was recrystallized using a mixed solvent of diethyl ether: ethanol = 5: 1 (v / v) to obtain 7.6 g (yield 84%) of 4-iodo-N-methylacetanilide as a yellow solid. It was.
(5) 4-iodo-N-methylacetanilide 1.80 g (6.55 mmol), 1,6-diiodododecafluorohexane 7.26 g (13.1 mmol), copper powder 0.83 g (13.1 mmol) and 2,2′-bipyridyl 132 mg (0.85 mmol) was reacted in 90 ml dimethyl sulfoxide for 9 hours at 120 ° C. under nitrogen atmosphere. After completion of the reaction, 300 ml of water and 200 ml of dichloromethane were added, the insoluble matter was filtered off, and the organic phase was separated. The separated organic phase was washed with water, dried over magnesium sulfate, and then dichloromethane was distilled off to obtain a reaction mixture. The reaction mixture was separated by column chromatography (Wakogel C-300) using the diethyl ether: hexane = 2: 1 (v / v) mixture as the effluent, and the desired 4- (6-iodododecafluoro) was obtained. 1.84 g of hexyl) -N-methylacetanilide was obtained (49% yield). This was recrystallized with a mixed solution of diethyl ether: n-hexane = 1: 1 (v / v) to obtain 1.58 g of a purified product as a colorless solid (yield 42%).
(6) 2.70 g of 4- (6-iodododecafluorohexyl) -N-methylacetanilide synthesized twice according to the above procedure was reacted at 90 ° C. for 5 hours in a mixture of concentrated hydrochloric acid 30 ml and methanol 60 ml. After completion of the reaction, the reaction mixture was neutralized by adding a saturated aqueous sodium hydrogen carbonate solution, and then extracted with diethyl ether. The extract was dehydrated with magnesium sulfate and the solvent was distilled off to obtain 2.45 g of a yellow oil. This oily substance was subjected to separation operation by column chromatography (Wakogel C-300) using dichloromethane: hexane = 1: 2 (v / v) as an effluent to obtain the desired 4- (6-iodododecafluorohexyl). 1.82 g of -N-methylaniline was obtained as a colorless solid (yield 73%).
Melting point : 42-44 ° C
1 H-NMR (CDCl 3 , 300 MHz) δ (TMS standard):
2.87ppm (singlet, 3H, N b 3 )
4.05ppm (brs, 1H, H a )
6.61ppm (doublet, 2H c, H c)
7.36ppm (doublet, 2H d , H d )
19 F-NMR (CDCl 3 , 300 MHz) δ (CFCl 3 standard):
-59.7ppm (s, 2F, F f )
-110.3ppm (s, 2F, F a )
-114.1ppm (s, 2F, F e ))
-122.1ppm (s, 2F, F b )
-122.4ppm (s, 2F, F c )
-123.1ppm (s, 2F, F d )
IR (neat) γ:
3,420cm -1
1,610cm -1
1,150cm -1
実施例
参考例1で得られた、少量のフッ化セシウムおよびテトラグライムを含む含フッ素ジカルボン酸フルオリド(l+m=80)18g(約1.3ミリモル)を、含フッ素系溶媒(住友3M製品HFE-7100)50mlに溶解し、トリエチルアミン0.40g(3.9ミリモル)およびジエチルエーテル10mlを加えた。そこに、参考例2で得られた4-(6-ヨードドデカフルオロヘキシル)-N-メチルアニリン1.8g(3.4ミリモル)を加え、室温条件下で4時間反応を行った。得られた反応混合物を飽和食塩水に加え、分離した有機相を水で数回洗浄した後、無水硫酸マグネシウムで乾燥、ろ過した。減圧下でろ液から含フッ素系溶媒およびジエチルエーテルを留去した後、得られた粘稠な液体をジエチルエーテルで数回洗浄し、次いで減圧下でジエチルエーテルを完全に留去した。このようにして、含フッ素ポリエーテル化合物
を、僅かに黄色味を帯びた透明な液体として15g得た。E型粘度計(東機産業製TEV-22)により粘度を測定したところ、12Pa・s(25℃)であった。
19F-NMR(ケミカルシフトはCFCl3基準): -124ppm(Fa)
-147ppm(Fb)
-110ppm(Fc)
-122ppm(Fd~f)
-110ppm(Fg)
-60ppm(Fh)
1H-NMR(ケミカルシフトはTMS基準): 7.5ppm(Ha)
6.6ppm(Hb)
3.1ppm(Hc)
IR(neat): 1704cm−1(C=O)
1610cm−1(Ar)
Examples Fluorine-containing dicarboxylic acid fluoride (l + m = 80) 18 g (about 1.3 mmol) containing a small amount of cesium fluoride and tetraglyme obtained in Reference Example 1 was added to a fluorine-containing solvent (Sumitomo 3M product HFE- 7100) was dissolved in 50 ml, and 0.40 g (3.9 mmol) of triethylamine and 10 ml of diethyl ether were added. Thereto was added 1.8 g (3.4 mmol) of 4- (6-iodododecafluorohexyl) -N-methylaniline obtained in Reference Example 2, and the reaction was performed at room temperature for 4 hours. The obtained reaction mixture was added to saturated brine, and the separated organic phase was washed several times with water, dried over anhydrous magnesium sulfate, and filtered. After the fluorine-containing solvent and diethyl ether were distilled off from the filtrate under reduced pressure, the resulting viscous liquid was washed several times with diethyl ether, and then diethyl ether was completely distilled off under reduced pressure. Thus, a fluorine-containing polyether compound
Was obtained as a slightly yellowish transparent liquid. When the viscosity was measured with an E-type viscometer (TEV-22 manufactured by Toki Sangyo), it was 12 Pa · s (25 ° C.).
19 F-NMR (Chemical shift is based on CFCl 3 ): -124 ppm (F a )
-147ppm (F b )
-110ppm (F c)
-122ppm (F d ~ f )
-110ppm (F g)
-60ppm (F h)
1 H-NMR (chemical shift is based on TMS): 7.5 ppm (H a )
6.6ppm (H b )
3.1 ppm (H c )
IR (neat): 1704cm -1 (C = O)
1610cm -1 (Ar)
参考例3
実施例で得られた含フッ素ポリエーテル化合物 100重量部
2,2′-アゾビス(イソブチロニトリル) 3重量部
トリアリルイソシアヌレート 12重量部
1,3-ビス(トリフルオロメチル)ベンゼン 400重量部
以上の各成分を窒素雰囲気下、室温条件下で10分間混合し、次いで減圧下で揮発性成分を留去した。
Reference example 3
100 parts by weight of the fluorinated polyether compound obtained in the examples
2,2'-azobis (isobutyronitrile) 3 parts by weight triallyl isocyanurate 12 parts by weight
Each component of 400 parts by weight or more of 1,3-bis (trifluoromethyl) benzene was mixed for 10 minutes at room temperature under a nitrogen atmosphere, and then volatile components were distilled off under reduced pressure.
得られた混合物に、
アセチレンカーボンブラック 13重量部
をプラネタリーミキサを用いて混合し、硬化性組成物を調製した。
In the resulting mixture,
13 parts by weight of acetylene carbon black was mixed using a planetary mixer to prepare a curable composition.
この硬化性組成物について、モンサントディスクレオメーターを使用して、130℃、30分間の硬化挙動を測定し、次のような結果を得た。
ML 0.4 dN・m
MH 17.9 dN・m
t10 0.6 分
t50 1.3 分
t90 12.9 分
With respect to this curable composition, the curing behavior at 130 ° C. for 30 minutes was measured using a Monsanto disc rheometer, and the following results were obtained.
ML 0.4 dN ・ m
MH 17.9 dN ・ m
t10 0.6 min
t50 1.3 minutes
t90 12.9 minutes
さらに、130℃で30分間圧縮成形してP24 Oリングを成形し、次いで100℃、5時間および230℃、10時間のオーブン加硫(二次加硫)を、窒素雰囲気下で行った。これについて、圧縮永久歪(ASTM D395 Method B準拠;200℃、70時間)の測定を行い、30%という値を得た。 Further, a P24 O-ring was formed by compression molding at 130 ° C. for 30 minutes, and then oven vulcanization (secondary vulcanization) at 100 ° C. for 5 hours and 230 ° C. for 10 hours was performed in a nitrogen atmosphere. The compression set (according to ASTM D395 Method B; 200 ° C., 70 hours) was measured and a value of 30% was obtained.
また、このP24 Oリングのガラス転移温度Tgを、示差走査熱量分析計(SIIナノテクノロジー社製DSC6220)を用いて測定すると、-55℃という値が得られた。 Further, when the glass transition temperature Tg of the P24 O-ring was measured using a differential scanning calorimeter (DSC6220 manufactured by SII Nanotechnology), a value of −55 ° C. was obtained.
Claims (7)
(ここで、R1は水素原子または炭素数1〜3のアルキル基であり、lおよびmはそれぞれ独立に10以上の整数であって、l+mは30〜200であり、nは4〜10の整数である)で表わされる含フッ素ポリエーテル化合物。 General formula
(Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, l and m are each independently an integer of 10 or more, l + m is 30 to 200, and n is 4 to 4) A fluorine-containing polyether compound represented by an integer of 10.
(ここで、lおよびmはそれぞれ独立に10以上の整数であって、l+mは30〜200である)で表わされる含フッ素ジカルボン酸フルオリド化合物に、一般式
(ここで、R1は水素原子または炭素数1〜3のアルキル基であり、R2は水素原子またはトリメチルシリル基であって、nは4〜10の整数である)で表わされるω-ヨードパーフルオロアルキル置換アニリン誘導体を反応させることを特徴とする請求項1記載の含フッ素ポリエーテル化合物の製造法。 General formula
(Wherein l and m are each independently an integer of 10 or more, and l + m is 30 to 200), a fluorine-containing dicarboxylic acid fluoride compound represented by the general formula
(Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2 is a hydrogen atom or a trimethylsilyl group, and n is an integer of 4 to 10). The method for producing a fluorine-containing polyether compound according to claim 1, wherein a fluoroalkyl-substituted aniline derivative is reacted.
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