JP5054300B2 - イミノオキサジアジンジオン基含有ポリイソシアネートの製造方法 - Google Patents
イミノオキサジアジンジオン基含有ポリイソシアネートの製造方法 Download PDFInfo
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- JP5054300B2 JP5054300B2 JP2005293524A JP2005293524A JP5054300B2 JP 5054300 B2 JP5054300 B2 JP 5054300B2 JP 2005293524 A JP2005293524 A JP 2005293524A JP 2005293524 A JP2005293524 A JP 2005293524A JP 5054300 B2 JP5054300 B2 JP 5054300B2
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- JP
- Japan
- Prior art keywords
- acid
- enoic acid
- catalyst
- group
- enoic
- 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.)
- Expired - Fee Related
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- 239000005056 polyisocyanate Substances 0.000 title claims description 30
- 229920001228 polyisocyanate Polymers 0.000 title claims description 30
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000003054 catalyst Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 20
- -1 9,9,9,8,8,7,7,6,6, 5,5,4,4,3,3-pentadecafluorononanoic acid 10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3, 3-heptadecafluorodecanoic acid Chemical compound 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 9
- KSNKQSPJFRQSEI-UHFFFAOYSA-N 3,3,3-trifluoropropanoic acid Chemical group OC(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-N 0.000 claims description 6
- UVLNQGHDUGHTGV-UHFFFAOYSA-N 3,3,4,4,4-pentafluorobutanoic acid Chemical compound OC(=O)CC(F)(F)C(F)(F)F UVLNQGHDUGHTGV-UHFFFAOYSA-N 0.000 claims description 5
- PMNVMTIBUIRJHZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexanoic acid Chemical compound OC(=O)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PMNVMTIBUIRJHZ-UHFFFAOYSA-N 0.000 claims description 5
- KDHKNZMUAYFSHV-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptanoic acid Chemical compound OC(=O)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KDHKNZMUAYFSHV-UHFFFAOYSA-N 0.000 claims description 5
- KJBJUTSBUKQIKR-UHFFFAOYSA-N 3,3-difluoroprop-2-enoic acid Chemical compound OC(=O)C=C(F)F KJBJUTSBUKQIKR-UHFFFAOYSA-N 0.000 claims description 5
- WKAYWQKZZYEPTI-UHFFFAOYSA-N 3,4,4,4-tetrafluorobut-2-enoic acid Chemical compound OC(=O)C=C(F)C(F)(F)F WKAYWQKZZYEPTI-UHFFFAOYSA-N 0.000 claims description 5
- ZJJJWFMRGDMLHL-UHFFFAOYSA-N 3,4,4,5,5,5-hexafluoropent-2-enoic acid Chemical compound OC(=O)C=C(F)C(F)(F)C(F)(F)F ZJJJWFMRGDMLHL-UHFFFAOYSA-N 0.000 claims description 5
- CMFAKTRZLATJOA-UHFFFAOYSA-N 3,4,4,5,5,6,6,6-octafluorohex-2-enoic acid Chemical compound OC(=O)C=C(F)C(F)(F)C(F)(F)C(F)(F)F CMFAKTRZLATJOA-UHFFFAOYSA-N 0.000 claims description 5
- WDFZDAAAOFRNFY-UHFFFAOYSA-N 4,4,5,5,6,6,6-heptafluoro-3,3-bis(trifluoromethyl)hexanoic acid Chemical compound OC(=O)CC(C(F)(F)F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F WDFZDAAAOFRNFY-UHFFFAOYSA-N 0.000 claims description 5
- LRWIIEJPCFNNCZ-UHFFFAOYSA-N 62FTA Chemical compound OC(=O)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LRWIIEJPCFNNCZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000004714 phosphonium salts Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- NLAGAXIWWHZGCK-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanoic acid Chemical compound OC(=O)CC(F)(F)C(F)(F)C(F)(F)F NLAGAXIWWHZGCK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 13
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- VLQRWBZMXZAWNQ-UHFFFAOYSA-N 3,4,4,5,5,6,6,7,7,7-decafluorohept-2-enoic acid Chemical compound OC(=O)C=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VLQRWBZMXZAWNQ-UHFFFAOYSA-N 0.000 description 4
- BKOBFLVYTXYFQZ-UHFFFAOYSA-N 6:2 fluorotelomer unsaturated carboxylic acid Chemical compound OC(=O)C=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BKOBFLVYTXYFQZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000007942 carboxylates Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 3
- YLXMZWSVIPOWNY-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoropentane Chemical compound CCC(F)(F)C(F)(F)C(F)(F)F YLXMZWSVIPOWNY-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RAEAYTICAPHWJW-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)propanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)F RAEAYTICAPHWJW-UHFFFAOYSA-N 0.000 description 1
- IRCSJTPOPWQKAA-UHFFFAOYSA-N 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)butanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)C(F)(F)F IRCSJTPOPWQKAA-UHFFFAOYSA-N 0.000 description 1
- MYSBKPZZBHPIES-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoro-2-(trifluoromethyl)pentanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F MYSBKPZZBHPIES-UHFFFAOYSA-N 0.000 description 1
- IWZYOERZELTLQI-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluoro-2-(trifluoromethyl)hexanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F IWZYOERZELTLQI-UHFFFAOYSA-N 0.000 description 1
- BAKGKNAGKNZJSL-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)heptanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BAKGKNAGKNZJSL-UHFFFAOYSA-N 0.000 description 1
- HVQYIRJJPIREIV-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-2-(trifluoromethyl)octanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HVQYIRJJPIREIV-UHFFFAOYSA-N 0.000 description 1
- MFKFLPFCGLSKFM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2-(trifluoromethyl)decanoic acid Chemical compound OC(=O)C(C(F)(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)F MFKFLPFCGLSKFM-UHFFFAOYSA-N 0.000 description 1
- DGVAQXFINLZTET-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)nonanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DGVAQXFINLZTET-UHFFFAOYSA-N 0.000 description 1
- WGIXJOMRYLUUNW-UHFFFAOYSA-N 3,4,4,5,5,6,6,7,7,8,8,9,9,9-tetradecafluoronon-2-enoic acid Chemical compound OC(=O)C=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WGIXJOMRYLUUNW-UHFFFAOYSA-N 0.000 description 1
- XVGVNOVEJAWYEO-UHFFFAOYSA-N 3,4-dihydro-2h-oxadiazine Chemical compound C1NNOC=C1 XVGVNOVEJAWYEO-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- LYLOBGBQGGNMAV-UHFFFAOYSA-N 4,4,5,5,6,6,7,7,7-nonafluoro-3,3-bis(trifluoromethyl)heptanoic acid Chemical compound OC(=O)CC(C(F)(F)F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LYLOBGBQGGNMAV-UHFFFAOYSA-N 0.000 description 1
- HXTUYPCJADHRHV-UHFFFAOYSA-N 4,4,5,5,6,6,7,7,8,8,8-undecafluoro-3,3-bis(trifluoromethyl)octanoic acid Chemical compound OC(=O)CC(C(F)(F)F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HXTUYPCJADHRHV-UHFFFAOYSA-N 0.000 description 1
- CDWHSORDBJATKG-UHFFFAOYSA-N 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-3,3-bis(trifluoromethyl)nonanoic acid Chemical compound OC(=O)CC(C(F)(F)F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDWHSORDBJATKG-UHFFFAOYSA-N 0.000 description 1
- WHZXTVOEGZRRJM-UHFFFAOYSA-N 8:2 fluorotelomer unsaturated carboxylic acid Chemical compound OC(=O)C=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WHZXTVOEGZRRJM-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000801643 Homo sapiens Retinal-specific phospholipid-transporting ATPase ABCA4 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000003810 Jones reagent Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- JTDWCIXOEPQECG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCCCC(C)(C)C JTDWCIXOEPQECG-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 102100033617 Retinal-specific phospholipid-transporting ATPase ABCA4 Human genes 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- IPSOQTFPIWIGJT-UHFFFAOYSA-N acetic acid;1-propoxypropane Chemical compound CC(O)=O.CCCOCCC IPSOQTFPIWIGJT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1883—Catalysts containing secondary or tertiary amines or salts thereof having heteroatoms other than oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
(Rf)n-CR’(3-n)-C(O)O− (I)
〔式中、
Rfは、必要に応じて分枝状、環状および/または不飽和の過フッ化C1〜C30基であり、
R’は、同一または異なって、H、C1〜C20アルキルおよび/またはアリールからなる群から選択される、必要に応じてヘテロ原子を含有する置換基であり、
nは、1または2である。〕
に対応するアニオンを含有する触媒の存在下、
イミノオキサジアジンジオン基を含有しないポリイソシアネートのイソシアネート基部分を三量体化することを含む、方法に関する。
適当な基材としては、既知の材料、特に金属、木材、プラスチックおよびセラミックが挙げられる。
0.5gの3,3,3-トリフルオロプロパン酸を、マグネチックスターラーロッドを使用して攪拌しながら1mlのメタノール中に溶解した。次いで、30%濃度のメタノール中のナトリウムメトキシドの溶液(0.7g)を滴下した。穏やかに加熱しながら、白色エマルジョンを形成させた。30分間攪拌した後、1mlのメタノールを添加し、その後、70%濃度のテトラブチルホスホニウムクロリドのイソプロパノール溶液(1.63g)を滴下した。室温にて2時間攪拌した後、混合物をろ過し(200μmのろ過板)、沈澱をメタノールで繰り返し洗浄し、次いで、合わせたろ液を、室温で10mbarの真空下濃縮した。1H NMR分光法によって決定された、得られた溶液のCF3CH2CO2 −Bu4P+含量は、92%であった。また、2%イソプロパノールおよび6%メタノールが検出された。19F NMRスペクトルにおいて、視認可能なシグナルは、−63.3ppmのCF3基のシグナルのみであった。
セプタムを有するガラス容器中で、50℃にて、窒素下、マグネチックスターラーロッドを使用して攪拌した、10.4g(61.8mmol)の新たに脱気したHDIを、24mgの触媒溶液I(0.06mmolのCF3CH2CO2 −Bu4P+;HDIに基づく0.1モル%の触媒に相当)と混合した。その後、定期的に、反応の進行を反応混合物の屈折率(20℃でのナトリウムスペクトルのD線の光の振動数、nD 20)(開始=変換なし=純粋なHDIのnD 20=1.4523)を測定することによって確認した。5.5時間後、nD 20=1.4635にて、反応の進行を、40%濃度のイソプロパノール中のp-トルエンスルホン酸の溶液(25mg)を添加することによって停止した。イミノオキサジアジンジオン基に対するイソシアヌレートのNMR-スペクトル比は、1:1であった。
攪拌機、内部温度計、触媒用計量手段および還流冷却器を備え、不活性ガスユニット(窒素)を設置した四つ口丸底フラスコ中、200g(1.19mol)のHDIを、真空(0.1mbar)下、60℃で30分間攪拌することによって、溶解したガスから解放させた。窒素の導入に続いて、0.55gの触媒溶液IIを30分間に渡って少量ずつ滴下した。この添加の間、反応混合物の内部温度は、わずかに62℃まで上昇した。60℃でさらに1時間攪拌した後、反応混合物のnD 20は、1.4588であった。その後、さらなる反応を、40%濃度のイソプロパノール中のp-トルエンスルホン酸の溶液(0.25g)を添加することにより停止した。イミノオキサジアジンジオン基に対するイソシアヌレートのNMR-スペクトル比は、53:47であった。0.1mbarおよび150℃での薄膜蒸留による反応混合物の残渣は、以下のデータを有するポリイソシアネート樹脂(32g)を与えた:
NCO含量:24.1%
粘度(23℃):640mPa・s。
44.6mgの触媒III(0.062mmolのCF3(CF2)7CH2CO2 −Bu4P+;HDIに基づく0.1モル%の触媒に相当)を使用した以外は、上記実施例1の手順を繰り返した。50℃で2時間攪拌した後、反応混合物のnD 20は、1.4789であった。その後、さらなる反応を、40%濃度のイソプロパノール中のp-トルエンスルホン酸の溶液(27mg)を添加することにより停止した。イミノオキサジアジンジオン基に対するイソシアヌレートのNMR-スペクトル比は、47:53であった。
44.6mgの触媒IV(0.05mmolのCF3(CF2)6CF=CHCO2 −Bu4P+;HDIに基づく0.09モル%の触媒に相当)を使用した以外は、上記実施例1の手順を繰り返した。50℃で2.5時間攪拌した後、反応混合物のnD 20は、1.4875であった。その後、さらなる反応を、40%濃度のイソプロパノール中のp-トルエンスルホン酸の溶液(2.3mg)を添加することにより停止した。イミノオキサジアジンジオン基に対するイソシアヌレートのNMR-スペクトル比は、62:38であった。
39.3mgの触媒V(0.06mmolのCF3(CF2)2C(CF3)2CH2CO2 −Bu4P+;HDIに基づく約0.1モル%の触媒に相当)を使用した以外は、上記実施例1の手順を繰り返した。50℃で2時間攪拌した後、粘性の反応混合物のnD 20は、1.4902であった。その後、さらなる反応を、40%濃度のイソプロパノール中のp-トルエンスルホン酸の溶液(25mg)を添加することにより停止した。イミノオキサジアジンジオン基に対するイソシアヌレートのNMR-スペクトル比は、64:36であった。
500gのHDIを15分間に渡って滴下して、反応混合物の内部温度が69℃以下に上昇するような速度で、合計3gの触媒溶液A1と混合した以外は、上記実施例2の手順を繰り返した。60℃でさらに1時間攪拌した後、反応混合物のnD 20は、1.4627であった。混合物の滴定されたNCO含量は、43.4%に低下した。その後、さらなる反応を、0.07gのリン酸ジブチルを添加することにより停止した。NMRスペクトルにおいて、イソシアヌレートおよびアロファネートに加えて、微量のみのイミノオキサジアジンジオンが検出された。0.1mbarおよび150℃での薄膜蒸留による反応混合物の残渣は、以下のデータを有するポリイソシアネート樹脂(114g)を与えた:
NCO含量:22.6%
粘度(23℃):1700mPa・s。
31mgの触媒A2(0.06mmolのCF3(CF2)2(CH2)2CO2 −Bu4P+;HDIに基づく0.1モル%の触媒に相当)を使用した以外は、上記実施例1の手順を繰り返した。50℃で3時間攪拌した後、反応混合物のnD 20は、1.4710に上昇した。NMRスペクトルにおいて、イソシアヌレートに加えて、微量のみのイミノオキサジアジンジオンが検出された。
448mgの触媒A3(0.6mmolのCF3(CF2)7CO2 −Bu4P+;HDIに基づく1モル%の触媒に相当)を使用した以外は、上記実施例1の手順を繰り返した。50℃で24時間攪拌した後、反応混合物のnD 20は、幾分上昇した(1.4608)。非常に高い触媒濃度および長い反応時間を考慮すると、このことは、A3は、所望のNCOオリゴマー化、特にイミノオキサジアジンジオンの形成に関して実質的に不活性であることを示す。
〔1〕イミノオキサジアジンジオン基含有ポリイソシアネートの製造方法であって、式I):
(Rf)n-CR’(3-n)-C(O)O− (I)
〔式中、
Rfは、必要に応じて分枝状、環状および/または不飽和の過フッ化C1〜C30基であり、
R’は、同一または異なって、H、C1〜C20アルキルおよび/またはアリールからなる群から選択される、必要に応じてヘテロ原子を含有する置換基であり、
nは、1または2である。〕
に対応するアニオンを含有する触媒の存在下、
イミノオキサジアジンジオン基を含有しないポリイソシアネートのイソシアネート基部分を三量体化することを含む、方法。
〔2〕上記イミノオキサジアジンジオン基を含有しないポリイソシアネートは、脂肪族的におよび/または脂環族的に結合したNCO基を有する、上記第〔1〕項に記載の方法。
〔3〕第四級アンモニウムカチオンまたはホスホニウムカチオンを、式I)で示されるアニオンの対イオンとして使用する、上記第〔1〕項に記載の方法。
〔4〕第四級アンモニウムカチオンまたはホスホニウムカチオンを、式I)で示されるアニオンの対イオンとして使用する、上記第〔2〕項に記載の方法。
〔5〕上記触媒は、3,3,3-トリフルオロプロパン酸、4,4,4,3,3-ペンタフルオロブタン酸、5,5,5,4,4,3,3-ヘプタフルオロペンタン酸、6,6,6,5,5,4,4,3,3-ノナフルオロヘキサン酸、7,7,7,6,6,5,5,4,4,3,3-ウンデカフルオロヘプタン酸、8,8,8,7,7,6,6,5,5,4,4,3,3-トリデカフルオロオクタン酸、9,9,9,8,8,7,7,6,6,5,5,4,4,3,3-ペンタデカフルオロノナン酸、10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-ヘプタデカフルオロデカン酸、3,3-ジフルオロプロパ-2-エン酸、4,4,4,3-テトラフルオロブタ-2-エン酸、5,5,5,4,4,3-ヘキサフルオロペンタ-2-エン酸、6,6,6,5,5,4,4,3-オクタフルオロヘキサ-2-エン酸、7,7,7,6,6,5,5,4,4,3-デカフルオロヘプタ-2-エン酸、8,8,8,7,7,6,6,5,5,4,4,3-ドデカフルオロオクタ-2-エン酸、9,9,9,8,8,7,7,6,6,5,5,4,4,3-テトラデカフルオロノナ-2-エン酸、10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3-ヘキサデカフルオロデカ-2-エン酸または3,3-ビス(トリフルオロメチル)-6,6,6,5,5,4,4-ヘプタフルオロヘキサン酸の第四級アンモニウム塩または第四級ホスホニウム塩を含んでなる、上記第〔1〕項に記載の方法。
〔6〕上記触媒は、3,3,3-トリフルオロプロパン酸、4,4,4,3,3-ペンタフルオロブタン酸、5,5,5,4,4,3,3-ヘプタフルオロペンタン酸、6,6,6,5,5,4,4,3,3-ノナフルオロヘキサン酸、7,7,7,6,6,5,5,4,4,3,3-ウンデカフルオロヘプタン酸、8,8,8,7,7,6,6,5,5,4,4,3,3-トリデカフルオロオクタン酸、9,9,9,8,8,7,7,6,6,5,5,4,4,3,3-ペンタデカフルオロノナン酸、10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-ヘプタデカフルオロデカン酸、3,3-ジフルオロプロパ-2-エン酸、4,4,4,3-テトラフルオロブタ-2-エン酸、5,5,5,4,4,3-ヘキサフルオロペンタ-2-エン酸、6,6,6,5,5,4,4,3-オクタフルオロヘキサ-2-エン酸、7,7,7,6,6,5,5,4,4,3-デカフルオロヘプタ-2-エン酸、8,8,8,7,7,6,6,5,5,4,4,3-ドデカフルオロオクタ-2-エン酸、9,9,9,8,8,7,7,6,6,5,5,4,4,3-テトラデカフルオロノナ-2-エン酸、10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3-ヘキサデカフルオロデカ-2-エン酸または3,3-ビス(トリフルオロメチル)-6,6,6,5,5,4,4-ヘプタフルオロヘキサン酸の第四級アンモニウム塩または第四級ホスホニウム塩を含んでなる、上記第〔2〕項に記載の方法。
Claims (3)
- イミノオキサジアジンジオン基含有ポリイソシアネートの製造方法であって、式I):
R f -CR’ 2 -C(O)O − (I)
または式II):
R f =CR’-C(O)O − (II)
〔式中、
Rfは、必要に応じて分枝状、環状および/または不飽和の過フッ化C1〜C30基であり、
R’は、同一または異なって、H、C1〜C20アルキルおよび/またはアリールからなる群から選択される、必要に応じてヘテロ原子を含有する置換基である〕
に対応するアニオンを含有する触媒の存在下、
イミノオキサジアジンジオン基を含有しないポリイソシアネートのイソシアネート基部分を三量体化することを含む、方法。 - 第四級アンモニウムカチオンまたはホスホニウムカチオンを、式I)で示されるアニオンの対イオンとして使用する、請求項1に記載の方法。
- 上記触媒は、3,3,3-トリフルオロプロパン酸、4,4,4,3,3-ペンタフルオロブタン酸、5,5,5,4,4,3,3-ヘプタフルオロペンタン酸、6,6,6,5,5,4,4,3,3-ノナフルオロヘキサン酸、7,7,7,6,6,5,5,4,4,3,3-ウンデカフルオロヘプタン酸、8,8,8,7,7,6,6,5,5,4,4,3,3-トリデカフルオロオクタン酸、9,9,9,8,8,7,7,6,6,5,5,4,4,3,3-ペンタデカフルオロノナン酸、10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-ヘプタデカフルオロデカン酸、3,3-ジフルオロプロパ-2-エン酸、4,4,4,3-テトラフルオロブタ-2-エン酸、5,5,5,4,4,3-ヘキサフルオロペンタ-2-エン酸、6,6,6,5,5,4,4,3-オクタフルオロヘキサ-2-エン酸、7,7,7,6,6,5,5,4,4,3-デカフルオロヘプタ-2-エン酸、8,8,8,7,7,6,6,5,5,4,4,3-ドデカフルオロオクタ-2-エン酸、9,9,9,8,8,7,7,6,6,5,5,4,4,3-テトラデカフルオロノナ-2-エン酸、10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3-ヘキサデカフルオロデカ-2-エン酸または3,3-ビス(トリフルオロメチル)-6,6,6,5,5,4,4-ヘプタフルオロヘキサン酸の第四級アンモニウム塩または第四級ホスホニウム塩を含んでなる、請求項1に記載の方法。
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ES2434990T3 (es) * | 2008-11-10 | 2013-12-18 | Dow Global Technologies Llc | Un sistema catalítico de trimerización de isocianato, una formulación precursora, un procedimiento para trimerizar isocianatos, espumas rígidas de poliisocianurato/poliuretano hechas a partir del mismo y un procedimiento para hacer dichas espumas |
US20110201707A1 (en) * | 2008-11-10 | 2011-08-18 | Dow Global Technologies Llc | Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams |
US9080074B2 (en) * | 2010-03-19 | 2015-07-14 | Bayer Materialscience Llc | Low temperature curing polyuretdione compositions |
DE102010038845A1 (de) * | 2010-08-03 | 2012-02-09 | Bayer Materialscience Aktiengesellschaft | Verfahren zur Herstellung von Polyisocyanaten und deren Verwendung |
US9440937B2 (en) * | 2011-11-29 | 2016-09-13 | Covestro Deutschland Ag | Method for producing polyisocyanates and use thereof |
WO2013079614A2 (de) | 2011-11-30 | 2013-06-06 | Bayer Intellectual Property Gmbh | Verfahren zur kontinuierlichen isocyanatmodifizierung |
EP2976373B1 (de) * | 2013-03-22 | 2020-10-14 | Covestro Intellectual Property GmbH & Co. KG | Verfahren zur herstellung von polyisocyanaten und katalysator-kit hierfür |
EP3024869B1 (de) * | 2013-07-25 | 2020-05-06 | Covestro Deutschland AG | Verfahren zur herstellung von polyisocyanaten und deren verwendung |
EP3024863B1 (de) * | 2013-07-25 | 2022-05-04 | Covestro Intellectual Property GmbH & Co. KG | Verfahren zur herstellung von iminooxadiazindiongruppen enthaltenden polyisocyanaten und deren verwendung. |
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GB201313423D0 (en) * | 2013-07-26 | 2013-09-11 | Innospec Ltd | Compositions and methods |
GB201413355D0 (en) * | 2014-07-28 | 2014-09-10 | Innospec Ltd | Compositons and methods |
CN107257784B (zh) * | 2014-12-19 | 2021-07-06 | 伊士曼化工公司 | 用于从水性料流中萃取c1至c4羧酸的季羧酸盐组合物 |
US9611209B1 (en) | 2015-12-18 | 2017-04-04 | Eastman Chemical Company | Quaternary arylcarboxylate compositions for extracting C1 to C4 carboxylic acids from aqueous streams |
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DE19611849A1 (de) * | 1996-03-26 | 1997-10-02 | Bayer Ag | Neue Isocyanattrimerisate und Isocyanattrimerisatmischungen, deren Herstellung und Verwendung |
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