JP5076404B2 - Catalyst composition for producing polyurethane resin and method for producing polyurethane resin - Google Patents
Catalyst composition for producing polyurethane resin and method for producing polyurethane resin Download PDFInfo
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- JP5076404B2 JP5076404B2 JP2006237843A JP2006237843A JP5076404B2 JP 5076404 B2 JP5076404 B2 JP 5076404B2 JP 2006237843 A JP2006237843 A JP 2006237843A JP 2006237843 A JP2006237843 A JP 2006237843A JP 5076404 B2 JP5076404 B2 JP 5076404B2
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- catalyst composition
- general formula
- polyurethane resin
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- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 86
- 239000000203 mixture Substances 0.000 title claims description 44
- 229920005749 polyurethane resin Polymers 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- -1 amine compound Chemical class 0.000 claims description 81
- 229910052757 nitrogen Inorganic materials 0.000 claims description 55
- 229920005862 polyol Polymers 0.000 claims description 34
- 150000003077 polyols Chemical class 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 17
- 239000005056 polyisocyanate Substances 0.000 claims description 16
- 229920001228 polyisocyanate Polymers 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- QHTUMQYGZQYEOZ-UHFFFAOYSA-N 2-(4-methylpiperazin-1-yl)ethanol Chemical compound CN1CCN(CCO)CC1 QHTUMQYGZQYEOZ-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WGJJZRVGLPOKQT-UHFFFAOYSA-K lanthanum(3+);trifluoromethanesulfonate Chemical compound [La+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WGJJZRVGLPOKQT-UHFFFAOYSA-K 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 claims description 4
- OMDXZWUHIHTREC-UHFFFAOYSA-N 1-[2-(dimethylamino)ethoxy]ethanol Chemical compound CC(O)OCCN(C)C OMDXZWUHIHTREC-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001923 cyclic compounds Chemical class 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- ADQQGJLCEXHTRW-UHFFFAOYSA-N 1-(dimethylamino)hexan-1-ol Chemical compound CCCCCC(O)N(C)C ADQQGJLCEXHTRW-UHFFFAOYSA-N 0.000 claims description 3
- GZGKPOCYYNKGCV-UHFFFAOYSA-N 5-(dimethylamino)-3-methylpentan-1-ol Chemical compound OCCC(C)CCN(C)C GZGKPOCYYNKGCV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- WYRSPTDNOIZOGA-UHFFFAOYSA-K neodymium(3+);trifluoromethanesulfonate Chemical compound [Nd+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WYRSPTDNOIZOGA-UHFFFAOYSA-K 0.000 claims description 3
- 125000004193 piperazinyl group Chemical group 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 claims description 3
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000002636 imidazolinyl group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 150000001412 amines Chemical class 0.000 description 18
- 239000006260 foam Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 13
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- 229920005830 Polyurethane Foam Polymers 0.000 description 12
- 239000011496 polyurethane foam Substances 0.000 description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical group 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000012970 tertiary amine catalyst Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- SOIRNMUAUJFUMN-UHFFFAOYSA-N 1-n,2-n,2-n-trimethylpropane-1,2-diamine Chemical compound CNCC(C)N(C)C SOIRNMUAUJFUMN-UHFFFAOYSA-N 0.000 description 3
- ZIKLHFPNSYDZSP-UHFFFAOYSA-N 1-n-(2-aminoethyl)-2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CNCCN ZIKLHFPNSYDZSP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 3
- ZUXUNWLVIWKEHB-UHFFFAOYSA-N n',n'-dimethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN ZUXUNWLVIWKEHB-UHFFFAOYSA-N 0.000 description 3
- DOPWEGPUPNAKSG-UHFFFAOYSA-N n'-[2-[2-[2-(dimethylamino)ethyl-methylamino]ethyl-methylamino]ethyl]-n'-methylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)CCN DOPWEGPUPNAKSG-UHFFFAOYSA-N 0.000 description 3
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 3
- DAKZISABEDGGSV-UHFFFAOYSA-N n-(2-aminoethyl)acetamide Chemical compound CC(=O)NCCN DAKZISABEDGGSV-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 2
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- CSYGAOIVENNFCX-UHFFFAOYSA-N 1-(2-methyl-1h-imidazol-5-yl)propan-1-ol Chemical compound CCC(O)C1=CN=C(C)N1 CSYGAOIVENNFCX-UHFFFAOYSA-N 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical group C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000013518 molded foam Substances 0.000 description 2
- KRDDBYPPQLOAPV-UHFFFAOYSA-N n'-[2-(dimethylamino)ethyl]-n'-methylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN KRDDBYPPQLOAPV-UHFFFAOYSA-N 0.000 description 2
- QEHDXKWFMDUZQV-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n'-methylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN QEHDXKWFMDUZQV-UHFFFAOYSA-N 0.000 description 2
- HOCDOONHBIWYNL-UHFFFAOYSA-N n'-[2-[2-[2-[2-(dimethylamino)ethyl-methylamino]ethyl-methylamino]ethyl-methylamino]ethyl]-n'-methylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)CCN(C)CCN HOCDOONHBIWYNL-UHFFFAOYSA-N 0.000 description 2
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
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- GWPUBAZPNRZCKG-UHFFFAOYSA-N n-(8-aminooctyl)acetamide Chemical compound CC(=O)NCCCCCCCCN GWPUBAZPNRZCKG-UHFFFAOYSA-N 0.000 description 1
- XTEATBQXCQNTRI-UHFFFAOYSA-N n-(9-aminononyl)acetamide Chemical compound CC(=O)NCCCCCCCCCN XTEATBQXCQNTRI-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000006485 reductive methylation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N trimethyl-ethylene Natural products CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、ポリウレタン樹脂製造用触媒組成物及びそれを用いたポリウレタン樹脂の製造方法に関する。 The present invention relates to a catalyst composition for producing a polyurethane resin and a method for producing a polyurethane resin using the same.
本発明の触媒組成物は、エポキシ硬化剤、ウレタン原料、界面活性剤、繊維処理剤、紙力増強剤、樹脂改質剤、潤滑油添加剤等としても有用であるが、とりわけ、ポリウレタン樹脂製造の際、揮発性のアミン触媒や有害の金属触媒をほとんど有しないポリウレタン樹脂又はポリウレタンフォームを製造するための組成物として極めて有用である。 The catalyst composition of the present invention is useful as an epoxy curing agent, urethane raw material, surfactant, fiber treatment agent, paper strength enhancer, resin modifier, lubricating oil additive, etc. In this case, the composition is extremely useful as a composition for producing a polyurethane resin or polyurethane foam having almost no volatile amine catalyst or harmful metal catalyst.
ポリウレタン樹脂はポリオールとポリイソシアネートとを触媒及び必要に応じて発泡剤、界面活性剤、難燃剤、架橋剤等の存在下に反応させて製造される。ポリウレタン樹脂の製造には数多くの金属系化合物や第三級アミン化合物を触媒として用いることが知られている。これらの触媒は単独で又は併用することにより工業的にも多用されている。 The polyurethane resin is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane resins. These catalysts are often used industrially by being used alone or in combination.
発泡剤として水及び／又は低沸点有機化合物を用いるポリウレタンフォームの製造においては、生産性、成形性に優れることから、これら触媒のうち、とりわけ第三級アミン化合物が広く用いられている。このような第三級アミン化合物としては、例えば、従来公知のトリエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，６−ヘキサンジアミン、ビス（２−ジメチルアミノエチル）エーテル、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジエチレントリアミン、Ｎ−メチルモルフォリン、Ｎ−エチルモルフォリン、Ｎ，Ｎ−ジメチルエタノールアミン等が挙げられる（例えば、非特許文献１参照）。金属系化合物は生産性、成形性が悪化することより、ほとんどの場合、第三級アミン触媒と併用されることが多く単独での使用は少ない。 In the production of polyurethane foam using water and / or a low-boiling organic compound as a foaming agent, among these catalysts, tertiary amine compounds are widely used because of their excellent productivity and moldability. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N , N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like (for example, see Non-Patent Document 1). In most cases, the metal compound is often used in combination with a tertiary amine catalyst because the productivity and moldability are deteriorated, and the metal compound is rarely used alone.
前記した第三級アミン触媒は、ポリウレタン製品から揮発性のアミンとして徐々に排出され、例えば、自動車内装材等では揮発性アミンによる臭気問題や他の材料、例えば表皮塩ビの変色問題を引き起こす。また、第三級アミン触媒は、一般に悪臭が強く、ポリウレタン樹脂製造時の作業環境が著しく悪化する。これら揮発性の第三級アミン触媒に対し、この問題を解決する方法として分子内にポリイソシアネートと反応しうる一級及び二級のアミノ基や水酸基を有するアミン触媒（以下、反応型触媒と称する場合がある）や、第三級アミノ基を分子内に有する２官能の架橋剤を使用する方法が提案されている（例えば、特許文献１〜４参照）。 The above-mentioned tertiary amine catalyst is gradually discharged from the polyurethane product as a volatile amine, and causes, for example, an odor problem due to the volatile amine and a discoloration problem of other materials such as skin PVC in an automobile interior material. In addition, the tertiary amine catalyst generally has a strong malodor, and the working environment during the production of the polyurethane resin is significantly deteriorated. For these volatile tertiary amine catalysts, as a method for solving this problem, amine catalysts having primary and secondary amino groups or hydroxyl groups capable of reacting with polyisocyanates in the molecule (hereinafter referred to as reactive catalysts). And a method using a bifunctional crosslinking agent having a tertiary amino group in the molecule has been proposed (see, for example, Patent Documents 1 to 4).
上記の反応型触媒を使用する方法は、当該触媒がポリイソシアネートと反応した形でポリウレタン樹脂骨格中に固定化されるため上記問題を回避できるとされている。確かに、この方法は、最終樹脂製品の臭気低減には有効であるが、これらのアミン触媒は樹脂化反応（ポリオールとポリイソシアネートの反応）の活性が劣るため、得られるポリウレタン樹脂の硬化性が低下する問題がある。また、上記の架橋剤を使用する方法は、最終樹脂製品の臭気低減及びポリウレタン樹脂製造時の作業環境を改善には有効であるが、ポリウレタン樹脂の硬度等の物性が不充分である。 The method using the above-mentioned reactive catalyst is said to be able to avoid the above problem because the catalyst is immobilized in the polyurethane resin skeleton in a form reacted with polyisocyanate. Certainly, this method is effective in reducing the odor of the final resin product, but these amine catalysts are inferior in the activity of the resinification reaction (reaction of polyol and polyisocyanate). There is a problem that decreases. The method using the above-mentioned crosslinking agent is effective in reducing the odor of the final resin product and improving the working environment when producing the polyurethane resin, but the physical properties such as hardness of the polyurethane resin are insufficient.
ヒドロキシル基、一級アミノ基及び二級アミノ基を分子中に有するアミン化合物を硬質ポリウレタンフォーム製造用触媒として用いる例は知られているが（特許文献５〜６参照）、フォームの流動性及び熱伝導率改良を目的とするものであり、臭気問題の改善については一切言及されていない。 Examples of using an amine compound having a hydroxyl group, a primary amino group and a secondary amino group in the molecule as a catalyst for producing a rigid polyurethane foam are known (see Patent Documents 5 to 6), but the fluidity and heat conduction of the foam are known. The purpose is to improve the rate, and no mention is made of improving the odor problem.
一方、金属系触媒は、前記したアミン触媒のような臭気問題や他の材料を劣化させる問題は起さないが、金属系触媒単独の使用では、上記したとおり、生産性、物性及び成形性が悪化し、更には製品中に残った重金属による毒性問題や環境問題が取り沙汰されて来ている。 On the other hand, the metal-based catalyst does not cause odor problems such as the above-described amine catalyst or problems of degrading other materials. However, when the metal-based catalyst is used alone, as described above, productivity, physical properties, and moldability are reduced. It is getting worse, and the problems of toxicity and environmental problems caused by heavy metals remaining in the products are being addressed.
本発明は、上記の背景技術に鑑みてなされたものであり、その目的は、新規なポリウレタン樹脂製造用触媒組成物、及びそれを用いた、臭気問題や毒性、環境問題を引き起こすことなくポリウレタン製品を生産性、成形性良く得ることができる製造方法を提供することである。 The present invention has been made in view of the above-described background art, and the object thereof is a novel catalyst composition for producing a polyurethane resin, and a polyurethane product using the same without causing odor problems, toxicity, and environmental problems. It is providing the manufacturing method which can obtain this with sufficient productivity and moldability.
本発明者らは上記問題を解決するために鋭意検討を重ねた結果、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
即ち、本発明は、以下に示すとおり、トリフルオロメタンスルホン酸金属塩とヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物からなるポリウレタン樹脂製造用触媒組成物及びそれを用いたポリウレタン樹脂の製造方法である。 That is, the present invention provides an amine compound having in its molecule one or more substituents selected from the group consisting of a metal salt of trifluoromethanesulfonic acid and a hydroxyl group, a primary amino group and a secondary amino group, as shown below. A catalyst composition for producing a polyurethane resin and a method for producing a polyurethane resin using the catalyst composition.
［１］下記一般式（１）
Ｍ（ＣＦ３ＳＯ３）３ （１）
（式中、Ｍは、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ又はＬｕを表す。）
で示されるトリフルオロメタンスルホン酸金属塩と、ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物からなるポリウレタン樹脂製造用触媒組成物。
[1] The following general formula (1)
M (CF 3 SO 3 ) 3 (1)
(In the formula, M represents Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu.)
A catalyst for producing a polyurethane resin comprising a metal salt of trifluoromethanesulfonic acid represented by formula (1) and an amine compound having in its molecule one or more substituents selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group Composition.
［２］一般式（１）で示されるトリフルオロメタンスルホン酸金属塩と、ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物との混合比率が、［一般式（１）で示されるトリフルオロメタンスルホン酸金属塩］／［ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物］（モル比）として、０．００１〜２０の範囲であることを特徴とする上記［１］に記載の製造方法。 [2] An amine having in its molecule one or more substituents selected from the group consisting of a metal salt of trifluoromethanesulfonic acid represented by the general formula (1) and a hydroxyl group, a primary amino group and a secondary amino group The mixing ratio with the compound is [one or two or more substituents selected from the group consisting of a metal salt of trifluoromethanesulfonic acid represented by the general formula (1)] / [hydroxyl group, primary amino group and secondary amino group] The production method according to the above item [1], wherein the amine compound (molar ratio) in the molecule is in the range of 0.001 to 20.
［３］一般式（１）で示されるトリフルオロメタンスルホン酸金属塩が、トリフルオロメタンスルホン酸スカンジウム、トリフルオロメタンスルホン酸イットリウム、トリフルオロメタンスルホン酸ランタン、トリフルオロメタンスルホン酸ネオジウム及びトリフルオロメタンスルホン酸イッテルビウムからなる群より選ばれる１種又は２種以上のトリフルオロメタンスルホン酸金属塩であることを特徴とする上記［１］又は［２］に記載のポリウレタン樹脂製造用触媒組成物。 [3] The trifluoromethanesulfonic acid metal salt represented by the general formula (1) is composed of scandium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, neodymium trifluoromethanesulfonate, and ytterbium trifluoromethanesulfonate. The catalyst composition for producing a polyurethane resin as described in [1] or [2] above, which is one or more metal salts of trifluoromethanesulfonic acid selected from the group.
［４］ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物が、下記一般式（２） [4] An amine compound having in its molecule one or more substituents selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group is represented by the following general formula (2):
で示されるアミン化合物であることを特徴とする上記［１］乃至［３］のいずれかに記載のポリウレタン樹脂製造用触媒組成物。
The catalyst composition for producing a polyurethane resin according to any one of the above [1] to [3], which is an amine compound represented by the formula:
［５］一般式（２）において、Ｒ１〜Ｒ８が、各々独立して、水素原子、メチル基、ヒドロキシエチル基、ヒドロキシプロピル基、アミノエチル基、アミノプロピル基、モノメチルアミノエチル基、モノメチルアミノプロピル基、ジメチルアミノエチル基又はジメチルアミノプロピル基を表す（但し、Ｒ７とＲ１又はＲ２とが結合してピペラジン構造を有する環状化合物となっても良い。）ことを特徴とする上記［４］に記載のポリウレタン樹脂製造用触媒組成物。 [5] In the general formula (2), R 1 to R 8 are each independently a hydrogen atom, methyl group, hydroxyethyl group, hydroxypropyl group, aminoethyl group, aminopropyl group, monomethylaminoethyl group, monomethyl It represents an aminopropyl group, a dimethylaminoethyl group or a dimethylaminopropyl group (however, R 7 and R 1 or R 2 may be bonded to form a cyclic compound having a piperazine structure). The catalyst composition for producing a polyurethane resin according to [4].
［６］一般式（２）で示されるアミン化合物が、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルプロピレンジアミン、Ｎ，Ｎ−ジメチルヘキサメチレンジアミン、Ｎ−アセチルエチレンジアミン、Ｎ，Ｎ，Ｎ’−トリメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”−テトラメチルトリエチレンテトラミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”’−ペンタメチルテトラエチレンペンタミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”’，Ｎ””−ヘキサメチルペンタエチレンヘキサミン、ポリオキシプロピレンジアミン、トリメチルエチレンジアミン、トリメチルプロピレンジアミン、トリメチルヘキサメチレンジアミン、テトラメチルジエチレントリアミン、ビス（Ｎ，Ｎ−ジメチルアミノプロピル）アミン、Ｎ−メチルピペラジン、Ｎ，Ｎ−ジメチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノイソプロパノール、Ｎ，Ｎ−ジメチルアミノエトキシエタノール、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノプロピル−Ｎ’−メチルアミノエタノール、Ｎ，Ｎ，Ｎ’−トリメチル−Ｎ’−ヒドロキシエチルビスアミノエチルエーテル、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエチル−Ｎ”−メチルアミノイソプロパノール、Ｎ，Ｎ−ビス（３−ジメチルアミノプロピル）−Ｎ−イソプロパノールアミン、Ｎ−（３−ジメチルアミノプロピル）−Ｎ，Ｎ−ジイソプロパノールアミン、Ｎ−（２−ヒドロキシエチル）−Ｎ’−メチルピペラジン、Ｎ，Ｎ−ジメチルアミノヘキサノール、及び５−ジメチルアミノ−３−メチル−１−ペンタノールからなる群より選ばれる１種又は２種以上のアミン化合物であることを特徴とする上記［４］又は［５］に記載のポリウレタン樹脂製造用触媒組成物。 [6] The amine compound represented by the general formula (2) is N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N-dimethylhexamethylenediamine, N-acetylethylenediamine, N, N, N ′. -Trimethyldiethylenetriamine, N, N, N ', N "-tetramethyltriethylenetetramine, N, N, N', N", N "'-pentamethyltetraethylenepentamine, N, N, N', N" , N "', N" "-hexamethylpentaethylenehexamine, polyoxypropylenediamine, trimethylethylenediamine, trimethylpropylenediamine, trimethylhexamethylenediamine, tetramethyldiethylenetriamine, bis (N, N-dimethylaminopropyl) amine, N- Methylpiperazine, N, N-dimethyl Minoethanol, N, N-dimethylaminoisopropanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethyl-N′-methylaminoethanol, N, N-dimethylaminopropyl-N′-methylaminoethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol, N, N-bis (3-dimethyl) Aminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N′-methylpiperazine, N, N-dimethylaminohexanol, And 5-dimethylamino-3-methyl-1-penta The [4] or a polyurethane resin for producing a catalyst composition according to [5], which is a one or more amine compounds selected from the group consisting Lumpur.
［７］ポリオールとポリイソシアネートを、上記［１］乃至［５］のいずれかに記載の触媒組成物の存在下で反応させることを特徴とするポリウレタン樹脂の製造方法。 [7] A method for producing a polyurethane resin, comprising reacting a polyol and a polyisocyanate in the presence of the catalyst composition according to any one of [1] to [5].
［８］触媒組成物の使用量が、ポリオール１００重量部に対して０．０１〜２０重量部であることを特徴とする上記［７］に記載の製造方法。 [8] The production method as described in [7] above, wherein the amount of the catalyst composition used is 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyol.
本発明の触媒組成物は、ポリウレタン樹脂から揮散するアミンがほとんどないため、従来のアミン触媒に起因する自動車インストルパネルのＰＶＣ変色、フォームからの揮発成分移行による窓ガラスの曇り現象防止に有効である。 Since the catalyst composition of the present invention has almost no amine volatilized from the polyurethane resin, it is effective in preventing PVC discoloration of automobile instrument panels caused by conventional amine catalysts and fogging phenomenon of window glass due to migration of volatile components from foam. .
更には、本発明の触媒組成物は、汎用触媒であるトリエチレンジアミンに匹敵する触媒活性及び反応プロファイルを示すため、軟質、硬質、半硬質、エラストマー等のポリウレタン製造の際に使用する触媒として極めて有効である。 Furthermore, since the catalyst composition of the present invention exhibits catalytic activity and reaction profile comparable to triethylenediamine, which is a general-purpose catalyst, it is extremely effective as a catalyst used in the production of polyurethanes such as soft, hard, semi-rigid and elastomers. It is.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明のポリウレタン樹脂製造用触媒組成物は、上記一般式（１）で示されるトリフルオロメタンスルホン酸金属塩と、ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物とからなる。 The catalyst composition for producing a polyurethane resin of the present invention is one or two selected from the group consisting of a metal salt of trifluoromethanesulfonic acid represented by the above general formula (1), a hydroxyl group, a primary amino group, and a secondary amino group. It consists of an amine compound having the above substituents in the molecule.
本発明において、上記一般式（１）で示されるトリフルオロメタンスルホン酸金属塩は、Ｍが、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ又はＬｕのトリフルオロメタンスルホン酸金属塩化合物であり、工業的に入手可能なことから、トリフルオロメタンスルホン酸スカンジウム、トリフルオロメタンスルホン酸イットリウム、トリフルオロメタンスルホン酸ランタン、トリフルオロメタンスルホン酸ネオジウム又はリフルオロメタンスルホン酸イッテルビウムが好ましい。 In the present invention, the metal salt of trifluoromethanesulfonic acid represented by the general formula (1) is such that M is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu trifluoromethanesulfonic acid metal salt compound, and since it is industrially available, it is scandium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, neodymium trifluoromethanesulfonate Or ytterbium trifluoromethanesulfonate is preferable.
本発明において、ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物としては、特に限定するものではないが、好ましくは、上記一般式（２）で示されるアミン化合物である。 In the present invention, the amine compound having in the molecule one or more substituents selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group is not particularly limited, It is an amine compound represented by the general formula (2).
上記一般式（２）で示されるアミン化合物の置換基Ｒ１〜Ｒ８としては、各々独立して、水素原子、メチル基、ヒドロキシエチル基、ヒドロキシプロピル基、アミノエチル基、アミノプロピル基、モノメチルアミノエチル基、モノメチルアミノプロピル基、ジメチルアミノエチル基又はジメチルアミノプロピル基が好ましく、Ｒ７とＲ１又はＲ２とが結合してピペラジン構造を有する環状化合物となっても良い。 The substituents R 1 to R 8 of the amine compound represented by the general formula (2) are each independently a hydrogen atom, methyl group, hydroxyethyl group, hydroxypropyl group, aminoethyl group, aminopropyl group, monomethyl. An aminoethyl group, a monomethylaminopropyl group, a dimethylaminoethyl group or a dimethylaminopropyl group is preferred, and R 7 and R 1 or R 2 may be bonded to form a cyclic compound having a piperazine structure.
本発明において、上記一般式（２）で示されるアミン化合物としては、特に限定するものではないが、具体的には、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルプロピレンジアミン、Ｎ，Ｎ−ジメチルテトラメチレンジアミン、Ｎ，Ｎ−ジメチルペンタメチレンジアミン、Ｎ，Ｎ−ジメチルヘキサメチレンジアミン、Ｎ，Ｎ−ジメチルヘプタメチレンジアミン、Ｎ，Ｎ−ジメチルオクタメチレンジアミン、Ｎ，Ｎ−ジメチルノナメチレンジアミン、Ｎ，Ｎ−ジメチルデカメチレンジアミン、Ｎ−メチルエチレンジアミン、Ｎ−メチルプロピレンジアミン、Ｎ−メチルテトラメチレンジアミン、Ｎ−メチルペンタメチレンジアミン、Ｎ−メチルヘキサメチレンジアミン、Ｎ−メチルヘプタメチレンジアミン、Ｎ−メチルオクタメチレンジアミン、Ｎ−メチルノナメチレンジアミン、Ｎ−メチルデカメチレンジアミン、Ｎ−アセチルエチレンジアミン、Ｎ−アセチルプロピレンジアミン、Ｎ−アセチルテトラメチレンジアミン、Ｎ−アセチルペンタメチレンジアミン、Ｎ−アセチルヘキサメチレンジアミン、Ｎ−アセチルヘプタメチレンジアミン、Ｎ−アセチルオクタメチレンジアミン、Ｎ−アセチルノナメチレンジアミン、Ｎ−アセチルデカメチレンジアミン、Ｎ，Ｎ，Ｎ’−トリメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”−テトラメチルトリエチレンテトラミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”’−ペンタメチルテトラエチレンペンタミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”’Ｎ””−ヘキサメチルペンタエチレンヘキサミン等の一級アミン化合物類、トリメチルエチレンジアミン、トリメチルプロピレンジアミン、トリメチルテトラメチレンジアミン、トリメチルペンタメチレンジアミン、トリメチルヘキサメチレンジアミン、トリメチルヘプタメチレンジアミン、トリメチルオクタメチレンジアミン、トリメチルノナメチレンジアミン、トリメチルデカメチレンジアミン、テトラメチルジエチレントリアミン、ペンタメチルトリエチレンテトラミン、ヘキサメチルテトラエチレンペンタミン、ヘプタメチルペンタエチレンヘキサミン、ビス（Ｎ，Ｎ−ジメチルアミノプロピル）アミン、Ｎ−メチルピペラジン等の二級アミン化合物類、Ｎ，Ｎ−ジメチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノイソプロパノール、Ｎ，Ｎ−ジメチルアミノエトキシエタノール、Ｎ，Ｎ−ジメチルアミノエトキシイソプロパノール、Ｎ，Ｎ−ジメチルアミノエトキシエトキシエタノール、Ｎ，Ｎ−ジメチルアミノエトキシエトキシイソプロパノール、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノイソプロパノール、Ｎ，Ｎ−ジメチルアミノプロピル−Ｎ’−メチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノプロピル−Ｎ’−メチルアミノイソプロパノール、Ｎ，Ｎ−ジメチル−Ｎ’−（２−ヒドロキシエチル）エチレンジアミン、Ｎ，Ｎ−ジメチル−Ｎ’−（２−ヒドロキシエチル）プロパンジアミン、Ｎ，Ｎ，Ｎ’−トリメチル−Ｎ’−ヒドロキシエチルビスアミノエチルエーテル、Ｎ，Ｎ，Ｎ’−トリメチル−Ｎ’−ヒドロキシイソプロピルビスアミノエチルエーテル、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエチル−Ｎ”−メチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエチル−Ｎ”−メチルアミノイソプロパノール、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエチル−Ｎ”−メチルアミノエチル−Ｎ”’−メチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエチル−Ｎ”−メチルアミノエチル−Ｎ”’−メチルアミノイソプロパノール、Ｎ，Ｎ−ビス（３−ジメチルアミノプロピル）−Ｎ−イソプロパノールアミン、Ｎ−（３−ジメチルアミノプロピル）−Ｎ，Ｎ−ジイソプロパノールアミン、Ｎ−（２−ヒドロキシエチル）−Ｎ’−メチルピペラジン、Ｎ，Ｎ−ジメチルアミノヘキサノール、５−ジメチルアミノ−３−メチル−１−ペンタノール、１−（２’−ヒドロキシエチル）イミダゾール、１−（２’−ヒドロキシプロピル）イミダゾール、１−（２’−ヒドロキシエチル）−２−メチルイミダゾール、１−（２’−ヒドロキシプロピル）−２−メチルイミダゾール等のアルカノールアミン類等が例示される。 In the present invention, the amine compound represented by the general formula (2) is not particularly limited. Specifically, N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N— Dimethyltetramethylenediamine, N, N-dimethylpentamethylenediamine, N, N-dimethylhexamethylenediamine, N, N-dimethylheptamethylenediamine, N, N-dimethyloctamethylenediamine, N, N-dimethylnonamethylenediamine, N, N-dimethyldecamethylenediamine, N-methylethylenediamine, N-methylpropylenediamine, N-methyltetramethylenediamine, N-methylpentamethylenediamine, N-methylhexamethylenediamine, N-methylheptamethylenediamine, N- Methyl octamethyle Diamine, N-methylnonamethylenediamine, N-methyldecamethylenediamine, N-acetylethylenediamine, N-acetylpropylenediamine, N-acetyltetramethylenediamine, N-acetylpentamethylenediamine, N-acetylhexamethylenediamine, N- Acetylheptamethylenediamine, N-acetyloctamethylenediamine, N-acetylnonamethylenediamine, N-acetyldecamethylenediamine, N, N, N′-trimethyldiethylenetriamine, N, N, N ′, N ″ -tetramethyltriethylene Primary amine compounds such as tetramine, N, N, N ′, N ″, N ″ ′-pentamethyltetraethylenepentamine, N, N, N ′, N ″, N ″ ′ N ″ ″-hexamethylpentaethylenehexamine , Trimethylethylene Amine, trimethylpropylenediamine, trimethyltetramethylenediamine, trimethylpentamethylenediamine, trimethylhexamethylenediamine, trimethylheptamethylenediamine, trimethyloctamethylenediamine, trimethylnonamethylenediamine, trimethyldecamethylenediamine, tetramethyldiethylenetriamine, pentamethyltriethylenetetramine , Secondary amine compounds such as hexamethyltetraethylenepentamine, heptamethylpentaethylenehexamine, bis (N, N-dimethylaminopropyl) amine, N-methylpiperazine, N, N-dimethylaminoethanol, N, N- Dimethylaminoisopropanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyisopropano N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethylaminoethoxyethoxyisopropanol, N, N-dimethylaminoethyl-N′-methylaminoethanol, N, N-dimethylaminoethyl-N′-methyl Aminoisopropanol, N, N-dimethylaminopropyl-N′-methylaminoethanol, N, N-dimethylaminopropyl-N′-methylaminoisopropanol, N, N-dimethyl-N ′-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N, N′-trimethyl-N′-hydroxy Isopropyl bisaminoethyl ether, N, N-dimethyl Ruaminoethyl-N′-methylaminoethyl-N ″ -methylaminoethanol, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol, N, N-dimethylaminoethyl-N′-methyl Aminoethyl-N ″ -methylaminoethyl-N ″ ′-methylaminoethanol, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoethyl-N ″ ′-methylaminoisopropanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N′-methylpiperazine, N , N-dimethylaminohexanol, 5-dimethylamino-3-methyl-1 Pentanol, 1- (2′-hydroxyethyl) imidazole, 1- (2′-hydroxypropyl) imidazole, 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl)- Examples include alkanolamines such as 2-methylimidazole.
これらのアミン化合物のうち、触媒活性が高いことから、一級アミン化合物類としては、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルプロピレンジアミン、Ｎ，Ｎ−ジメチルヘキサメチレンジアミン、Ｎ−アセチルエチレンジアミン、Ｎ，Ｎ，Ｎ’−トリメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”−テトラメチルトリエチレンテトラミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”’−ペンタメチルテトラエチレンペンタミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”’，Ｎ””−ヘキサメチルペンタエチレンヘキサミン、二級アミン化合物類としては、トリメチルエチレンジアミン、トリメチルプロピレンジアミン、トリメチルヘキサメチレンジアミン、テトラメチルジエチレントリアミン、ビス（Ｎ，Ｎ−ジメチルアミノプロピル）アミン、Ｎ−メチルピペラジン、アルカノールアミン類としては、Ｎ，Ｎ−ジメチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノイソプロパノール、Ｎ，Ｎ−ジメチルアミノエトキシエタノール、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノプロピル−Ｎ’−メチルアミノエタノール、Ｎ，Ｎ，Ｎ’−トリメチル−Ｎ’−ヒドロキシエチルビスアミノエチルエーテル、Ｎ，Ｎ−ジメチルアミノエチル−Ｎ’−メチルアミノエチル−Ｎ”−メチルアミノイソプロパノール、Ｎ，Ｎ−ビス（３−ジメチルアミノプロピル）−Ｎ−イソプロパノールアミン、Ｎ−（３−ジメチルアミノプロピル）−Ｎ，Ｎ−ジイソプロパノールアミン、Ｎ−（２−ヒドロキシエチル）−Ｎ’−メチルピペラジン、Ｎ，Ｎ−ジメチルアミノヘキサノール、５−ジメチルアミノ−３−メチル−１−ペンタノールが特に好ましい。 Among these amine compounds, since the catalytic activity is high, primary amine compounds include N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N-dimethylhexamethylenediamine, N-acetylethylenediamine, N, N, N′-trimethyldiethylenetriamine, N, N, N ′, N ″ -tetramethyltriethylenetetramine, N, N, N ′, N ″, N ″ ′-pentamethyltetraethylenepentamine, N, N , N ′, N ″, N ″ ′, N ″ ″-hexamethylpentaethylenehexamine, secondary amine compounds include trimethylethylenediamine, trimethylpropylenediamine, trimethylhexamethylenediamine, tetramethyldiethylenetriamine, bis (N, N -Dimethylaminopropyl) amine, N- As tilpiperazine and alkanolamines, N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethyl-N′-methylaminoethanol, N , N-dimethylaminopropyl-N′-methylaminoethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -Methylaminoisopropanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl)- N'-methylpiperazine, N, N-dimethyla Nohekisanoru, 5-dimethylamino-3-methyl-1-pentanol are particularly preferred.
本発明の触媒組成物として用いられる上記一般式（２）で示されるアミン化合物は、文献既知の方法にて容易に製造できる。例えば、ジオールとジアミンとの反応やアルコールのアミノ化による方法、モノアミノアルコール又はジアミンの還元メチル化による方法、アミン化合物とアルキレンオキサイドとの反応による方法等が挙げられる。 The amine compound represented by the general formula (2) used as the catalyst composition of the present invention can be easily produced by methods known in the literature. For example, a method of reaction of diol and diamine, a method of amination of alcohol, a method of reductive methylation of monoamino alcohol or diamine, a method of reaction of amine compound and alkylene oxide, and the like can be mentioned.
本発明において、上記一般式（１）で示されるトリフルオロメタンスルホン酸金属塩とヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物との混合比率は、特に限定するものではないが、通常、［一般式（１）で示されるトリフルオロメタンスルホン酸金属塩］／［ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物］のモル比が０．００１〜２０の範囲になるように混合比率を調節する。更に好ましくは０．００５〜１０の範囲である。モル比がこの範囲を超えると両触媒の相乗効果が得られない場合があり、ポリウレタン樹脂の物性及び触媒活性の点で満足できる性能を発揮しない場合がある。 In this invention, it has 1 type, or 2 or more types of substituents chosen from the group which consists of a trifluoromethanesulfonic acid metal salt shown by the said General formula (1), and a hydroxyl group, a primary amino group, and a secondary amino group in a molecule | numerator. The mixing ratio with the amine compound is not particularly limited, but is usually a group consisting of [metal salt of trifluoromethanesulfonic acid represented by the general formula (1)] / [hydroxyl group, primary amino group and secondary amino group] The mixing ratio is adjusted so that the molar ratio of the amine compound having one or more substituents selected in the molecule is in the range of 0.001-20. More preferably, it is the range of 0.005-10. If the molar ratio exceeds this range, the synergistic effect of both catalysts may not be obtained, and satisfactory performance may not be exhibited in terms of physical properties and catalytic activity of the polyurethane resin.
本発明において、触媒組成物として用いられる上記一般式（１）で示されるトリフルオロメタンスルホン酸金属塩、及びヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物は、予め混合して調製したものを反応時に添加しても良いし、反応の際に同時に添加しても良い。また、混合する際に溶媒に溶解して使用することもできる。溶媒としては特に限定するものではないが、例えば、エチレングリコール、ジエチレングリコール、ジプロピレングリコール、プロピレングリコール、ブタンジオール等のアルコール類、トルエン、キシレン、ミネラルターペン、ミネラルスピリット等の炭化水素類、酢酸エチル、酢酸ブチル、メチルグリコールアセテート、酢酸セルソルブ等のエステル類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類の有機溶媒、アセチルアセトン及びそのフッ素化置換体等のβ−ジケトン類、アセト酢酸メチル、アセト酢酸エチル等のケトエステル類等のキレート化可能な溶媒、水等が挙げられる。 In the present invention, the trifluoromethanesulfonic acid metal salt represented by the general formula (1) used as the catalyst composition, and one or more selected from the group consisting of a hydroxyl group, a primary amino group, and a secondary amino group As the amine compound having a substituent in the molecule, a compound prepared by mixing in advance may be added during the reaction, or may be added simultaneously during the reaction. Further, it can be used by dissolving in a solvent when mixing. The solvent is not particularly limited, for example, alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol and butanediol, hydrocarbons such as toluene, xylene, mineral terpenes, mineral spirits, ethyl acetate, Esters such as butyl acetate, methyl glycol acetate and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, organic solvents of amides such as N, N-dimethylformamide and N, N-dimethylacetamide, acetylacetone and its Examples include chelatable solvents such as β-diketones such as fluorinated substituents, ketoesters such as methyl acetoacetate and ethyl acetoacetate, water, and the like.
本発明の触媒組成物は、ポリオールとポリイソシアネートを、触媒及び必要に応じて発泡剤、界面活性剤、難燃剤、架橋剤等の存在下に反応させるポリウレタン樹脂の製造方法において、触媒組成物として使用することができる。以下、本発明のポリウレタン樹脂の製造方法について説明する。 The catalyst composition of the present invention is used as a catalyst composition in a process for producing a polyurethane resin in which a polyol and a polyisocyanate are reacted in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, and a crosslinking agent. Can be used. Hereafter, the manufacturing method of the polyurethane resin of this invention is demonstrated.
本発明のポリウレタン樹脂の製造方法において、本発明の触媒組成物の使用量は、使用されるポリオール１００重量部に対し、通常０．０１〜２０重量部の範囲であるが、好ましくは０．０５〜１０重量部の範囲である。０．０１重量部より少ないと触媒の効果が得られない場合がある。一方、２０重量部を超えると、触媒を増やした効果が得られないだけでなく、ポリウレタン樹脂の物性が悪化する場合がある。 In the method for producing a polyurethane resin of the present invention, the amount of the catalyst composition of the present invention is usually in the range of 0.01 to 20 parts by weight, preferably 0.05 to 100 parts by weight of the polyol used. It is the range of -10 weight part. If the amount is less than 0.01 parts by weight, the effect of the catalyst may not be obtained. On the other hand, if it exceeds 20 parts by weight, not only the effect of increasing the catalyst cannot be obtained, but the physical properties of the polyurethane resin may deteriorate.
本発明の製造方法において、使用されるポリオールとしては、例えば、従来公知のポリエーテルポリオール、ポリエステルポリオール、ポリマーポリオール、更にはリン含有ポリオールやハロゲン含有ポリオール等の難燃ポリオール等が挙げられる。これらのポリオールは単独で使用することもできるし、適宜混合して併用することもできる。 Examples of the polyol used in the production method of the present invention include conventionally known polyether polyols, polyester polyols, polymer polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. These polyols can be used alone or in combination as appropriate.
本発明の製造方法において、使用されるポリエーテルポリオールとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコール類、エチレンジアミンの等のアミン類、エタノールアミン、ジエタノールアミン等のアルカノールアミン類等の、少なくとも２個以上の活性水素基を有する化合物を出発原料として、これにエチレンオキシドやプロピレンオキシドに代表されるアルキレンオキサイドの付加反応により、製造されたものが挙げられる［例えば、Ｇｕｎｔｅｒ Ｏｅｒｔｅｌ，“Ｐｏｌｙｕｒｅｔｈａｎｅ Ｈａｎｄｂｏｏｋ”（１９８５） Ｈａｎｓｅｒ Ｐｕｂｌｉｓｈｅｒｓ社（ドイツ），ｐ．４２−５３に記載の方法を参照のこと］。 Examples of the polyether polyol used in the production method of the present invention include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and pentaerythritol, amines such as ethylenediamine, ethanolamine, and diethanolamine. Examples include compounds produced by addition reaction of alkylene oxides typified by ethylene oxide and propylene oxide, starting from compounds having at least two active hydrogen groups such as alkanolamines such as Gunter Oertel, “Polyurethane Handbook” (1985) Hanser Publishers (Germany), p. See the method described in 42-53].
本発明の製造方法において、使用されるポリエステルポリオールとしては、例えば、二塩基酸とグリコールの反応から得られるものや、ナイロン製造時の廃物、トリメチロールプロパン、ペンタエリストールの廃物、フタル酸系ポリエステルの廃物、廃品を処理し誘導したポリエステルポリオール等が挙げられる［例えば、岩田敬治「ポリウレタン樹脂ハンドブック」（１９８７）日刊工業新聞社 ｐ．１１７の記載を参照のこと］。 Examples of the polyester polyol used in the production method of the present invention include those obtained from the reaction of dibasic acid and glycol, wastes from the production of nylon, trimethylolpropane, pentaerythritol wastes, and phthalic polyesters. And polyester polyols obtained by treating and inducing waste [for example, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun, p. See description of 117].
本発明の製造方法において、使用されるポリマーポリオールとしては、例えば、ポリエーテルポリオールとエチレン性不飽和単量体（例えばブタジエン、アクリロニトリル、スチレン等）をラジカル重合触媒の存在下に反応させた重合体ポリオールが挙げられる。 In the production method of the present invention, the polymer polyol used is, for example, a polymer obtained by reacting a polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst. A polyol is mentioned.
本発明の製造方法において、使用される難燃ポリオールとしては、例えば、リン酸化合物にアルキレンオキシドを付加して得られるリン含有ポリオール、エピクロルヒドリンやトリクロロブチレンオキシドを開環重合して得られるハロゲン含有ポリオール、フェノールポリオール等が挙げられる。 Examples of the flame retardant polyol used in the production method of the present invention include a phosphorus-containing polyol obtained by adding alkylene oxide to a phosphoric acid compound, and a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide. And phenol polyol.
本発明の製造方法においては、平均水酸基価が２０〜１０００ｍｇＫＯＨ／ｇのポリオールが使用できるが、軟質ポリウレタン樹脂や半硬質ポリウレタン樹脂には２０〜１００ｍｇＫＯＨ／ｇのものが、硬質ポリウレタン樹脂には１００〜８００ｍｇＫＯＨ／ｇのものが、好適に使用される。 In the production method of the present invention, a polyol having an average hydroxyl value of 20 to 1000 mgKOH / g can be used. For a flexible polyurethane resin or a semi-rigid polyurethane resin, a polyol having a mean hydroxyl value of 20 to 100 mgKOH / g is used. 800 mg KOH / g is preferably used.
本発明の製造方法においてポリイソシアネートは、従来公知のものであればよく、特に限定するものではないが、例えば、トルエンジイソシアネート（以下、ＴＤＩと称する場合がある）、ジフェニルメタンジイソシアネート（以下、ＭＤＩと称する場合がある）、ナフチレンジイシシアネート、キシリレンジイソシアネート等の芳香族ポリイソシアネート類、ヘキサメチレンジイソシアネート等の脂肪族ポリイソシアネート類、ジシクロヘキシルジイソシアネート、イソホロンジイソシアネート等の脂環式ポリイソシアネート類及びこれらの混合体等が挙げられる。これらのうち好ましくはＴＤＩとその誘導体又はＭＤＩとその誘導体であり、これらは混合して使用しても差し支えない。 In the production method of the present invention, the polyisocyanate may be a conventionally known one, and is not particularly limited. For example, toluene diisocyanate (hereinafter sometimes referred to as TDI), diphenylmethane diisocyanate (hereinafter referred to as MDI). ), Aromatic polyisocyanates such as naphthylene diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and mixtures thereof Etc. Among these, TDI and its derivatives or MDI and its derivatives are preferable, and these may be used in combination.
ＴＤＩとその誘導体としては、２，４−ＴＤＩと２，６−ＴＤＩの混合物又はＴＤＩの末端イソシアネートプレポリマー誘導体を挙げることができる。ＭＤＩとその誘導体としては、ＭＤＩとその重合体のポリフェニルポリメチレンジイソシアネートの混合体、及び／又は末端イソシアネート基をもつジフェニルメタンジイソシアネート誘導体を挙げることができる。 Examples of TDI and its derivatives include a mixture of 2,4-TDI and 2,6-TDI or a terminal isocyanate prepolymer derivative of TDI. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenyl polymethylene diisocyanate, and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group.
これらポリイソシアネートの内、軟質ポリウレタン樹脂や半硬質ポリウレタン樹脂製品にはＴＤＩとその誘導体又は／及びＭＤＩとその誘導体が、硬質ポリウレタン樹脂にはＭＤＩとその重合体のポリフェニルポリメチレンジイソシアネートの混合体が好適に使用される。 Among these polyisocyanates, soft polyurethane resins and semi-rigid polyurethane resin products contain TDI and its derivatives or / and MDI and its derivatives, and hard polyurethane resins contain a mixture of MDI and its polymer polyphenyl polymethylene diisocyanate. Preferably used.
これらポリイソシアネートとポリオールの混合割合としては、特に限定されるものではないが、イソシアネートインデックス（イソシアネート基／イソシアネート基と反応しうる活性水素基）で表すと、一般に６０〜４００の範囲が好ましい。 The mixing ratio of these polyisocyanates and polyols is not particularly limited, but generally 60 to 400 is preferable in terms of isocyanate index (isocyanate group / active hydrogen group capable of reacting with isocyanate group).
本発明の製造方法において、上記一般式（１）で示されるトリフルオロメタンスルホン酸金属塩と、ヒドロキシル基、一級アミノ基及び二級アミノ基からなる群より選ばれる一種又は二種以上の置換基を分子中に有するアミン化合物からなる本発明の触媒組成物に加え、本発明の趣旨を逸脱しない範囲で、その他の有機金属触媒、カルボン酸金属塩触媒、第三級アミン触媒、及び第四級アンモニウム塩触媒からなる群より選ばれる触媒（以下、その他の触媒と称する）を併用しても良い。 In the production method of the present invention, one or more substituents selected from the group consisting of a metal salt of trifluoromethanesulfonic acid represented by the general formula (1) and a hydroxyl group, a primary amino group, and a secondary amino group are used. In addition to the catalyst composition of the present invention comprising an amine compound in the molecule, other organometallic catalyst, carboxylic acid metal salt catalyst, tertiary amine catalyst, and quaternary ammonium are within the scope of the present invention. A catalyst selected from the group consisting of salt catalysts (hereinafter referred to as other catalysts) may be used in combination.
有機金属触媒としては、従来公知のものであればよく、特に限定するものではないが、例えば、スタナスジアセテート、スタナスジオクトエート、スタナスジオレエート、スタナスジラウレート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジクロライド、ジオクチル錫ジラウレート、オクタン酸鉛、ナフテン酸鉛、ナフテン酸ニッケル、ナフテン酸コバルト等が挙げられる。 The organometallic catalyst may be any conventionally known one, and is not particularly limited. Examples include acetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, and the like.
カルボン酸金属塩触媒としては、従来公知のものであればよく、特に限定するものではないが、例えば、カルボン酸のアルカリ金属塩やアルカリ土類金属塩が挙げられる。カルボン酸としては、特に限定するものではないが、例えば、酢酸、プロピオン酸、２−エチルヘキサン酸、アジピン酸等の脂肪族モノ及びジカルボン酸類、安息香酸、フタル酸等の芳香族モノ及びジカルボン酸類等が挙げられる。また、カルボン酸塩を形成すべき金属としては、リチウム、ナトリウム、カリウム等のアルカリ金属、カルシウム、マグネシウム等のアルカリ土類金属が好適な例として挙げられる。 The carboxylic acid metal salt catalyst is not particularly limited as long as it is a conventionally known one, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. The carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Etc. Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.
第三級アミン触媒としては、従来公知のものであればよく、特に限定するものではないが、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロピレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチル−（３−アミノプロピル）エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジプロピレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルグアニジン、１，３，５−トリス（Ｎ，Ｎ−ジメチルアミノプロピル）ヘキサヒドロ−Ｓ−トリアジン、１，８−ジアザビシクロ［５．４．０］ウンデセン−７、トリエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサメチレンジアミン、Ｎ，Ｎ’−ジメチルピペラジン、ジメチルシクロヘキシルアミン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン、ビス（２−ジメチルアミノエチル）エーテル、１−メチルイミダゾール、１，２−ジメチルイミダゾール、１−イソブチル−２−メチルイミダゾール、１−ジメチルアミノプロピルイミダゾール等の第三級アミン化合物類が挙げられる。 The tertiary amine catalyst may be any conventionally known one, and is not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′ -Tetramethylpropylenediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethyl Piperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethyl And tertiary amine compounds such as aminopropylimidazole.
第四級アンモニウム塩触媒としては、従来公知のものであればよく、特に限定するものではないが、例えば、テトラメチルアンモニウムクロライド等のテトラアルキルアンモニウムハロゲン化物、水酸化テトラメチルアンモニウム塩等のテトラアルキルアンモニウム水酸化物、テトラメチルアンモニウム２−エチルヘキサン酸塩、２−ヒドロキシプロピルトリメチルアンモニウムギ酸塩、２−ヒドロキシプロピルトリメチルアンモニウム２−エチルヘキサン酸塩等のテトラアルキルアンモニウム有機酸塩類が挙げられる。 The quaternary ammonium salt catalyst is not particularly limited as long as it is a conventionally known quaternary ammonium salt catalyst. Examples thereof include tetraalkylammonium halides such as tetramethylammonium chloride, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salt. Examples thereof include tetraalkylammonium organic acid salts such as ammonium hydroxide, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.
本発明の製造方法において、上記したその他の触媒の使用量は、本発明の趣旨を逸脱しない範囲で、必要に応じて使用すればよく、特に限定するものではないが、本発明の触媒組成物１重量部に対し、通常０〜１００重量部の範囲、好ましくは０．０１〜１０重量部の範囲で使用される。 In the production method of the present invention, the use amount of the other catalyst described above may be used as necessary without departing from the spirit of the present invention, and is not particularly limited, but the catalyst composition of the present invention. It is used in the range of usually 0 to 100 parts by weight, preferably 0.01 to 10 parts by weight with respect to 1 part by weight.
本発明の製造方法において、本発明の触媒組成物は、上記したように単独で又はその他の触媒と混合して使用することができるが、混合調整にあたって、必要ならば、ジプロピレングリコール、エチレングリコール、１，４−ブタンジオール又は水等の溶媒が使用できる。溶媒の量は、特に限定するものではないが、好ましくは触媒の全量に対して３重量倍以下である。３重量倍を超えると、フォームの物性に影響を及ぼし、経済上の理由からも好ましくない。このように調整された触媒は、ポリオールに添加して使用しても良いし、種々のアミン触媒を別々にポリオールに添加しても良く、特に限定されるものではない。 In the production method of the present invention, the catalyst composition of the present invention can be used alone or mixed with other catalysts as described above, but dipropylene glycol, ethylene glycol can be used for mixing adjustment if necessary. A solvent such as 1,4-butanediol or water can be used. The amount of the solvent is not particularly limited, but is preferably 3 times or less by weight based on the total amount of the catalyst. If it exceeds 3 times by weight, it will affect the physical properties of the foam, which is not preferred for economic reasons. The catalyst adjusted in this way may be used by adding to the polyol, or various amine catalysts may be added separately to the polyol, and is not particularly limited.
本発明の製造方法において、必要であれば、発泡剤を使用することができる。発泡剤としては、特に限定するものではないが、例えば、１，１−ジクロロ−１−フルオロエタン（ＨＣＦＣ−１４１ｂ）、１，１，１，３，３−ペンタフルオロプロパン（ＨＦＣ−２４５ｆａ）、１，１，１，３，３−ペンタフルオロブタン（ＨＦＣ−３６５ｍｆｃ）、１，１，２−テトラフルオロエタン（ＨＦＣ−１３４ａ）、１，１，１，２，３，３，３−ヘプタフルオロプロパン（ＨＦＣ−２２７ｅａ）等のフロン系化合物、ＨＦＥ−２５４ｐｃ等のハイドロフルオロエーテル類、低沸点炭化水素、水から選ばれる１種以上であり混合物を使用することができる。低沸点炭化水素としては、通常、沸点が通常−３０〜７０℃の炭化水素が使用され、その具体例としては、プロパン、ブタン、ペンタン、シクロペンタン、ヘキサン、及びこれらの混合物が挙げられる。 In the production method of the present invention, a foaming agent can be used if necessary. The foaming agent is not particularly limited, and examples thereof include 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3-heptafluoro One or more kinds selected from chlorofluorocarbon compounds such as propane (HFC-227ea), hydrofluoroethers such as HFE-254pc, low-boiling hydrocarbons, and water, and a mixture can be used. As the low-boiling hydrocarbons, hydrocarbons having a boiling point of usually −30 to 70 ° C. are usually used, and specific examples thereof include propane, butane, pentane, cyclopentane, hexane, and mixtures thereof.
発泡剤の使用量は、所望の密度やフォーム物性に応じて決定されるが、具体的には、得られるフォーム密度が、通常５〜１０００ｋｇ／ｍ３、好ましくは１０〜５００ｋｇ／ｍ３となるように選択される。 The amount of the foaming agent used is determined according to the desired density and foam physical properties. Specifically, the foam density obtained is usually 5 to 1000 kg / m 3 , preferably 10 to 500 kg / m 3. Selected as
本発明の製造方法において、必要であれば、整泡剤として界面活性剤を用いることができる。使用される界面活性剤としては、例えば、従来公知の有機シリコーン系界面活性剤が挙げられ、具体的には、有機シロキサン−ポリオキシアルキレン共重合体、シリコーン−グリース共重合体等の非イオン系界面活性剤、又はこれらの混合物等が例示される。それらの使用量は、ポリオール１００重量部に対して通常０．１〜１０重量部である。 In the production method of the present invention, if necessary, a surfactant can be used as a foam stabilizer. Examples of the surfactant to be used include conventionally known organosilicone surfactants, and specifically, nonionic systems such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Surfactant or a mixture thereof is exemplified. Their use amount is usually 0.1 to 10 parts by weight per 100 parts by weight of polyol.
本発明の製造方法において、必要であれば、架橋剤又は鎖延長剤を用いることができる。架橋剤又は鎖延長剤としては、例えば、エチレングリコール、１，４−ブタンジオール、グリセリン等の低分子量の多価アルコール類、ジエタノールアミン、トリエタノールアミン等の低分子量のアミンポリオール類、又はエチレンジアミン、キシリレンジアミン、メチレンビスオルソクロルアニリン等ポリアミン類を挙げることができる。 In the production method of the present invention, if necessary, a crosslinking agent or a chain extender can be used. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine and xylylene. Examples include polyamines such as range amine and methylene bisorthochloroaniline.
本発明の製造方法において、必要であれば、難燃剤を用いることができる。使用される難燃剤としては、例えば、リン酸とアルキレンオキシドとの付加反応によって得られるプロポキシル化リン酸、プロポキシル化ジブチルピロリン酸等の含リンポリオールの様な反応型難燃剤、トリクレジルホスフェート等の第３リン酸エステル類、トリス（２−クロロエチル）ホスフェート、トリス（クロロプロピル）ホスフェート等のハロゲン含有第３リン酸エステル類、ジブロモプロパノール、ジブロモネオペンチルグリコール、テトラブロモビスフェノールＡ等のハロゲン含有有機化合物類、酸化アンチモン、炭酸マグネシウム、炭酸カルシウム、リン酸アルミニウム等の無機化合物等が挙げられる。その量は特に限定されるものではなく、要求される難燃性に応じて異なるが、通常ポリオール１００重量部に対して４〜２０重量部である。 In the production method of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant used include reactive flame retardants such as phosphorus-containing polyols such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, tricresyl Tertiary phosphates such as phosphate, halogen-containing tertiary phosphates such as tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, halogens such as dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol A Examples include organic compounds, inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The amount is not particularly limited and varies depending on the required flame retardancy, but is usually 4 to 20 parts by weight with respect to 100 parts by weight of the polyol.
本発明の製造方法において、必要であれば、着色剤や、老化防止剤、その他従来公知の添加剤等も使用できる。これらの添加剤の種類、添加量は、使用される添加剤の通常の使用範囲でよい。 In the production method of the present invention, if necessary, a colorant, an antioxidant, and other conventionally known additives can be used. The type and amount of these additives may be within the normal usage range of the additive used.
本発明の製造方法は、前記原料を混合した混合液を急激に混合、攪拌した後、適当な容器又はモールドに注入して発泡成型することにより通常行われる。混合、攪拌は一般的な攪拌機や専用のポリウレタン発泡機を使用して実施すれば良い。ポリウレタン発泡機としては高圧、低圧及びスプレー式の機器が使用できる。 The production method of the present invention is usually carried out by rapidly mixing and stirring the mixed solution in which the raw materials are mixed, and then injecting the mixture into a suitable container or mold to perform foam molding. Mixing and stirring may be performed using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming machine, high-pressure, low-pressure and spray-type devices can be used.
本発明の製造方法で得られるポリウレタン樹脂製品としては、発泡剤を使用しないエラストマーや発泡剤を使用するポリウレタンフォームが挙げられるが、中でもポリウレタンフォーム製品の製造が好ましい。ポリウレタンフォーム製品としては、軟質ポリウレタンフォーム、半硬質ポリウレタンフォーム、硬質ポリウレタンフォーム等が挙げられるが、特に自動車内装材として用いられる軟質ポリウレタンフォームのカーシート、半硬質ポリウレタンフォームのインスツルメントパネルやハンドル、及び硬質ポリウレタンフォームにて製造される断熱材が好ましい。 Examples of the polyurethane resin product obtained by the production method of the present invention include an elastomer that does not use a foaming agent and a polyurethane foam that uses a foaming agent. Among them, the production of a polyurethane foam product is preferred. Examples of polyurethane foam products include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam, etc., especially soft polyurethane foam car seats used as automotive interior materials, semi-rigid polyurethane foam instrument panels and handles, And a heat insulating material made of rigid polyurethane foam is preferred.
以下、実施例、比較例に基づいて説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, although demonstrated based on an Example and a comparative example, this invention is not limited only to these Examples.
実施例１：
窒素置換した２００ｍｌの三角フラスコに、ジエチレングリコール（ＤＥＧ）の濃度が０．１５ｍｏｌ／Ｌになるように調製したＤＥＧ含有ベンゼン溶液５０ｍｌを採取し、これに触媒としてトリフルオロメタンスルホン酸ランタンを４１．０３ｍｇ（０．０７ｍｍｏｌ）、Ｎ−メチル−Ｎ’−ヒドロキシエチルピペラジン４０．３８ｍｇ（０．２８ｍｍｏｌ）を加え、Ａ液とした。次に、窒素置換した１００ｍｌの三角フラスコに、２，６−トルエンジイソシアネート（ＴＤＩ）の濃度が０．１５ｍｏｌ／Ｌになるように調製したＴＤＩ含有ベンゼン溶液５０ｍｌを採取し、Ｂ液とした。Ａ液及びＢ液をそれぞれ３０℃にて３０分間保温後、Ｂ液をＡ液に加えて、攪拌しながら反応を開始した。反応開始後、１０分毎に反応液を約１０ｍｌ採取し、未反応のイソシアナートを過剰のジ−ｎ−ブチルアミン（ＤＢＡ）溶液と反応させ、残存したＤＢＡを０．２Ｎ塩酸エタノール溶液で逆滴定して未反応イソシアナート量を定量した。
Example 1:
In a 200 ml Erlenmeyer flask purged with nitrogen, 50 ml of a DEG-containing benzene solution prepared so that the concentration of diethylene glycol (DEG) was 0.15 mol / L was collected, and 41.03 mg of lanthanum trifluoromethanesulfonate (41.03 mg as a catalyst) 0.07 mmol) and 40.38 mg (0.28 mmol) of N-methyl-N′-hydroxyethylpiperazine were added to prepare a solution A. Next, 50 ml of a TDI-containing benzene solution prepared so that the concentration of 2,6-toluene diisocyanate (TDI) was 0.15 mol / L was collected in a 100 ml Erlenmeyer flask purged with nitrogen and used as solution B. The liquid A and the liquid B were each kept at 30 ° C. for 30 minutes, and then the liquid B was added to the liquid A and the reaction was started while stirring. About 10 ml of the reaction solution is collected every 10 minutes after the reaction starts, the unreacted isocyanate is reacted with an excess of di-n-butylamine (DBA) solution, and the remaining DBA is back titrated with 0.2 N hydrochloric acid ethanol solution. Thus, the amount of unreacted isocyanate was quantified.
反応速度定数ｋ（ｌ／ｍｏｌ・ｈ）は、ポリイソシアネートとアルコールの反応（樹脂化反応）が各々の濃度に１次であると仮定して求めた。また、触媒あたりの速度定数Ｋｃ（ｌ２／ｅｑ・ｍｏｌ・ｈ）は反応速度定数ｋを触媒濃度で除することで求めた。結果を表１に示す。 The reaction rate constant k (l / mol · h) was determined on the assumption that the reaction between the polyisocyanate and the alcohol (resinification reaction) was first-order at each concentration. The rate constant Kc (l 2 / eq · mol · h) per catalyst was determined by dividing the reaction rate constant k by the catalyst concentration. The results are shown in Table 1.
触媒としてトリフルオロメタンスルホン酸塩及びアミン化合物を表１に示した配合比にて使用した以外は実施例１と同じ手法を用いた。結果を表１にあわせて示す。
The same procedure as in Example 1 was used except that trifluoromethanesulfonate and an amine compound were used as the catalyst at the blending ratio shown in Table 1. The results are shown in Table 1.
比較例１〜比較例９：
触媒としてトリフルオロメタンスルホン酸塩又はアミン化合物を表１に示した配合比にて使用した以外は実施例１と同じ手法を用いた。結果を表１にあわせて示す。
Comparative Example 1 to Comparative Example 9:
The same procedure as in Example 1 was used except that trifluoromethanesulfonate or an amine compound was used as a catalyst at the blending ratio shown in Table 1. The results are shown in Table 1.
表１から明らかなように、実施例１〜実施例１２では、トリフルオロメタンスルホン酸塩及び特定のアミン化合物を併用して使用することで、それらの単独系（比較例１〜比較例８）より著しい触媒活性の向上が見られ、ウレタン形成反応（樹脂化反応）を相乗的に促進する。特に、実施例１及び実施例２では、従来触媒のＴＥＤＡに匹敵する触媒活性を発現する。 As is clear from Table 1, in Examples 1 to 12, by using trifluoromethanesulfonate and a specific amine compound in combination, those single systems (Comparative Examples 1 to 8) are used. Significant improvement in catalytic activity is observed, and the urethane formation reaction (resinification reaction) is synergistically accelerated. In particular, Example 1 and Example 2 exhibit catalytic activity comparable to that of the conventional catalyst TEDA.
実施例１３：
ポリオール、水、整泡剤を表２に示した原料配合比にてプレミックスＡを調合した。
Example 13:
Premix A was prepared with the raw material blending ratio shown in Table 2 for polyol, water, and foam stabilizer.
（１）反応性の測定項目
クリームタイム：発泡開始時間、フォームが上昇開始する時間を目視にて測定
ゲルタイム：反応が進行し液状物質より、樹脂状物質に変わる時間を測定
ライズタイム：フォームの上昇が停止する時間を目視にて測定。
（２）フォームコア密度
モールド成型フォームの中心部を７×７×５ｃｍの寸法にカットし、寸法、重量を正確に測定してコア密度を算出した。
（３）フォームの臭気
フォームコア密度を測定したフォームから５×５×５ｃｍ寸法のフォームをカットしマヨネーズ瓶の中に入れ蓋をした後、１０人のモニターにそのフォームの臭いを嗅いで貰い、臭いの強さを測定した。
(1) Reactive measurement items Cream time: Measure foaming start time, foam start time visually. Gel time: Measure time when reaction progresses and change from liquid to resinous material. Rise time: Foam rise Visually measure the time to stop.
(2) Foam Core Density The core density was calculated by cutting the center part of the molded foam into a size of 7 × 7 × 5 cm and measuring the size and weight accurately.
(3) Odor of foam After cutting a foam of 5 x 5 x 5 cm from the foam core density measured and putting it in a mayonnaise bottle, the smell of the foam was sniffed on 10 monitors, The intensity of odor was measured.
○：ほとんど臭い無し、△：臭気あり、×：強い臭気有り ○: Almost no odor, △: Odor, ×: Strong odor
Ｎ−メチル−Ｎ’−ヒドロキシエチルピペラジンの代わりに１−ヒドロキシプロピル−２−メチルイミダゾールを使用した以外は、実施例１３と同じ手法を用いた。結果をあわせて表３に示す。
The same procedure as in Example 13 was used, except that 1-hydroxypropyl-2-methylimidazole was used instead of N-methyl-N′-hydroxyethylpiperazine. The results are shown in Table 3.
比較例１０：
トリフルオロメタンスルホン酸ランタン及びＮ−メチル−Ｎ’−ヒドロキシエチルピペラジンの代わりにＬ３３を使用した以外は、実施例１３と同じ手法を用いた。結果をあわせて表３にあわせて示す。
Comparative Example 10:
The same procedure was used as in Example 13, except that L33 was used instead of lanthanum trifluoromethanesulfonate and N-methyl-N′-hydroxyethylpiperazine. The results are also shown in Table 3.
実施例１３、１４は本発明の触媒を使用した例であるが、触媒活性が高く、フォームからアミン触媒の臭気はほとんどしない。一般に触媒として使用されているＬ３３（比較例１０）と反応プロファイルが近いため、Ｌ３３の代替が可能である。一方、Ｌ３３を触媒として用いた場合（比較例１０）、フォームからアミン触媒の臭気が確認され、アミン触媒に起因する自動車インストルパネルのＰＶＣ変色、窓ガラスの曇り現象を防止することができない。 Examples 13 and 14 are examples in which the catalyst of the present invention was used. However, the catalytic activity is high, and the odor of the amine catalyst is almost absent from the foam. Since L33 (Comparative Example 10), which is generally used as a catalyst, has a similar reaction profile, L33 can be substituted. On the other hand, when L33 is used as a catalyst (Comparative Example 10), the odor of the amine catalyst is confirmed from the foam, and the PVC discoloration of the automobile instrument panel and the fogging phenomenon of the window glass due to the amine catalyst cannot be prevented.
実施例１５：
表４に示す処方にて各触媒の反応性を評価した。ポリオール２０．０ｇを１００ｍｌポリエチレンカップに秤取り、触媒としてトリフルオロメタンスルホン酸ランタン及びＮ−メチル−Ｎ’−ヒドロキシエチルピペラジンを表４に示した配合比にて添加し、７０℃に温度調整した。これに、別容器で７０℃に温度調整したポリイソシアネート液を、イソシアネートインデックス［＝イソシアネート基／ＯＨ基（モル比）×１００］が１０５となる量を入れ、素早くヘラにて混合攪拌した。混合攪拌した液をホットプレート上にて１００℃に温度調節したＳＵＳ３０４製モールド（内寸法、２０×２０×２ｍｍ）に充填し反応液の反応性を測定した。結果を表４に示す。なお、各測定項目の測定方法は以下のとおりである。
Example 15:
The reactivity of each catalyst was evaluated according to the formulation shown in Table 4. 20.0 g of polyol was weighed in a 100 ml polyethylene cup, and lanthanum trifluoromethanesulfonate and N-methyl-N′-hydroxyethylpiperazine were added as a catalyst at a blending ratio shown in Table 4, and the temperature was adjusted to 70 ° C. The amount of the isocyanate index [= isocyanate group / OH group (molar ratio) × 100] of 105 was added to the polyisocyanate liquid whose temperature was adjusted to 70 ° C. in a separate container, and the mixture was quickly mixed and stirred with a spatula. The mixed and stirred liquid was filled in a SUS304 mold (inner dimensions, 20 × 20 × 2 mm) whose temperature was adjusted to 100 ° C. on a hot plate, and the reactivity of the reaction solution was measured. The results are shown in Table 4. The measurement method for each measurement item is as follows.
ポットライフ：モールドに注入された原料の反応が進行し液状物質より、樹脂状物質に変わる時間を測定した。 Pot life: The time required for the reaction of the raw material injected into the mold to change from a liquid material to a resinous material was measured.
硬化時間：モールドに注入されたウレタン樹脂が硬化し、表面のべとつきがなくなる時間を測定した。 Curing time: The time when the urethane resin injected into the mold was cured and the surface was not sticky was measured.
Ｎ−メチル−Ｎ’−ヒドロキシエチルピペラジンの代わりに１−ヒドロキシプロピル−２−メチルイミダゾールを使用した以外は、実施例１５と同じ手法を用いた。結果を表４にあわせて示す。
The same procedure as in Example 15 was used, except that 1-hydroxypropyl-2-methylimidazole was used instead of N-methyl-N′-hydroxyethylpiperazine. The results are shown in Table 4.
比較例１１：
トリフルオロメタンスルホン酸ランタン及びＮ−メチル−Ｎ’−ヒドロキシエチルピペラジンの代わりにＬ３３を使用した以外は、実施例１５と同じ手法を用いた。結果を表４にあわせて示す。
Comparative Example 11:
The same procedure was used as in Example 15 except that L33 was used instead of lanthanum trifluoromethanesulfonate and N-methyl-N′-hydroxyethylpiperazine. The results are shown in Table 4.
実施例１５、１６は本発明の触媒を使用した例であるが、触媒活性が高く、触媒として一般に使用されているトリエチレンジアミン（比較例１１）とほぼ同等の活性を示す。また、成形されたウレタン樹脂に発泡は認められず、良好な樹脂を製造することができる。一方、トリエチレンジアミンを触媒として用いた場合（比較例１１）、ウレタン樹脂に発泡が生じており、非発泡のウレタン分野では使用が難しい場合がある。
Examples 15 and 16 are examples in which the catalyst of the present invention was used, but the catalytic activity was high and the activity was almost the same as that of triethylenediamine (Comparative Example 11) generally used as a catalyst. Moreover, foaming is not recognized by the shape | molded urethane resin, but favorable resin can be manufactured. On the other hand, when triethylenediamine is used as a catalyst (Comparative Example 11), foaming occurs in the urethane resin, which may be difficult to use in the non-foamed urethane field.
Claims (6)
Ｍ（ＣＦ３ＳＯ３）３ （１）
（式中、Ｍは、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ又はＬｕを表す。）
で示されるトリフルオロメタンスルホン酸金属塩と、ヒドロキシル基を分子中に有し、下記一般式（２）
で示されるアミン化合物からなるポリウレタン樹脂製造用触媒組成物。 The following general formula (1)
M (CF 3 SO 3 ) 3 (1)
(In the formula, M represents Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu.)
And a metal having a hydroxyl group in the molecule, represented by the following general formula (2)
A catalyst composition for producing a polyurethane resin comprising an amine compound represented by the formula:
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| CN114907753A (en) * | 2021-10-13 | 2022-08-16 | 南京伊戈高分子复合新材料科技有限公司 | Closed type aqueous polyurethane resin composition |
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| CN102551268B (en) * | 2011-11-10 | 2013-05-22 | 杨红光 | Silica gel health-care shoe and making method thereof as well as silica gel insole and making method thereof |
| US11859043B2 (en) | 2020-07-17 | 2024-01-02 | Momentive Performance Materials Inc. | Moisture-curable silylated polymer resin composition with reduced moisture sensitivity |
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