CN115466201A - 一种磺酸改性多异氰酸酯及其制备方法 - Google Patents
一种磺酸改性多异氰酸酯及其制备方法 Download PDFInfo
- Publication number
- CN115466201A CN115466201A CN202110650822.4A CN202110650822A CN115466201A CN 115466201 A CN115466201 A CN 115466201A CN 202110650822 A CN202110650822 A CN 202110650822A CN 115466201 A CN115466201 A CN 115466201A
- Authority
- CN
- China
- Prior art keywords
- component
- diisocyanate
- polyisocyanate
- sulfonic acid
- cyclohexylamine
- 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.)
- Granted
Links
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 93
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 93
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- -1 p-methylcyclohexyl Chemical group 0.000 claims description 28
- 150000003512 tertiary amines Chemical class 0.000 claims description 22
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 claims description 2
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- PQNQOHDLTYFBHE-UHFFFAOYSA-N 1-ethyl-2h-quinoline Chemical compound C1=CC=C2N(CC)CC=CC2=C1 PQNQOHDLTYFBHE-UHFFFAOYSA-N 0.000 claims description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 2
- VORLTHPZWVELIX-UHFFFAOYSA-N 1-methyl-2h-quinoline Chemical compound C1=CC=C2N(C)CC=CC2=C1 VORLTHPZWVELIX-UHFFFAOYSA-N 0.000 claims description 2
- LKWOOKWVBNSLGN-UHFFFAOYSA-N 2,3-dimethylcyclohexan-1-amine Chemical compound CC1CCCC(N)C1C LKWOOKWVBNSLGN-UHFFFAOYSA-N 0.000 claims description 2
- FEUISMYEFPANSS-UHFFFAOYSA-N 2-methylcyclohexan-1-amine Chemical compound CC1CCCCC1N FEUISMYEFPANSS-UHFFFAOYSA-N 0.000 claims description 2
- ZGMQLPDXPUINCQ-UHFFFAOYSA-N 3,3,5-trimethylcyclohexan-1-amine Chemical compound CC1CC(N)CC(C)(C)C1 ZGMQLPDXPUINCQ-UHFFFAOYSA-N 0.000 claims description 2
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 claims description 2
- OQNQLWFDIGLWIA-UHFFFAOYSA-N 4-tert-butyl-n-ethylcyclohexan-1-amine Chemical compound CCNC1CCC(C(C)(C)C)CC1 OQNQLWFDIGLWIA-UHFFFAOYSA-N 0.000 claims description 2
- INGRKTXZUZXXPB-UHFFFAOYSA-N 4-tert-butyl-n-methylcyclohexan-1-amine Chemical compound CNC1CCC(C(C)(C)C)CC1 INGRKTXZUZXXPB-UHFFFAOYSA-N 0.000 claims description 2
- BGNLXETYTAAURD-UHFFFAOYSA-N 4-tert-butylcyclohexan-1-amine Chemical compound CC(C)(C)C1CCC(N)CC1 BGNLXETYTAAURD-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- BHCFVCRRNLIOGM-UHFFFAOYSA-J C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] Chemical compound C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] BHCFVCRRNLIOGM-UHFFFAOYSA-J 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002015 acyclic group Chemical group 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- VDVKGXYMSAXWME-UHFFFAOYSA-K aluminum 2-ethyl-3-oxobutanoate Chemical compound [Al+3].CCC(C(C)=O)C([O-])=O.CCC(C(C)=O)C([O-])=O.CCC(C(C)=O)C([O-])=O VDVKGXYMSAXWME-UHFFFAOYSA-K 0.000 claims description 2
- 150000004982 aromatic amines Chemical group 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- QXKMIZHVHZMDPQ-UHFFFAOYSA-N cyclopentanone;ethyl acetate Chemical compound CCOC(C)=O.O=C1CCCC1 QXKMIZHVHZMDPQ-UHFFFAOYSA-N 0.000 claims description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- ZNYHMFMQFFSNIH-UHFFFAOYSA-N n,2,3-trimethylcyclohexan-1-amine Chemical compound CNC1CCCC(C)C1C ZNYHMFMQFFSNIH-UHFFFAOYSA-N 0.000 claims description 2
- HMDSHIZGTPRJHT-UHFFFAOYSA-N n,2-dimethylcyclohexan-1-amine Chemical compound CNC1CCCCC1C HMDSHIZGTPRJHT-UHFFFAOYSA-N 0.000 claims description 2
- YBPHGVBAJQGYDH-UHFFFAOYSA-N n,4-dimethylcyclohexan-1-amine Chemical compound CNC1CCC(C)CC1 YBPHGVBAJQGYDH-UHFFFAOYSA-N 0.000 claims description 2
- HPWAWIARLCZKBB-UHFFFAOYSA-N n-ethyl-2,3-dimethylcyclohexan-1-amine Chemical compound CCNC1CCCC(C)C1C HPWAWIARLCZKBB-UHFFFAOYSA-N 0.000 claims description 2
- UCFBHIZLPWZXBO-UHFFFAOYSA-N n-ethyl-2-methylcyclohexan-1-amine Chemical compound CCNC1CCCCC1C UCFBHIZLPWZXBO-UHFFFAOYSA-N 0.000 claims description 2
- NKSZFKLFWWMCGB-UHFFFAOYSA-N n-ethyl-4-methylcyclohexan-1-amine Chemical compound CCNC1CCC(C)CC1 NKSZFKLFWWMCGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 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 claims 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 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 claims 2
- HXYDAOXNYINGCS-UHFFFAOYSA-J 2-ethylhexanoate;tin(4+) Chemical compound [Sn+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O HXYDAOXNYINGCS-UHFFFAOYSA-J 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 1
- XQWSLHIYGMOJHI-UHFFFAOYSA-N n-(cyclohexylmethyl)ethanamine Chemical compound CCNCC1CCCCC1 XQWSLHIYGMOJHI-UHFFFAOYSA-N 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 abstract description 22
- 238000003860 storage Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000012948 isocyanate Substances 0.000 description 13
- 150000002513 isocyanates Chemical class 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 9
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- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 8
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- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- UVNLRRQVXHIOKC-UHFFFAOYSA-N 3-[(4-methylcyclohexyl)amino]propane-1-sulfonic acid Chemical compound CC1CCC(NCCCS(O)(=O)=O)CC1 UVNLRRQVXHIOKC-UHFFFAOYSA-N 0.000 description 1
- XNPKNHHFCKSMRV-UHFFFAOYSA-N 4-(cyclohexylamino)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCNC1CCCCC1 XNPKNHHFCKSMRV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种磺酸改性多异氰酸酯及其制备方法,通过控制原料中环己基胺组分的含量,促进氨基磺酸与多异氰酸酯反应速率加快,从而使制备得到得产品具有颜色浅、浊度低的优点,且存储稳定性好。
Description
技术领域
本发明涉及改性异氰酸酯领域,具体地涉及一种磺酸亲水改性多异氰酸酯及其制备方法,本发明还涉及所制备的磺酸亲水改性多异氰酸酯在涂覆剂、粘合剂、密封剂等领域中的应用。
背景技术
随着日益增加的环保压力,水性涂料、粘合剂组合物成为了溶剂型涂料、粘合剂的最佳环保替代品。但亲水组分的引入以及生产工艺决定其耐水性、耐溶剂性、耐热性能较差,而水性异氰酸酯固化剂的引入能够有效改善水性涂料、粘合剂的耐性。
水性异氰酸酯固化剂根据亲水基团可分为两类,一类是聚醚改性的异氰酸酯固化剂,另外一类则是磺酸改性的异氰酸酯固化剂。其中聚醚改性的异氰酸酯固化剂虽然获得了广泛的市场认可,但为了获得好的亲水性需要引入大量的聚醚,高聚醚含量为其带来了有效异氰酸酯含量低以及耐性差的缺点,这些固有的缺点限制了它的应用。磺酸改性的异氰酸酯固化剂因具有官能度高易于分散等优点其应用也越来越广泛。
专利CN1190450C使用3-(环己基氨基)-丙磺酸和2-(环己基氨基)-乙磺酸固体粉末制备磺酸改性多异氰酸酯,所得改性的多异氰酸酯不需要高剪切力就能够在水中均匀分散。CN104448232B使用4-(环己基氨基)-乙磺酸固体粉末制备磺酸改性多异氰酸酯,同样获得了性能优异的磺酸改性多异氰酸酯。但是现有技术中采用固体磺酸化合物改性异氰酸酯固化剂的方法存在一定的缺陷:首先固体粉末磺酸与异氰酸酯的相容性差,界面反应导致反应时间长、产品颜色深;其次,未完全反应的固体粉末会引起产品浊度高且随着存储时间的延长颜色加深。
发明内容
本专利的目的是提供一种磺酸改性多异氰酸酯及其制备方法,可以有效改善现有的磺酸改性异氰酸酯方法中反应速率慢、产品浊度高、储存颜色易加深的缺点,使得反应速率较快,产品浊度低,储存稳定性好。
为了实现以上发明目的,本发明提供如下技术方案:
一种磺酸改性多异氰酸酯,所述磺酸改性多异氰酸酯是采用包含以下组分的反应得到的反应产物:
a)至少一种多异氰酸酯组分;
b)至少一种带有一个以上磺酸和/或磺酸根基团的有机化合物,且该化合物含有至少一个巯基、伯氨基或仲氨基;
c)至少一种叔胺;
d)至少一种具有以下结构的环己基胺:
其中,中R1是环己基、环己甲基、对甲基环己基、2-甲基环己基、2,3-二甲基环己基、3,3,5-三甲基环己基、4-叔丁基环己基中的一种,R2是氢或具有1至18个碳原子的饱和或不饱和、直链或支化、脂族或脂环族或芳族有机基团。
优选的,以组分a)的质量为1000份计,组分b)加入的质量为5~150份,优选15-120份。
优选的,组分c)与组分b)的摩尔比为0.5~1.5:1。优选的,所述多异氰酸酯组分a)为平均异氰酸酯官能度为2.0-5.0,NCO含量为7.0-32.0wt%的脂族、脂环族、芳脂族和/或芳族的多异氰酸酯或改性多异氰酸酯中的一种或多种。
上述的改性多异氰酸酯可以是含有脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的改性多异氰酸酯,它们可通过简单的脂肪族、脂环族、芳香族和/或芳脂族的二异氰酸酯中的一种或多种,可按照DE1670666A,DE1954093A,DE2414413A,DE2452532A,DE2641380A,DE3700209A,DE3900053A、DE3928503A、EP0336205A、EP0339396A以及EP0798299A等专利中的方法改性制备;
用于制备上述含有脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的改性多异氰酸酯的适合的二异氰酸酯是那些可以用光气法或者非光气法得到的,例如由氨基甲酸乙酯热分解得到的任何二异氰酸酯。
优选的,所述多异氰酸酯是分子量在100-500、具有脂肪性、脂环性、芳脂性或者芳香性键接的二异氰酸酯,例如四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、4,4'-二环己基丙烷二异氰酸酯、1,4-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-和2,4'-二苯基甲烷二异氰酸酯、四甲基二甲苯基二异氰酸酯和对苯二甲基二异氰酸酯或这些二异氰酸酯的混合物。
优选的,多异氰酸酯为基于1,6-己二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)和4,4’-二环己基甲烷二异氰酸酯(H12MDI)中的一种或多种的具有异氰脲酸酯基团的改性多异氰酸酯。
上述含有脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的改性多异氰酸酯在制备过程中可添加抗氧剂、自由基清除剂、抑制剂等助剂。
优选的,所述组分b)是带有氨基官能团的磺酸和/或磺酸盐,优选带有仲氨基的磺酸和/或磺酸盐。
进一步的,组分b)为带有仲氨基的磺酸有机化合物具有如下结构:
其中R3为环己基、环己甲基、对甲基环己基、2-甲基环己基、2,3-二甲基环己基、3,3,5-三甲基环己基、4-叔丁基环己基中的一种,R4为是具有2至6个碳原子的直链或支化脂族基团。
所述组分b)在反应前、反应中和/或反应后可被叔胺c)部分或全部中和成盐。所述叔胺一方面用来中和组分b)中的磺酸/或磺酸根基团,形成磺酸盐,另一方面作为反应的相转移催化剂来催化多异氰酸酯和氨基磺酸的反应。
所述的叔胺c)为脂肪族和/或脂环族取代的、非环状和/或环状的叔胺,可选自三甲胺、三乙胺、三丙胺、N,N-二甲基丁基胺、N,N-二乙基甲基胺、N,N-二异丙基乙基胺、N,N-二甲基环己基胺、N-甲基哌啶、N-甲基喹啉、N-乙基喹啉和/或N-乙基吗啉或本领域其他用于催化异氰酸酯组分与组分b)反应的叔胺中的一种或多种,优选为N,N-二甲基环己基胺。
优选的,所述改性多异氰酸酯中还可以加入聚氨酯学科中通常使用的催化剂与叔胺c)混合使用,比如其他有机金属催化剂:三(乙基-乙酸乙酰)铝、正辛酸锡、正辛酸锌、2-乙基-1-己酸锡(Ⅱ)、二氯化二丁基锡(Ⅳ)、二乙酸二丁基锡(Ⅳ)、二月桂酸二丁基锡(Ⅳ)、二乙酸二辛基锡(Ⅳ)或者乙醇酸钼中的一种或多种的混合物。
优选的,所述组分d)的环己基胺为环己胺、环己甲基胺、对甲基环己胺、2-甲基环己胺、2,3-二甲基环己胺、3,3,5-三甲基环己胺、4-叔丁基环己胺、N-甲基环己胺、N-甲基环己甲基胺、N-甲基对甲基环己胺、N-甲基-2-甲基环己胺、N-甲基-2,3-二甲基环己胺、N-甲基-3,3,5-三甲基环己胺、N-甲基-4-叔丁基环己胺、N-乙基环己胺、N-乙基环己甲基胺、N-乙基对甲基环己胺、N-乙基-2-甲基环己胺、N-乙基-2,3-二甲基环己胺、N-乙基-3,3,5-三甲基环己胺、N-乙基-4-叔丁基环己胺中的一种或多种。
优选的,以组分a)的质量为1000份计,组分d)的加入的质量为0.05-2份,优选0.2-1.6份。本申请发明人惊喜的发现,当加入组分d)的含量控制在一定范围内时,可以有效改善氨基磺酸与多异氰酸酯的相容性,加快反应速率,且得到的产品浊度较低,储存稳定性好。组分d)的环己基胺用量太少无法起到改善氨基磺酸与多异氰酸酯相容性的作用,用量太多组分b)与多异氰酸酯反应太快,容易在组分b)颗粒表面形成高黏表层阻止其进一步溶解与多异氰酸酯反应。
为了更好的增加氨基磺酸与多异氰酸酯相容性,加快反应速率,获得颜色浅、浊度低的产品,优选的,所述组分d)的环己基胺含有与组分b)的有机化合物中的R3相同基团的环己基胺。
本发明还涉及到一种磺酸改性多异氰酸酯的制备方法,在组分c)叔胺的存在下,使组分a)多异氰酸酯组分、组分b)、组分d)在70-110℃条件下反应,其中组分a)多异氰酸酯可一步或多步投入。在制备过程中,可加入抗氧剂降低其色号。所述抗氧剂可以是能消除自由基的芳香胺和受阻酚等化合物及其衍生物,也可以是能分解氢过氧化物的抗氧剂有含磷和含硫的有机化合物,或者是它们的组合物。
在本发明所述的方法中,该反应可选择在NCO反应惰性的溶剂中进行。例如丙酮、丁酮、环戊酮乙酸乙酯、乙酸丁酯、N-乙基吡咯烷酮、N-甲基吡咯烷酮、甲苯、二甲苯、氯苯、丙二醇甲醚醋酸酯、1-甲氧基丙-2-基乙酸酯、3-甲氧基-正丁基乙酸酯、芳香化合物、碳酸二甲酯、碳酸二乙酯、丁内酯、己内酯以及甲基己内酯等溶剂中的一种或者任意多种的混合物。
本发明还提供所述的磺酸亲水改性的多异氰酸酯以及采用本发明方法制备的改性多异氰酸酯作为交联剂用在水分散性双组份涂料、粘合剂中的用途。其颜色浅、浊度低、具有优异的常温储存稳定性和优异的水分散性能。
本发明还提供氨基磺酸亲水改性的多异氰酸酯作为起始组分在制备水分散性或在水中以分散体形式存在的封闭多异氰酸酯中的用途。适合的封闭剂有例如丙二酸二乙酯、乙酰乙酸乙酯、3,5-二甲基吡唑、咪唑、ε-己内酰胺等或者这些封闭剂的混合物。
本发明的磺酸改性的多异氰酸酯,除了用作双组份的涂料和粘合剂作为交联成分以外,本发明的氨基磺酸改性的多异氰酸酯还可以作为交联剂用于织物整理、印花涂料粘合剂、以及用来交联其他水分散体或者作为助剂对纸张进行增湿处理。
本发明通过将环己基胺引入到多异氰酸酯中,增大了多异氰酸酯与带有至少一个磺酸和/或磺酸根基团的有机化合物的相容性,使反应速率加快,在大大增加生产效率的同时获得了颜色浅、浊度低的磺酸亲水改性多异氰酸酯产品。
具体实施方式:
下面结合实施例对本发明作进一步的说明,需要说明的是,实施例并不构成对本发明要求保护范围的限制。
多异氰酸酯a2(拜耳NZ1,基于HDI和IPDI的多异氰酸酯,NCO=20wt%)氨基磺酸b1:2-环己胺基乙磺酸,购买自阿拉丁试剂,纯度≥99%
氨基磺酸b2:3-环己胺基丙磺酸,购买自百灵威试剂,纯度99%
氨基磺酸b3:4-环己胺基丁磺酸,在二氧六环溶剂中,用环己胺和1,4-丁磺酸内酯以摩尔比3:1在80℃反应6h,收集固体,用丙酮洗涤至白色。
氨基磺酸b4:3-对甲基环己胺基丙磺酸,在二氧六环溶剂中,用对甲基环己胺和1,4-丁磺酸内酯以摩尔比3:1在80℃反应6h,收集固体,用丙酮洗涤至白色。
叔胺c1:N,N-二甲基环己胺,购买自百灵威试剂,纯度99%
叔胺c2:N-乙基吗啉,购买自百灵威试剂,纯度99%
伯胺d1:环己胺,购买自百灵威试剂,纯度99%
伯胺d2:4-甲基环己胺,购买自百灵威试剂,纯度95%
伯胺d3:环己甲胺,购买自百灵威试剂,纯度98%
仲胺d4:N-甲基环己胺,购买自百灵威试剂,纯度98%
仲胺d5:N-乙基环己胺,购买自百灵威试剂,纯度99%
实施例1
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,50℃,200rpm搅拌下将0.32g环己基胺d1(0.003mol)滴加到380g多异氰酸酯a1中,反应10min后,将17.39g(0.084mol)氨基磺酸b1和10.67g(0.084mol)叔胺c1加入到反应体系中,混合均匀,加热到80℃反应3h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.5wt%
平均NCO官能度:3.39
粘度(25℃):5600mPa·s
SO3-含量:1.65wt%
色号:6
浊度:0.2
实施例2
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将将17.39g(0.084mol)氨基磺酸b1和6.4g(0.042mol)叔胺c1加入到380g多异氰酸酯a1中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.6g(0.006mol)环己基胺d1加入到反应体系中并反应3h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.59wt%
平均NCO官能度:3.39
粘度(25℃):5500mPa·s
SO3-含量:1.66wt%
色号:4
浊度:0
实施例3
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将将17.39g(0.084mol)氨基磺酸b1和16g(0.126mol)叔胺c1加入到380g多异氰酸酯a1中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.08g(0.001mol)环己基胺d1加入到反应体系中并反应4h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.40wt%
平均NCO官能度:3.40
粘度(25℃):5500mPa·s
SO3-含量:1.63wt%
色号:14
浊度:0.6
实施例4
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将将18.57g(0.084mol)氨基磺酸b2和10.67g(0.084mol)叔胺c1加入到380g多异氰酸酯a1中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.32g(0.003mol)环己基胺d1加入到反应体系中并反应3h,停止反应,冷却至室温,经325目滤网过滤,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.35wt%
平均NCO官能度:3.39
粘度(25℃):5800mPa·s
SO3-含量:1.64wt%
色号:4
浊度:0.2
实施例5
本实施例与实施例4的主要区别之处在于,加入的环己基胺d1的量为0.75g,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.39wt%
平均NCO官能度:3.39
粘度(25℃):5600mPa·s
SO3-含量:1.64wt%
色号:26
浊度:1.3
实施例6
本实施例与实施例4的主要区别之处在于,加入的环己基胺d1的量为0.60g,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.45wt%
平均NCO官能度:3.39
粘度(25℃):6000mPa·s
SO3-含量:1.64wt%
色号:9
浊度:0.2
实施例7
本实施例与实施例4的主要区别之处在于,加入的环己基胺d1的质量为0.10g,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.48wt%
平均NCO官能度:3.40
粘度(25℃):5600mPa·s
SO3-含量:1.64wt%
色号:15
浊度:0.8
实施例8
本实施例与实施例4的主要区别之处在于,加入的环己基胺d1的质量为0.02g得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.44wt%
平均NCO官能度:3.40
粘度(25℃):5700mPa·s
SO3-含量:1.64wt%
色号:25
浊度:1.1
实施例9
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将18.57g(0.084mol)氨基磺酸b2和10.67g(0.084mol)叔胺c1加入到380g多异氰酸酯a1中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.42g环己基胺d5加入到反应体系中并反应3h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.48wt%
平均NCO官能度:3.39
粘度(25℃):5600mPa·s
SO3-含量:1.64wt%
色号:9
浊度:0.2
实施例10
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将18.57g(0.084mol)氨基磺酸b2和9.66g(0.084mol)叔胺c2加入到380g多异氰酸酯a1中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.37g环己基胺d2加入到反应体系中并反应3h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.5wt%
平均NCO官能度:3.39
粘度(25℃):6000mPa·s
SO3-含量:1.64wt%
色号:7
浊度:0.2
实施例11
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将19.75g(0.084mol)氨基磺酸b3和10.67g(0.084mol)叔胺c1加入到380g多异氰酸酯a2中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.38g环己基胺d3加入到反应体系中并反应5h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:17.54wt%
平均NCO官能度:3.24
粘度(25℃):5100mPa·s
SO3-含量:1.64wt%
色号:11
浊度:0.3
实施例12
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将9.28g(0.042mol)氨基磺酸b2和5.33g(0.042mol)叔胺c1加入到380g多异氰酸酯a1中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.4g环己基胺d4加入到反应体系中并反应3h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:20.59wt%
平均NCO官能度:3.47
粘度(25℃):3800mPa·s
SO3-含量:0.85wt%
色号:4
浊度:0.1
实施例13
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中,将37.12g(0.17mol)氨基磺酸b2和21.33g(0.17mol)叔胺c1加入到380g多异氰酸酯a1中,200rpm搅拌混合均匀并加热到80℃,逐滴将0.32g(0.003mol)环己基胺d1加入到反应体系中并反应4h,停止反应,经325目滤网过滤,冷却至室温,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:17.20wt%
平均NCO官能度:3.24
粘度(25℃):7700mPa·s
SO3-含量:3.06wt%
色号:17
浊度:0.7
对比例1
本对比例与实施例4的主要区别之处在于,所述环己基胺d1的加入量为0.01g,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.50wt%
平均NCO官能度:3.4
粘度(25℃):5900mPa·s
SO3-含量:1.64wt%
色号:61
浊度:4.7
对比例2
本对比例与实施例4的主要区别之处在于,制备过程中不加入环己基胺d1,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.44wt%
平均NCO官能度:3.4
粘度(25℃):5300mPa·s
SO3-含量:1.64wt%
色号:82
浊度:7.2
对比例3
本对比例与实施例4的主要区别之处在于,加入的环己基胺d1的量为0.85g,得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯:
固体含量:100%
NCO含量:19.31wt%
平均NCO官能度:3.38
粘度(25℃):6400mPa·s
SO3-含量:1.64wt%
色号:96
浊度:12
由实施例1-13以及对比例1-2可看出,在体系中引入少量环己基胺可提升氨基磺酸与多异氰酸酯的反应速率,获得颜色浅、浊度低的磺酸亲水改性多异氰酸酯,由对比例1、3可看出,引入的伯胺过量或过少均无法起到较好的作用,无法获得颜色浅/浊度低的产品。
存储稳定性测试:将200g所制备的氨基磺酸改性的多异氰酸酯装入250ml铝瓶(使用前在100℃烘箱热烘1h)中,用氮气吹扫30s后放入50℃烘箱中储存,30天后测试NCO含量、粘度、色号变化,具体数据如下表所示:
表1储存稳定性测试数据
由实施例1-13以及对比例1-3可看出,在本发明所述含量的环己基胺存在条件下所制备得到的磺酸亲水改性多异氰酸酯色号更低、储存稳定性更好,经热储后颜色变化不明显。
Claims (10)
2.根据权利要求1所述的磺酸改性多异氰酸酯,其特征在于,以组分a)的质量为1000份计,组分b)加入的质量为5~150份,优选15-120份。
优选的,组分c)与组分b)的摩尔比为0.5~1.5:1。
3.根据权利要求1所述的磺酸改性多异氰酸酯,其特征在于,所述多异氰酸酯组分a)为平均异氰酸酯官能度为2.0-5.0,NCO含量为7.0-32.0wt%的脂族、脂环族、芳脂族和/或芳族的多异氰酸酯或改性多异氰酸酯中的一种或多种;
优选的,所述多异氰酸酯组分是分子量在100-500、具有脂肪性、脂环性、芳脂性或者芳香性键接的二异氰酸酯,优选四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、4,4'-二环己基丙烷二异氰酸酯、1,4-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-和2,4'-二苯基甲烷二异氰酸酯、四甲基二甲苯基二异氰酸酯和对苯二甲基二异氰酸酯或这些二异氰酸酯的混合物;
优选的,多异氰酸酯组分为基于1,6-己二异氰酸酯、异佛尔酮二异氰酸酯和4,4’-二环己基甲烷二异氰酸酯中的一种或多种的具有异氰脲酸酯基团的改性多异氰酸酯。
4.根据权利要求1所述的磺酸改性多异氰酸酯,其特征在于,所述组分b)是带有氨基官能团的磺酸和/或磺酸盐,优选带有仲氨基的磺酸和/或磺酸盐。
6.根据权利要求1-5任一项所述的磺酸改性多异氰酸酯,其特征在于,所述的叔胺c)为脂肪族和/或脂环族取代的、非环状和/或环状的叔胺,可选自三甲胺、三乙胺、三丙胺、N,N-二甲基丁基胺、N,N-二乙基甲基胺、N,N-二异丙基乙基胺、N,N-二甲基环己基胺、N-甲基哌啶、N-甲基喹啉、N-乙基喹啉和/或N-乙基吗啉中的一种或多种,优选为N,N-二甲基环己基胺。
7.根据权利要求1-6任一项所述的磺酸改性多异氰酸酯,其特征在于,所述改性多异氰酸酯中还可以加入聚氨酯学科中通常使用的催化剂与叔胺c)混合使用,比如其他有机金属催化剂:三(乙基-乙酸乙酰)铝、正辛酸锡、正辛酸锌、2-乙基-1-己酸锡(Ⅱ)、二氯化二丁基锡(Ⅳ)、二乙酸二丁基锡(Ⅳ)、二月桂酸二丁基锡(Ⅳ)、二乙酸二辛基锡(Ⅳ)或者乙醇酸钼中的一种或多种的混合物。
8.根据权利要求1-6任一项所述的磺酸改性多异氰酸酯,其特征在于,所述组分d)的环己基胺为环己胺、环己甲基胺、对甲基环己胺、2-甲基环己胺、2,3-二甲基环己胺、3,3,5-三甲基环己胺、4-叔丁基环己胺、N-甲基环己胺、N-甲基环己甲基胺、N-甲基对甲基环己胺、N-甲基-2-甲基环己胺、N-甲基-2,3-二甲基环己胺、N-甲基-3,3,5-三甲基环己胺、N-甲基-4-叔丁基环己胺、N-乙基环己胺、N-乙基环己甲基胺、N-乙基对甲基环己胺、N-乙基-2-甲基环己胺、N-乙基-2,3-二甲基环己胺、N-乙基-3,3,5-三甲基环己胺、N-乙基-4-叔丁基环己胺中的一种或多种;
优选的,以组分a)的质量为1000份计,组分d)的加入的质量为0.05-2份,优选0.2-1.6份;
优选的,所述组分d)的环己基胺含有与组分b)的有机化合物中的R3相同基团的环己基胺。
9.根据权利要求1-8任一项所述的磺酸改性多异氰酸酯的制备方法,其特征在于,在组分c)叔胺的存在下,使组分a)多异氰酸酯组分、组分b)、组分d)在70-110℃条件下反应,其中组分a)多异氰酸酯可一步或多步投入;
优选的,所述制备方法中,还可加入抗氧剂;
优选的,所述抗氧剂是能消除自由基的芳香胺和受阻酚类化合物及其衍生物或能分解氢过氧化物的抗氧剂有含磷和含硫的有机化合物,或者是它们的组合物。
10.根据权利要求9所述的制备方法,其特征在于,该反应可选择在NCO反应惰性的溶剂中进行;优选丙酮、丁酮、环戊酮乙酸乙酯、乙酸丁酯、N-乙基吡咯烷酮、N-甲基吡咯烷酮、甲苯、二甲苯、氯苯、丙二醇甲醚醋酸酯、1-甲氧基丙-2-基乙酸酯、3-甲氧基-正丁基乙酸酯、芳香化合物、碳酸二甲酯、碳酸二乙酯、丁内酯、己内酯以及甲基己内酯溶剂中的一种或者任意多种的混合物。
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