CN102604041A - Silicon modified double cross-linking type aqueous polyurethane curing agent and preparation method thereof - Google Patents
Silicon modified double cross-linking type aqueous polyurethane curing agent and preparation method thereof Download PDFInfo
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- CN102604041A CN102604041A CN2011104532047A CN201110453204A CN102604041A CN 102604041 A CN102604041 A CN 102604041A CN 2011104532047 A CN2011104532047 A CN 2011104532047A CN 201110453204 A CN201110453204 A CN 201110453204A CN 102604041 A CN102604041 A CN 102604041A
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- Prior art keywords
- curing agent
- silicon
- polyurethane curing
- modified double
- aqueous polyurethane
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Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 238000004132 cross linking Methods 0.000 title claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 organo silicon Chemical compound 0.000 claims abstract description 31
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 29
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 25
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 229920000570 polyether Polymers 0.000 claims description 44
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 36
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical group ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 125000005375 organosiloxane group Chemical group 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 230000004580 weight loss Effects 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 3
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920005606 polypropylene copolymer Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003973 paint Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 125000000962 organic group Chemical group 0.000 abstract 2
- 229920001296 polysiloxane Polymers 0.000 abstract 2
- 238000011056 performance test Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 16
- 239000002202 Polyethylene glycol Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 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 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 5
- 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 4
- 238000009835 boiling Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(I)[U](*)(*CC=C)N=C Chemical compound CC(C)(I)[U](*)(*CC=C)N=C 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a silicon modified double cross-linking type aqueous polyurethane curing agent and a preparation method thereof. The aqueous polyurethane curing agent is formed by mixing and reacting polyisocyanate, organo silicone modified polyethylene oxide ether, organo silicone, a catalyst, a terminator and a proper amount of solvent. The invention relates to a synthesis method of the curing agent as well as a performance test and application of the curing agent. The hardness, water-resistance chemical resistance performance aspects of a paint film prepared by using the organo silicon modified curing agent is improved in the aspects of hardness, water resistance and chemical resistance.
Description
Technical Field
The invention relates to a silicon modified double-crosslinking waterborne polyurethane curing agent and a preparation method thereof.
Background
Due to the combination of environmental protection and cost effectiveness, more and more chemists are being motivated to develop new coatings that reduce VOC emissions without affecting resin properties. Therefore, the formation of water-based coatings is an important means.
The use of polyether water-soluble polymers for the nonionic modification of polyisocyanates has been described in a large number of documents. For example, in document US5468804, the addition product of toluene diisocyanate and trimethylolpropane is easily dispersed in water by using polyethylene glycol monomethyl ether to modify the TDI/TMP addition product; in document US4663377, HDI trimer is modified by polyethylene glycol monomethyl ether in a hydrophilic manner, so that the modified HDI trimer can be easily dispersed in water; in document US5731396, a waterborne polyurethane curing agent is prepared by using caprolactone to modify polyethylene glycol monomethyl ether so that the polyethylene glycol monomethyl ether does not crystallize due to excessively regular molecular chains, and then serving as a hydrophilic modifier of HDI trimer; document US6426414, CN00816661.7, discloses that the active hydrogen of the carbamate group of a polyethylene glycol monomethyl ether hydrophilic modified HDI trimer reacts with the isocyanate group of another HDI trimer by adding a catalyst to form allophanate, and the product can be emulsified into particularly fine particles in water.
Nonionic modified aqueous polyurethane curing agents have been reported in many documents, but there are many problems. For example, poor dispersibility in water, large particle size, and short pot life. In addition, the use of molecular chain-structured polyethers having a molecular weight of more than 800 is often accompanied by the problem of easy crystallization of the product, which leads to a reduction in the storage stability of the product.
Disclosure of Invention
The invention aims to provide a silicon modified double-crosslinking waterborne polyurethane curing agent and a preparation method thereof. The curing agent can improve the performance and stability of a coating film, a polyurethane curing agent which can be manually stirred and stably dispersed in a water-based system is synthesized, and besides a traditional crosslinking group, the curing agent also increases a hydrolysis crosslinking structure of an alkoxy group, namely: the-Si-O-Si-bond forms a double cross-linked coating film, and the hardness, water resistance and chemical resistance of the coating film are fully improved.
To achieve the above object, a silicon-modified double-crosslinking aqueous polyurethane curing agent is prepared fromThe molecular structure of the aqueous polyisocyanate dispersion synthesized by mixing and reacting aromatic or aliphatic polyisocyanate, polyoxyethylene polyether, organosiloxane, catalyst, terminator and solvent is as follows:
or
In the above-mentioned molecular structure, the polymer,
r is aliphatic, unbranched or branched C1～C10A group;
R1a reactive group that is amino, epoxy, or carboxyl;
R2and R3Is H, CH3，CH2CH3，CH2CH2CH3Or C4H9Or is OCH or3，OCH2CH3，OCH2CH2CH3Or OC4H9Or an aromatic chain;
R4an aliphatic or aromatic chain linked to various diisocyanate groups;
x is aliphatic, unbranched or branched C1～C10A group; or is CH2CH2OCH2CH2The polyether segment of (a);
n is an integer of 1 to 30.
The preparation method of the silicon modified double-crosslinking waterborne polyurethane curing agent comprises the following steps: firstly, adding 1 to percent by weight of polyoxyethylene polyether and 0.01 to 20 percent by weight of organosiloxane into a reaction kettle provided with a stirrer, a thermometer and fractional condensation, reacting at 80 to 220 ℃, stopping the reaction when weight loss or collected effluent reaches a theoretical value, and cooling to form modified polyoxyethylene polyether;
adding 50-95 wt% of aromatic or aliphatic polyisocyanate and 1.01-55 wt% of the modified polyoxyethylene polyether into another reaction kettle provided with a stirrer, a thermometer and a constant-pressure dropping device, and reacting for 2.5-3 hours at 100-110 ℃; during the reaction, 0-0.1 wt% of catalyst and 0-48 wt% of solvent are added, and 0-0.1 wt% of terminator is added to terminate the reaction;
after the reaction, the above aqueous polyisocyanate dispersion is finally obtained.
In the invention, organosilicon monomer or siloxane with low fatty chain is introduced into polyether chain, and the modified polyether chain is grafted to polyisocyanate, so that the curing agent has higher functionality and water dispersion performance. The polyurethane curing agent is mainly used for two-component coatings in the field of coatings, and a reticular cross-linked structure is formed through the reaction between functional groups in the film forming process to cure a coating film. In addition, the product of the invention can also be used in the field of aqueous adhesives and used for bonding various materials. Can also be used as an additive in textile finishing and a cross-linking agent in water-based ink.
The invention aims to improve the performance and stability of a coating film, synthesizes a polyurethane curing agent which can be manually stirred and stably dispersed in a water-based system, and the curing agent not only adds the traditional crosslinking group (isocyanate and hydroxyl), but also adds the hydrolytic crosslinking structure (-Si-O-Si-bond) of an alkoxy group to form a double-crosslinking coating film, thereby fully improving the hardness, water resistance and chemical resistance of the coating film.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The silicon modified double-crosslinking waterborne polyurethane curing agent is a waterborne polyisocyanate dispersion synthesized by mixing and reacting aromatic or aliphatic polyisocyanate, polyoxyethylene polyether, organic siloxane, a catalyst, a terminator and a solvent, and has a molecular structure as follows:
In the above-mentioned molecular structure, the polymer,
r is aliphatic, unbranched or branched C1～C10A group; preferably H, CH3，CH2CH3，CH2CH2CH3，C4H9。
R1A reactive group that is amino, epoxy, or carboxyl;
R2and R3Is H, CH3，CH2CH3，CH2CH2CH3Or C4H9Or is OCH or3，OCH2CH3，OCH2CH2CH3Or OC4H9Or an aromatic chain, preferably phenyl, tolyl.
R4Aliphatic or aromatic chains bound for various diisocyanate groups, preferably C6H12。
X is aliphatic, unbranched or branched C1～C10Radicals, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; or is CH2CH2OCH2CH2The polyether segment of (1).
n is an integer of 1 to 30, preferably 3 to 11.
If the molecular structural formula after the mixing reaction is as follows:
the following chemical reactions occur during the mixing reaction:
if the molecular structural formula after the mixed reaction process is as follows:
the following chemical reactions occur during the mixing reaction:
according to the above R1When R is selected1In the case of an amino-reactive group, the graft-modified polyether chain is grafted to the polyisocyanate by reacting the amino group with the isocyanate, so that monofunctional polyethers such as polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, etc. can be used as follows:
when R is1In the case of epoxy groups, it is possible to use the reaction of epoxy groups with isocyanatesThe modified polyether is grafted to polyisocyanate under the condition of generating oxazolidone, and can be used for a high-temperature-resistant curing agent, and the reaction is as follows:
in the present invention, the polyoxyethylene polyether used for preparing the modified polyoxyethylene polyether may be propylene oxide having an average molecular weight of 100 to 5000, or a homopolymer or copolymer of ethylene oxide containing 4 to 20, preferably 8 to 11 polyoxyethylene units, such as polyethylene glycol, polypropylene glycol and other dihydroxy functional polyethers having a molecular weight of 500,600, 700. It is also possible to use polyethylene oxides starting from alkoxy units, such as mono-hydroxy-functional polyethers, for example polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, etc. Polyethers which are synthesized with, for example, trihydroxypropane or other trihydroxy-and polyhydroxyl-functional compounds and which have a hydroxyl functionality of greater than 2 can also be used.
The organosiloxanes according to the invention may be alkoxysilanes of the silicon-functional silanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, ethyl orthosilicate, trimethylmethoxysilane, trimethoxyethylsilane, dimethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane. It may also be an amino-or epoxyhydrocarbyl silane of the class of carbon-functional organosilanes, in particular H2NCH2CH2CH2Si(OMe)3，H2NCH2CH2CH2Si(OEt)3，PhHNCH2Si(OMe)3，H2NC2H4HNC3H6Si(OMe)3，EoCH2OC3H6Si(OMe)3，EoCH2OC3H6SiMe (OEt) in EoCH2OC3H6Me in SiMe (OEt) is methyl, Et is ethyl and Eo is epoxy group; such compounds are also commonly referred to in the market as silane coupling agents. In addition, it is also possible to useOne or any mixture of several of the modified polyether is added in the process to synthesize the modified polyether.
After the silicon modified double-crosslinking waterborne polyurethane curing agent is synthesized, the residual methoxyl or ethoxyl can be subjected to hydrolysis reaction with each other in the process of preparing the waterborne paint to remove methanol or ethanol, so that a-Si-O-Si-crosslinking structure is formed, and the double-crosslinking structure is formed together with a urethane bond, so that the hardness of a coating film and the water and chemical resistance are improved. The reaction form is as follows:
the polyisocyanate used in the preparation can be any compound containing an isocyanate (NCO) functionality of 2 or more. The most common are aliphatic and aromatic polyisocyanates having a molecular weight of less than 600, such as Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), dicyclohexylmethane diisocyanate (HMDI), Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hexahydrotolylene diisocyanate (HTDI), and dimers or trimers of the above-mentioned various diisocyanates, such as HDI trimer, TDI trimer, IPDI trimer, MDI trimer, etc. Also, there may be mentioned adducts of various diisocyanates and polyols, such as an adduct of TDI and trimethylolpropane, an adduct of MDI and trimethylolpropane, etc. It is of course also possible to use mixtures of several different polyisocyanates as starting materials.
The present invention also selectively uses the reported catalytic allophanatization reaction, and the document U.S. Pat. No. 6,26414 reports the catalytic allophanatization reaction by zinc compounds. After the polyether is grafted with polyisocyanate, the invention adds a compound catalytic monomer such as zinc isooctanoate, zinc naphthenate or cobalt naphthenate to react with the prepolymer to form an allophanate bond.
The invention can be carried out in a solvent which is inert to isocyanate, hydroxyl, amino, epoxy and alkoxy groups, such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate or ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, toluene, xylene, chlorobenzene, white spirit, acetone, butanone, cyclohexanone, N-methylpyrrolidone and N-methylcaprolactam, or any mixture of the above solvents.
In the present invention, the terminator is a compound which terminates the activity of the energy catalyst, and the selected terminator is benzoyl chloride.
After the polyisocyanate prepolymer is prepared, the known blocking agent can be selectively used for protecting isocyanate groups, so that the curing agent can be used in aqueous two-component or single-component baking paint, and the commonly used blocking agent comprises methyl ethyl ketoxime, phenol, caprolactam, diethyl malonate, ethyl acetoacetate, methyl ethyl ketonic amine, pyrazole, imidazole, sodium bisulfite and the like.
The waterborne polyurethane curing agent can be used in various waterborne coating systems, can be used on various substrates such as metal, glass, wood, stone, ceramic, plastic, concrete and the like, and can also be pre-coated with various conventional primers before coating. After the coating is formed into a film, the film can be dried at room temperature, and can also be baked and cured at the highest temperature of 280 ℃.
Ethyl acetate and propylene glycol methyl ether acetate may be added as solvents as appropriate, and a high boiling point solvent should be selected at a higher temperature. In order to meet the environmental protection requirement, no solvent is added under normal conditions.
The catalyst may be a compound that catalyzes the reaction of hydroxyl groups with isocyanate groups, typically an organotin compound, and is generally not added. Also useful are the organic zinc and organic cobalt compounds which catalyze allophanatization. In the case of adding a catalyst, a terminator such as benzoyl chloride should be added at the end of the reaction to poison the catalyst and avoid affecting the pot life of the curing agent.
The following are some cases of synthesizing modified polyoxyethylene polyethers.
Synthesizing modified polyoxyethylene polyether A:
a500 mL four-necked flask equipped with a stirrer, a thermometer and a fractional condensation was charged with 280g of polyethylene glycol having an average molecular weight of 600 and 64g of methyltrimethoxysilane. The reaction is heated to 120 ℃, and methanol generated in the reaction gradually flows out of the fractional condensation device due to the low boiling point (64.8 ℃). And stopping the reaction when the amount of the collected methanol reaches a theoretical value. The reaction can also be stopped by the weight loss in the reaction process reaching the theoretical value. Cooling and discharging for later use to form the modified polyoxyethylene polyether A.
Synthesizing modified polyoxyethylene polyether B:
a500 mL four-necked flask equipped with a stirrer, a thermometer and a fractional condensation was charged with 280g of polyethylene glycol having an average molecular weight of 600 and 81g of triethylmethoxysilane. Heating to 130-135 ℃, preferably 132 ℃, wherein the ethanol generated in the reaction gradually flows out of the fractional condensation device due to low boiling point (78.4 ℃). And stopping the reaction when the amount of the collected ethanol reaches a theoretical value. The reaction can also be stopped by the value after the weight loss in the reaction process reaches the theoretical value. Cooling and discharging for later use to form the modified polyoxyethylene polyether B.
Synthesizing modified polyoxyethylene polyether C:
a500 mL four-necked flask equipped with a stirrer, a thermometer and a fractional condensation was charged with 280g of methoxypolyethylene glycol having an average molecular weight of 700 and 88.4g of aminopropyltriethoxysilane. Heating to 140-150 ℃, preferably 145 ℃, and gradually flowing out low-boiling point ethanol generated in the reaction from a fractionation condensing device in the process. And stopping the reaction when the amount of the collected ethanol reaches a theoretical value. The reaction can also be stopped by the weight loss in the reaction process reaching the theoretical value. Cooling and discharging for later use to obtain the modified polyoxyethylene polyether C.
Polyisocyanate prepolymer a: TDI/TMP adduct Synthesis:
adding 402g of toluene diisocyanate and 217g of ethyl acetate into a 1000mL reaction kettle provided with a stirrer and a thermometer, heating to 50 ℃, adding 99.26g of trimethylolpropane batch by batch, controlling the temperature to be stable at 70 ℃ after the addition, reacting for 2.5 hours, cooling, discharging and reserving for later use.
Example 1
300g of HDI trimer is added into a 500mL four-mouth bottle provided with a stirrer, a thermometer and a constant pressure dropping funnel, 45g of modified polyoxyethylene polyether A is gradually dripped into the four-mouth bottle, the dripping is completed half an hour, the temperature is kept for 100-110 ℃ in the process, the total reaction time is 2.5 hours, and the temperature reduction and discharging are completed.
Wherein,
NCO content: 16.13 percent
Solid content: 100 percent
Viscosity (23 ℃): 3200 mPas.
Example 2
300g of HDI trimer and 51g of modified polyoxyethylene polyether B are added into a 500mL reaction kettle provided with a stirrer and a thermometer, the temperature is raised to 100-110 ℃, and the temperature is reduced and the discharging is finished after the reaction is carried out for 2.5 hours.
Wherein,
NCO content: 15.79 percent
Solid content: 100 percent
Viscosity (23 ℃): 3700 mPas.
Example 3
300g of HDI trimer is added into a 500mL four-mouth bottle provided with a stirrer, a thermometer and a constant pressure dropping funnel, 39g of modified polyoxyethylene polyether C is gradually dripped into the four-mouth bottle, the dripping is completed half an hour, the temperature is kept for 100-110 ℃, the total reaction time is 2.5 hours, and the temperature reduction and discharging are completed.
Wherein,
NCO content: 16.72 percent
Solid content: 100 percent
Viscosity (23 ℃): 3100 mPas.
Example 4
Adding 300g of HDI trimer into a 500mL four-mouth bottle provided with a stirrer, a thermometer and a constant-pressure dropping funnel, gradually dropwise adding 45g of modified polyoxyethylene polyether A into the four-mouth bottle, keeping the temperature of 100-110 ℃ in the process after the dropwise adding is completed for half an hour, adding 1 drop of zinc isooctanoate after the total reaction time is 2 hours, continuing to react for 45 minutes, adding benzoyl chloride to terminate the reaction, cooling and discharging.
Wherein,
NCO content: 15.89 percent
Solid content: 100 percent
Viscosity (23 ℃): 7300 mPas.
Example 5
Adding 300g of HDI tripolymer and 45g of modified polyoxyethylene polyether C into a 500mL reaction kettle provided with a stirrer and a thermometer, heating to 100 ℃, keeping the temperature at 100-110 ℃ in the reaction process, adding 1 drop of zinc naphthenate after reacting for 2 hours, adding benzoyl chloride after continuing to react for 45 minutes, cooling and discharging.
Wherein,
NCO content: 16.02 percent
Solid content: 100 percent
Viscosity (23 ℃): 6800 mPas.
Example 6
300g of polyisocyanate A and 21g of propylene glycol methyl ether acetate are added into a 500mL four-mouth bottle provided with a stirrer, a thermometer and a constant pressure dropping funnel, 51g of modified polyether C is gradually dripped into the four-mouth bottle, the dripping is completed for half an hour, the temperature is kept for 70 ℃ in the process, and the temperature is reduced after the total reaction time is 2 hours and the material is discharged.
Wherein,
NCO content: 6.94 percent
Solid content: 70 percent of
Viscosity (23 ℃): 4700 mPas.
Example 7
The embodiment is a waterborne polyurethane curing agent which is not modified by silicon, and the preparation method comprises the following steps:
300g of HDI trimer is added into a 500mL four-mouth bottle provided with a stirrer, a thermometer and a constant pressure dropping funnel, 45g of polyethylene glycol is gradually dripped into the four-mouth bottle, the dripping is completed half an hour, the temperature is kept at 100-110 ℃ in the process, the total reaction time is 2.5 hours, and the cooling and discharging are finished. Wherein,
NCO content: 15.28 percent
Solid content: 100 percent
Viscosity (23 ℃): 4100 mPas.
Example 8
This example is the application of a silicon-modified double-crosslinking aqueous polyurethane curing agent.
120g of aqueous resin varnish prepared from Bayer 2470 resin was weighed and divided into six groups of 20g each. 5g of each of the synthesized silicon modified waterborne polyurethane curing agents 1, 2, 3, 4, 5, 6 and 7 is weighed and mixed with resin varnish, and 5g of water is quantitatively added into each group. Stirring by hand, filtering, drawing film on a 5 × 12cm tin plate with a 100-mesh wire rod, and recording the film drawing time, surface drying time and shelf life. After being dried for two weeks at room temperature, the paint film performance is tested by various national standards, including: adhesion GB/T1720-79; pencil hardness GB/T6739; impact resistance GB/T1732-93; the gloss of the coating film was also measured with a gloss tester (60 ℃).
The test data are as follows:
the tests show that the paint film prepared by the curing agent has higher performances in hardness, adhesive force, flexibility and water resistance. Compared with a paint film prepared by a curing agent which is not modified by silicon, the paint film has improved hardness, luster and water resistance.
Claims (10)
1. The silicon modified double-crosslinking waterborne polyurethane curing agent is characterized by comprising the following components in percentage by weight: the aqueous polyisocyanate dispersion is synthesized by mixing and reacting aromatic or aliphatic polyisocyanate, polyoxyethylene polyether, organic siloxane, a catalyst, a terminator and a solvent, and has a molecular structure as follows:
In the above-mentioned molecular structure, the polymer,
r is aliphatic, unbranched or branched C1～C10A group;
R1a reactive group that is amino, epoxy, or carboxyl;
R2and R3Is H, CH3，CH2CH3，CH2CH2CH3Or C4H9Or is OCH or3，OCH2CH3，OCH2CH2CH3Or OC4H9Or an aromatic chain;
R4an aliphatic or aromatic chain linked to various diisocyanate groups;
x is aliphatic, unbranched or branched C1～C10A group; or is CH2CH2OCH2CH2The polyether segment of (a);
n is an integer of 1 to 30.
2. The silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 1, wherein: r is H or CH3，CH2CH3，CH2CH2CH3Or C4H9(ii) a The aromatic chain is phenyl or tolyl; said R4Selecting C6H12(ii) a Aliphatic, unbranched or branched C of the above X1～C10The radical is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
3. The silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 1, wherein: the aqueous polyisocyanate dispersion is prepared by mixing the following components in percentage by weight:
4. the silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 1 or 3, wherein: the polyoxyethylene polyether is homopolymer or copolymer of propylene oxide and ethylene oxide with average molecular weight of 100-5000, and comprises 4-20 polyoxyethylene units; polyethylene oxide polyethers or polyethylene oxides started with alkoxy units; polyethylene oxide polyethers are also used which are synthesized from compounds such as trimethylolpropane or other trihydroxy and polyhydroxyl functional compounds, and which have a hydroxyl functionality of greater than 2.
5. The silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 1 or 3, wherein: the organosiloxane is alkoxy silane of silicon functional silane; or aminohydrocarbylsilanes and epoxyhydrocarbylsilanes which are carbon functional organosilanes.
6. The silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 1 or 3, wherein: the polyisocyanate is prepared by any compound containing an isocyanate (NCO) functionality of 2 or more; or adducts of various diisocyanates and polyols; or a mixture of several different polyisocyanates can be selected as the starting material.
7. The silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 1 or 3, wherein: the catalysts used are zinc isooctanoate and zinc naphthenate; the terminator is a compound capable of terminating the activity of the catalyst, and the selected terminator is benzoyl chloride.
8. A preparation method of a silicon modified double-crosslinking waterborne polyurethane curing agent comprises the following steps: firstly, adding 1 to percent by weight of polyoxyethylene polyether and 0.01 to 20 percent by weight of organosiloxane into a reaction kettle provided with a stirrer, a thermometer and fractional condensation, reacting at 80 to 220 ℃, stopping the reaction when weight loss or collected effluent reaches a theoretical value, and cooling to form modified polyoxyethylene polyether;
adding 50-95 wt% of aromatic or aliphatic polyisocyanate and 1.01-55 wt% of the modified polyoxyethylene polyether into another reaction kettle provided with a stirrer, a thermometer and a constant-pressure dropping device, and reacting for 2.5-3 hours at 100-110 ℃; during the reaction, 0-0.1 wt% of catalyst and 0-48 wt% of solvent are added, and 0-0.1 wt% of terminator is added to terminate the reaction;
after the reaction, an aqueous polyisocyanate dispersion is finally obtained, the molecular structure of which is:
In the above-mentioned molecular structure, the polymer,
r is aliphatic, unbranched or branched C1～C10A group;
R1a reactive group that is amino, epoxy, or carboxyl;
R2and R3Is H, CH3，CH2CH3，CH2CH2CH3Or C4H9Or is OCH or3，OCH2CH3，OCH2CH2CH3Or OC4H9Or an aromatic chain;
R4an aliphatic or aromatic chain linked to various diisocyanate groups;
x is aliphatic, unbranchedOr branched C1～C10A group; or is CH2CH2OCH2CH2The polyether segment of (a);
n is an integer of 1 to 30.
9. The method for preparing the silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 8, wherein the method comprises the following steps: in the above preparation method, the following chemical reactions occur:
10. the method for preparing the silicon-modified double-crosslinking aqueous polyurethane curing agent according to claim 8, wherein the method comprises the following steps: in the above preparation method, the following chemical reactions occur:
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