CN100406487C - 芳族聚氨酯多元醇 - Google Patents
芳族聚氨酯多元醇 Download PDFInfo
- Publication number
- CN100406487C CN100406487C CNB018096778A CN01809677A CN100406487C CN 100406487 C CN100406487 C CN 100406487C CN B018096778 A CNB018096778 A CN B018096778A CN 01809677 A CN01809677 A CN 01809677A CN 100406487 C CN100406487 C CN 100406487C
- Authority
- CN
- China
- Prior art keywords
- base composition
- paint base
- diisocyanate
- glycol
- polyurethane polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229920005862 polyol Polymers 0.000 title claims abstract description 56
- 150000003077 polyols Chemical class 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 125000003118 aryl group Chemical group 0.000 title abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 150000002009 diols Chemical class 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- -1 diols Diols Chemical class 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 239000003973 paint Substances 0.000 claims description 13
- 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 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 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 7
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims description 2
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 claims description 2
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims 1
- 229920000178 Acrylic resin Polymers 0.000 claims 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims 1
- 235000019437 butane-1,3-diol Nutrition 0.000 claims 1
- 229960005082 etohexadiol Drugs 0.000 claims 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 claims 1
- 230000009257 reactivity Effects 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000008199 coating composition Substances 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000004848 polyfunctional curative Substances 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000007655 standard test method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- 235000012241 calcium silicate Nutrition 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000007654 immersion Methods 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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Polymers C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- 229940031723 1,2-octanediol Drugs 0.000 description 1
- 150000000185 1,3-diols Chemical class 0.000 description 1
- 150000000190 1,4-diols Chemical class 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 239000005083 Zinc sulfide Substances 0.000 description 1
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- 239000004178 amaranth Substances 0.000 description 1
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
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- XMYLSWOTJKUSHE-UHFFFAOYSA-N cyanamide;lead Chemical compound [Pb].NC#N XMYLSWOTJKUSHE-UHFFFAOYSA-N 0.000 description 1
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明涉及适合在涂料组合物中，尤其在用于金属底材的底漆中使用的芳族聚氨酯多元醇，其包含(A)至少一种选自α，β二醇、α，γ二醇及其混合物中的二醇，(B)至少一种三异氰酸酯以及(C)至少一种二异氰酸酯的反应产物，其中至少一种异氰酸酯是芳族异氰酸酯，并且聚氨酯多元醇的分子量(Mn)低于约3000。本发明还涉及用该涂料组合物涂覆底材的方法。
Description
发明背景
本发明涉及在涂料组合物中使用且尤其是在用于金属底材的底漆中使用的芳族聚氨酯多元醇。更具体地讲，本发明涉及包含二异氰酸酯、三异氰酸酯和二醇的反应产物的芳族聚氨酯多元醇，其中至少一种异氰酸酯是芳族异氰酸酯。得到的芳族聚氨酯多元醇是低分子量低聚物(数均分子量(Mn)一般＜3000)，其被设计成涂料组合物的一部分，当该涂料组合物固化时制得具有良好机械和化学性能的涂层。
这些芳族聚氨酯多元醇由特定种类的二醇(α，β和/或α，γ)制备，以提供选择性，并生产具有低分子量和较低粘度的聚氨酯多元醇。
应该注意的是本文所使用的术语“聚氨酯多元醇”指其中反应物(二醇成分和多异氰酸酯成分)基本上只通过氨基甲酸酯键连接的反应产物。这与聚酯-氨基甲酸酯和氨基甲酸酯改性的丙烯酸系多元醇不同，后两者的反应物通过氨基甲酸酯键和酯键连接。
目前，机动车和汽车修补工业正越来越多地使用含有底漆、底色漆和透明涂层的涂料体系。在这些体系中，一般将着色涂层涂装在合适的底漆上，然后将无色罩光清漆涂装在有色的底色漆上从而完成涂料体系。某些情况下可使用有色的单层涂料。这些涂料组合物一般以“单组分”或“双组分”体系提供。在典型的单组分体系中，将所有的涂料组分合并成一个储存稳定的混合物。使用时多元醇组分一般用氨基塑料树脂(如三聚氰胺树脂)或封闭异氰酸酯在120℃或更高温度的热固化条件下交联。在典型的双组分体系中，多元醇组分与交联剂(一般为异氰酸酯)在涂装前不久合并，固化在室温或至多80℃的高温下进行。
对于典型的高固体分涂料体系，为了达到可接受的溶液粘度(20-30s，#4福特杯，约25℃)，必要的是成膜聚合物的重均分子量(Mw)低于约5000。为了使这些体系交联后获得良好的漆膜性能，亦必要的是聚合物的数均分子量(Mn)应该超过约800，并且每种聚合物应该含有至少两个反应性的羟基官能团。这些基本规则适用于聚酯多元醇、丙烯酸类多元醇以及聚氨酯多元醇。在底漆体系中，要求具有下列性能：良好的附着力、耐腐蚀性和硬度。使用聚氨酯多元醇(脂族)一般成本过高，因此很少用在底漆体系中。整个涂料体系的耐久性主要由面漆提供。这就是为什么常使用环氧树脂底漆的缘故。
然而，环氧树脂通常具有高分子量，从而具有高粘度。正如从上面的讨论可明显地看到：对于可接受的溶液粘度以及良好的漆膜性能的要求导致相互矛盾的分子量要求，因为在低溶液粘度下分子量应该低，但对于良好漆膜性能，分子量应该高。
目前使用的许多高性能、高固体分机动车和汽车修补涂料是以包含环氧树脂(广泛使用于底漆体系)或聚酯基或聚丙烯酸基多元醇的聚合物体系为基础。在本发明中，我们提供了优于丙烯酸系树脂和聚酯的化学和物理性能，如优异的附着力、改善的硬度和优异的耐溶剂性。我们提供了优于高分子量环氧树脂的VOC。
有关含有聚氨酯多元醇的涂料人们已经作了大量的工作。制备聚氨酯多元醇的一种方法是将二异氰酸酯或多官能团的异氰酸酯与化学计量大大过量的二元醇反应。反应完成后，优选通过蒸馏除去过量的二元醇。这种制备低分子量聚氨酯多元醇的方法的明显缺点在于二元醇的蒸馏不方便、不实用并且成本高。描述利用化学计量过量的二元醇来制备聚氨酯多元醇的美国专利包括：于1985年9月24日授予Ambrose等人的美国专利4,543,405和于1981年9月8日授予McShane，Jr.的美国专利4,288,577。
美国专利5,155,201公开了包含n-官能团多异氰酸酯(n＝2-5)与羟基被3个或少于3个碳原子隔开的实质上为单体的二元醇的反应产物的聚氨酯多元醇，该专利引入本文供参考。
美国专利5,175,227公开了包含聚氨酯多元醇和羟基反应性交联剂的耐酸蚀的涂料组合物。该聚氨酯多元醇包含羟基被3个或少于3个碳原子隔开的实质上为单体的不对称二元醇与n-官能团多异氰酸酯(n＝2-5)的反应产物。该专利引入本文供参考。
另外，美国专利5,130,405公开了包含(1)由对称1，3-二醇成分和多异氰酸酯制备的聚氨酯多元醇和(2)羟基反应性交联剂的耐酸蚀涂料，该专利引入本文供参考。
WO 96/40813公开了由n-官能团异氰酸酯与至少一种二元醇或三元醇或其混合物和一种含有异氰酸酯反应性官能团的化合物(优选单官能团的醇或硫醇)制备的聚氨酯多元醇成膜组合物，以及制备这些聚氨酯多元醇的方法。WO 96/40813引入本文供参考。
在大量上述专利中，聚氨酯多元醇由α，β和/或α，γ二醇和多异氰酸酯制备。然而，已经确定的是：仅由α，β和/或α，γ二醇和芳族三异氰酸酯制备的聚氨酯多元醇具有极高的粘度，不能用在低VOC涂料组合物中，因为高粘度会导致高VOC。
因此，有利的是提供经济的适合用在高固体分涂料中的多元醇，该多元醇不仅具有理想的性能范围，而且制备还相当方便。现已发现由α，β和/或α，γ二醇和三异氰酸酯与二异氰酸酯的共混物(其中至少一种异氰酸酯是芳族异氰酸酯)制备的聚氨酯多元醇没有上述缺点。
由这些聚氨酯多元醇制备的底漆表现出增强的性能。它们与涂料工业中常用的底漆相比，意想不到地表现出快速室温固化、改进了的硬度、优异的耐溶剂性和优异的与底材、甚至与金属底材的附着力。
发明概述
根据本发明，提供了一种适合用在高固体分涂料组合物中的特别有利的芳族聚氨酯多元醇，其在总体概念上为包含下列成分的反应产物的聚氨酯多元醇：
(A)至少一种选自α，β二醇、α，γ二醇及其混合物的二醇成分，
(B)至少一种三异氰酸酯以及
(C)至少一种二异氰酸酯，
其中至少一种异氰酸酯是芳族异氰酸酯，并且聚氨酯多元醇的分子量(Mn)低于约3000。
发明详述
本发明的芳族聚氨酯多元醇组合物可利用芳族或脂族二异氰酸酯来合成。这些二异氰酸酯的实例包括但不限于甲苯二异氰酸酯(TDI)(可从例如Bayer以MONDUR TD或MONDUR TDS得到)、1，6-六亚甲基二异氰酸酯(HDI)(可从例如Bayer以DESMODUR H得到)、异佛尔酮二异氰酸酯(IPDI)(可从例如Creanova得到)、四甲基亚二甲苯基二异氰酸酯(TMXDI)(可从例如Cytek得到)、2，2，4-三甲基-1，6-六亚甲基二异氰酸酯(可从Creanova得到)、二苯甲烷二异氰酸酯(可从例如Bayer以MONDUR M或MONDUR ML得到)、亚甲基(二(4-环己基异氰酸酯))(可从例如Bayer以Desmodur W得到)以及这些二异氰酸酯的缩二脲和缩脲二酮(uretdione)。
可用于本发明的芳族聚氨酯多元醇的三异氰酸酯包括芳族和脂族三异氰酸酯。这些三异氰酸酯的实例包括但不限于TDI的三聚异氰酸酯(可从例如Bayer以Desmodur IL得到)、三羟甲基丙烷(TMP)和TDI的加合物(可从例如Bayer以Desmodur CB-72得到)、HDI的三聚异氰酸酯(可从例如Bayer以Desmodur N-3300得到)以及IPDI的三聚异氰酸酯(可从例如Bayer以Desmodur Z4470S得到)。
能用于本发明的芳族聚氨酯多元醇中的α，β和/或α，γ二醇的实例包括但不限于2-丁基-2-乙基-1，3-丙二醇(BEPD)(可从例如NESTEChemicals得到)、2-乙基-1，3-己二醇(EHDO)(可从例如Dixie Chemicals得到)、1，2-丙二醇(可从例如Eastman Chemicals得到)、1，3-丁二醇(可从例如Aldrich得到)、2，2，4-三甲基-1，3戊二醇(可从例如Neste Corporation得到)、1，2-己二醇(可从例如Aldrich得到)、1，2-辛二醇(可从例如Aldrich得到)、1，2-癸二醇(可从例如Aldrich得到)以及2，2-二甲基-1，3-丙二醇(从Eastman Chemicals以NPG得到)。
优选的二醇包括含有2-18个碳原子并更优选含有2-10个碳原子的二醇。
另外，如下面实施例所示，使用α，β二醇和/或α，γ二醇在较高固含量时提供的粘度比其它二醇如1，4-二醇、1，5-二醇或1，6-二醇要低。它们(α，β二醇和/或α，γ二醇)具有较低的分子量值，尤其是Mw，从而提供较低的多分散值。
本发明更优选的芳族聚氨酯-多元醇的数均分子量(Mn)为约800-约2000，重均分子量(Mw)与数均分子量的比例(即分散度)为约1.1-约2，OH值为约165-约240mg KOH/g。
本发明的组分可任选地在聚氨酯催化剂存在下反应。适合的聚氨酯催化剂是传统催化剂并可以传统量使用。特定催化剂的选择根据多种因素如所用特定成分和反应条件来确定。这些以及其它因素对于本领域熟练的技术人员而言是公知的，他们能作出相应的适当选择。一些优选的催化剂包括含有锡和叔胺的化合物，如有机金属锡化合物和烷基叔胺。
可使用的各种交联剂包括但不限于异氰酸酯、封闭异氰酸酯和/或三聚氰胺和/或其它对聚氨酯多元醇的羟基具有反应性的交联剂。
本发明的涂料组合物还可包括约1-约50重量％的树脂(基料)如丙烯酸系树脂、聚酯、醇酸树脂、酚醛塑料、环氧树脂、聚醚、聚氨酯和它们的混合物。此处描述的涂料组合物可用于底漆、底色漆、面漆和透明清漆，但优选用作底漆。
本发明的涂料组合物中可任选存在颜料。有用的颜料是本领域常用的各类颜料，其包括但不限于二氧化钛、石墨、碳黑、氧化锌、硫化钙、氧化铬、硫化锌、铬酸锌、铬酸锶、铬酸钡、铬酸铅、氰胺化铅、硅铬酸铅、钛镍黄、钛铬黄、氧化铁红、氧化铁黄、氧化铁黑、萘酚红和棕、蒽醌、二噁嗪紫(dioxa zinc violet)、二氢异吲哚黄、芳基黄和橙、群青色、酞菁复合物、苋菜红、喹吖啶酮、卤代硫靛颜料、体质颜料如硅酸镁、硅酸铝、硅酸钙、碳酸钙、热解法二氧化硅、硫酸钡和磷酸锌。
本发明的涂料组合物也可包含其他成分如溶剂、催化剂、稳定剂、填料、流变调节剂、流动添加剂、流平添加剂、分散剂以及其它对本领域熟练技术人员而言公知的成分。
本发明还涉及含有本发明的芳族聚氨酯多元醇和交联剂的涂料组合物。
本发明的芳族聚氨酯多元醇的涂料组合物可通过众多传统施用方法中的任何一种用于任何公知的底材。一种优选的底材是金属。该组合物在修补工业中，尤其是在车身修理厂(修补汽车和运输工具)以及在涂装大型运输工具如火车、卡车、公共汽车和飞机中特别适合。尽管上述双组分体系的固化优选在室温条件下，一般在室温到约60℃下进行，但本发明涂料的固化可在各种对于本领域熟练技术人员而言公知的条件下进行。
该组合物在修补工业中，尤其是在车身修理厂中(修理汽车和运输工具)以及在涂装大型运输工具如火车、卡车、公共汽车和飞机中特别适合。本发明优选的应用是用作汽车修补底漆。通过下列具体但非限定性实施例将进一步阐述本发明的上述总体论述。
方法
在下列实施例中，Brookfied粘度(布氏粘度)在25℃下使用#4锭和20RPM的转速测定。成膜试验按ASTM D 1640-95，室温下有机涂料的干燥、固化或成膜的标准试验方法进行。附着力和硬度在浸水24小时后按ASTM D 870-92，用浸水试验测试涂料的耐水性的标准测试方法测试。附着力按ASTM D 3359-95，用胶带试验测定附着力的标准测试方法测试。硬度按ASTM D 4366-95，通过摆杆阻尼试验测定有机涂料硬度的标准测试方法，B-Persoz摆杆硬度测试方法测试。
实施例
芳族聚氨酯多元醇的合成
实施例1
在一个装有搅拌器、冷凝器、加热套、带温度显示的热电偶、氮气和加料入口的5升三口圆底烧瓶中充入下列组分：233.1g 2-庚酮、1057.7g2-丁基-2-乙基-1，3-丙二醇以及2.2g二月桂酸二丁基锡(10％的乙酸丁酯溶液)。将混合物在氮气保护下加热到70℃。
当温度达到并稳定在70℃时，将下列混合物在180分钟内表外(supersurface)加入烧瓶中：600.0g的2-庚酮、1082.4g的DesmodurCB-72[甲苯二异氰酸酯(TDI)与三羟甲基丙烷(TMP)的三官能团异氰酸酯加合物(72％NV时的当量＝328g/当量)]、293.24g的2，4-甲苯二异氰酸酯(96％NV时的当量＝90.71g/当量)。在加入该混合物的过程中，反应温度保持在70℃左右。混合物加入完毕之后，反应温度在70℃再保持2个小时，此时通过富立叶变换红外光谱(FTIR)确定没有残余异氰酸酯存在。
得到的芳族聚氨酯多元醇溶液中非挥发成分含量为65.4％，布氏粘度为3680cps(25℃，#4锭，转速20RPM)，羟基数为174.0(mg KOH/g)。
聚合物的分子量用Waters’Associates的凝胶渗透色谱仪(GPC)和Phenomenex聚苯乙烯标准物测定。聚氨酯多元醇的Mn为1109，Mw为1594，分散度D为1.43。
实施例2-9
实施例2-9的聚氨酯多元醇以与实施例1中的聚氨酯多元醇相似的方式由下表1列出的组分来制备。
表1
＊Desmodur N-3300：以六亚甲基二异氰酸酯(HDI)为基础的三官能异氰酸酯(100％NV时的当量＝194g/当量)。
＊IPDI：异佛尔酮二异氰酸酯(100％NV时的当量＝111.1g/当量)。
实施例2-9得到的聚氨酯多元醇的性能列在下表2中。该表也比较了由α，β二醇或α，γ二醇与由其它类型的二醇制备的芳族聚氨酯多元醇的表征结果。
表2
性能实施例
下述底漆配方实施例按下列重量百分比配制：芳族聚氨酯多元醇2.2％、聚酯改性的丙烯酸系树脂20.5％、分散剂0.7％、防沉降剂1.1％、常用溶剂15.5％、碳酸钙21％、滑石8.5％、磷酸锌10％、TiO2 20％以及触变剂0.5％。
实施例10
原始底漆以由市购聚酯改性的丙烯酸系树脂(可从Akzo Nobel ResinsInc.得到的Setalux 2152)/聚酯的90/10共混物组成的基料体系为基础。该底漆组合物还含有两种催化剂。(含量分别为0.9重量％和0.3重量％的三亚乙基二胺的10％异丙醇溶液和石油溶剂油中的18％锆)。为了评价芳族聚氨酯多元醇，用实施例1中的芳族聚氨酯多元醇替换共混物中的聚酯。体系中不另加催化剂(二月桂酸二丁基锡是与硬化剂1一起加入的催化剂)。完全配制好的漆分别用两种不同的硬化剂活化；硬化剂1含有以40重量％固含量存在于乙酸丁酯中的以六亚甲基二异氰酸酯(HDI)为基础的多异氰酸酯(缩二脲)和0.005重量％的二月桂酸二丁基锡的10％酯/芳族混合溶剂溶液；硬化剂2含有HDI基/IPDI基多异氰酸酯(三聚异氰酸酯)的60/40共混物，其固含量为69重量％，NCO∶OH比为1.05。将每个试样用以酮为基础的混合溶剂稀释得到4.79lbs/gal(575g/l)的即喷VOC。
表3
干燥时间/适用期
实施例11
用芳族聚氨酯多元醇实施例2(1.0当量BEPD/0.25当量DesmodurCB-72N/0.25当量IPDI)和实施例1(1.0当量BEPD/0.25当量DesmodurCB-72N/0.25当量TDI)按a％固体(如上述的10％)代替原始底漆配方中的聚酯。未打磨底漆用硬化剂1以105％交联，然后用酮溶剂共混物稀释至VOC为4.65lbs/gal(558g/l)。打磨底漆用硬化剂3(它是两种以不含溶剂的脂族HDI为基础的多异氰酸酯共混物)以105％交联，并用传统溶剂共混物稀释至固含量为42重量％，然后用以酮溶剂为基础的稀释剂稀释至VOC为4.2lbs/gal(504g/l)。以底色漆/透明涂层配方对板涂面漆，然后在60℃下热老化4小时。
每个体系的附着力和硬度在已用专有的市购磷化底漆(Akzo NobelCoatings Inc.的磷化底漆EMCF)处理的冷轧钢板(CRS)上以简单的室温浸水试验评估。
表4
浸水
实施例12
将含有实施例2和实施例1的芳族聚氨酯多元醇的两个配方代替原始底漆配方中的聚酯(如上述的10％)来评价。另外，第一个配方含有Wollastocoat 10ES，第二个配方含有Wollastocoat 10AS。未打磨施用以100体积份漆/50体积份硬化剂1和30体积份酮溶剂的共混物活化。打磨施用以3体积份漆/1体积份硬化剂3+10体积％酮溶剂的共混物活化。
冷轧钢板用市购磷化底漆(Akzo Nobel Coatings Inc.的磷化底漆EMCF)处理，然后用底色漆/透明涂层涂面漆。将板在60℃下热老化4小时。
表5
浸水
Wallastocoat ES：环氧硅烷处理的偏硅酸钙。
Wollastocoat AS：氨基硅烷处理的偏硅酸钙。
结论
上面只是描述了本发明有限的几个优选实施方案。然而本领域熟练技术人员会认识到在不背离下列权利要求限定的本发明精神和范围下所作的大量代替、改进和改变。
Claims (10)
1.一种底漆组合物，含有包含下列成分的反应产物的聚氨酯多元醇：
(a)至少一种选自α，β二醇、α，γ二醇及其混合物中的二醇成分，
(b)至少一种三异氰酸酯以及
(c)至少一种二异氰酸酯，
其中至少一种异氰酸酯是芳族异氰酸酯，三异氰酸酯选自甲苯二异氰酸酯的三聚异氰酸酯、三羟甲基丙烷和甲苯二异氰酸酯的加合物、六亚甲基二异氰酸酯的三聚异氰酸酯和异佛尔酮二异氰酸酯的三聚异氰酸酯，并且聚氨酯多元醇的分子量Mn为800-3000，以及交联剂。
2.如权利要求1所述的底漆组合物，其中α，β二醇和/或α，γ二醇选自2-丁基-2-乙基-1，3-丙二醇、2-乙基-1，3-己二醇、1，2-丙二醇、1，3-丁二醇、2，2，4-三甲基-1，3-戊二醇、1，2-己二醇、1，2-辛二醇、1，2-癸二醇以及2，2-二甲基-1，3-丙二醇。
3.如权利要求1所述的底漆组合物，其中二异氰酸酯选自甲苯二异氰酸酯、1，6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、四甲基亚二甲苯基二异氰酸酯、2，2，4-三甲基-1，6-六亚甲基二异氰酸酯、二苯甲烷二异氰酸酯、亚甲基(二(4-环己基异氰酸酯))以及这些二异氰酸酯的缩二脲和缩脲二酮。
4.如权利要求1所述的底漆组合物，其中交联剂选自异氰酸酯、封闭异氰酸酯和三聚氰胺。
5.如权利要求1所述的底漆组合物，其中交联剂对聚氨酯多元醇的羟基具有反应性。
6.如权利要求1所述的底漆组合物，还包含树脂。
7.如权利要求6所述的底漆组合物，其中树脂选自丙烯酸系树脂、聚酯、醇酸树脂、酚醛塑料、环氧树脂、聚醚、聚氨酯和它们的混合物。
8.一种涂覆底材的方法，包括将权利要求1所述的底漆组合物施用于底材。
9.一种涂覆底材的方法，包括将权利要求6所述的底漆组合物施用于底材。
10.一种修补汽车的方法，包括施用前述权利要求1-7中任一项所述的底漆组合物。
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| WO2006044653A1 (en) * | 2004-10-14 | 2006-04-27 | Akzo Nobel Coatings International B.V. | Iron carbonyl containing coating composition |
| US20070055026A1 (en) * | 2005-09-07 | 2007-03-08 | Yahkind Alexander L | Melamine polyols and coatings thereof |
| EP1922347B1 (en) * | 2005-09-07 | 2009-03-25 | Akzo Nobel Coatings International BV | Melamine polyols and coatings thereof |
| DE102005058891A1 (de) * | 2005-12-09 | 2007-06-14 | Basf Coatings Ag | Flüssige, thermisch härtbare Gemische, Verfahren zu ihrer Herstellung und ihre Verwendung |
| CN102417787A (zh) * | 2011-10-27 | 2012-04-18 | 铜陵市新泰电容电器有限责任公司 | 一种覆盖电容器铝壳涂料及其制备方法 |
| RU2534773C1 (ru) * | 2013-06-07 | 2014-12-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Казанский национальный исследовательский технологический университет" | Полиуретановая композиция для покрытий |
| CN103740256B (zh) * | 2013-12-30 | 2015-10-28 | 江苏标榜装饰新材料股份有限公司 | 适合uv油墨铝塑复合板打印的聚氨酯涂料及其制备方法 |
| US10179830B2 (en) | 2014-06-13 | 2019-01-15 | Covestro Deutschland Ag | Thioallophanate polyisocyanates containing silane groups |
| AU2016279054B2 (en) * | 2015-06-19 | 2018-11-22 | Prc-Desoto International, Inc. | Flexible non-chromate corrosion inhibitive primer |
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| JP2003533568A (ja) | 2003-11-11 |
| ATE366761T1 (de) | 2007-08-15 |
| CN1437624A (zh) | 2003-08-20 |
| AU2001261642B2 (en) | 2005-07-28 |
| AU6164201A (en) | 2001-11-26 |
| DE60129321D1 (en) | 2007-08-23 |
| ES2288512T3 (es) | 2008-01-16 |
| US20050119439A1 (en) | 2005-06-02 |
| ZA200209272B (en) | 2003-07-18 |
| WO2001088012A2 (en) | 2001-11-22 |
| EP1287054A2 (en) | 2003-03-05 |
| WO2001088012A3 (en) | 2002-03-28 |
| DE60129321T2 (de) | 2008-03-20 |
| RU2278138C2 (ru) | 2006-06-20 |
| BR0110808A (pt) | 2003-12-30 |
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