CN112566957B - 具有改善的干燥性能的离子亲水化多异氰酸酯 - Google Patents
具有改善的干燥性能的离子亲水化多异氰酸酯 Download PDFInfo
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- CN112566957B CN112566957B CN201980039268.7A CN201980039268A CN112566957B CN 112566957 B CN112566957 B CN 112566957B CN 201980039268 A CN201980039268 A CN 201980039268A CN 112566957 B CN112566957 B CN 112566957B
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- Prior art keywords
- polyisocyanate
- sulfonic acid
- mixture according
- weight
- polyisocyanate component
- Prior art date
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- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 236
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 236
- 238000001035 drying Methods 0.000 title description 14
- 239000000203 mixture Substances 0.000 claims abstract description 100
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 59
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000008199 coating composition Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 6
- -1 hydroxy- Chemical class 0.000 claims description 173
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 125000001931 aliphatic group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000004814 polyurethane Substances 0.000 claims description 15
- 150000001298 alcohols Chemical class 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- 230000002209 hydrophobic effect Effects 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- PJWWRFATQTVXHA-UHFFFAOYSA-N Cyclohexylaminopropanesulfonic acid Chemical compound OS(=O)(=O)CCCNC1CCCCC1 PJWWRFATQTVXHA-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 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 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 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 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 5
- MKWKNSIESPFAQN-UHFFFAOYSA-N N-cyclohexyl-2-aminoethanesulfonic acid Chemical compound OS(=O)(=O)CCNC1CCCCC1 MKWKNSIESPFAQN-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- GHSGJYANZVSEPH-UHFFFAOYSA-N 2-(propan-2-ylamino)ethanesulfonic acid Chemical compound CC(C)NCCS(O)(=O)=O GHSGJYANZVSEPH-UHFFFAOYSA-N 0.000 claims description 3
- ZBSWKBYXONRLTM-UHFFFAOYSA-N 3-(propan-2-ylamino)propane-1-sulfonic acid Chemical compound CC(C)NCCCS(O)(=O)=O ZBSWKBYXONRLTM-UHFFFAOYSA-N 0.000 claims description 3
- ZCVOCAWBPMHJPF-UHFFFAOYSA-N 4-(propan-2-ylamino)butane-1-sulfonic acid Chemical compound C(C)(C)NCCCCS(=O)(=O)O ZCVOCAWBPMHJPF-UHFFFAOYSA-N 0.000 claims description 3
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- XNPKNHHFCKSMRV-UHFFFAOYSA-N 4-(cyclohexylamino)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCNC1CCCCC1 XNPKNHHFCKSMRV-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000006384 oligomerization reaction Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 42
- 239000011248 coating agent Substances 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 20
- 239000004971 Cross linker Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 239000010408 film Substances 0.000 description 13
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920002396 Polyurea Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004922 lacquer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- GSVWUPPSQAZZTF-UHFFFAOYSA-N n-ethyl-n-methylhexan-1-amine Chemical compound CCCCCCN(C)CC GSVWUPPSQAZZTF-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 5
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000005829 trimerization reaction Methods 0.000 description 4
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 3
- HLNRRPIYRBBHSQ-UHFFFAOYSA-N 1-propylpyrrolidine Chemical compound CCCN1CCCC1 HLNRRPIYRBBHSQ-UHFFFAOYSA-N 0.000 description 3
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 3
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 239000003960 organic solvent Substances 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
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- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 3
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- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 2
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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Abstract
本发明涉及多异氰酸酯混合物,其包含具有脂族和/或脂环族键合的异氰酸酯基团的多异氰酸酯组分A)和具有芳脂族和/或芳族键合的异氰酸酯基团的多异氰酸酯组分B),其特征在于多异氰酸酯组分A)包含至少0.85重量%的化学键合形式的磺酸根基团(以SO3计算;摩尔量=80 g/mol),并且多异氰酸酯组分B)的比例为组分A)和B)的总量的7至43重量%。本发明还涉及其用途以及包含该多异氰酸酯混合物的涂料组合物和涂布有这些涂料组合物的基底。
Description
本发明涉及多异氰酸酯混合物及其用于生产聚氨酯塑料的用途。本发明还涉及包含至少一种这样的多异氰酸酯混合物的涂料组合物以及涂布有这些涂料组合物的基底。
现在牢固地建立了作为溶剂型涂料组合物的生态友好替代品用于各种应用领域的水性涂料体系。在这种情况下,亲水改性的多异氰酸酯作为在质量上高价值的水性涂料的原材料起到特别的作用,因为作为水分散性交联剂组分,它们使得能够配制水性双组分聚氨酯(2K-PUR)涂料。
水性2K-PUR涂料在机械和化学品耐受性方面显然可与溶剂型涂料材料相比,有时甚至更好。它们的主要缺点是它们明显较慢的干燥行为,这阻碍了其在市场中(特别是在木材和家具涂料材料中)的进一步渗透。在溶剂型2K-PUR体系的领域中,常常依赖于芳族或混合的芳族/脂族多异氰酸酯交联剂来加速干燥。在通过使用具有芳族异氰酸酯基团的高反应性多异氰酸酯来缩短水性2K-PUR涂料的干燥时间方面也不乏尝试。
例如,EP-A 0 645 410描述了包含通过与单官能聚环氧乙烷聚醚的反应进行亲水改性的氨基甲酸酯基团的基于2,4-和/或2,6-二异氰酸根合甲苯(甲苯二异氰酸酯,TDI)的多异氰酸酯及其作为水性2K-PUR涂料的交联剂组分的用途。使用这些纯芳族多异氰酸酯配制的水性涂料体系表现出木材和家具涂料所需的快速干燥,但是与常规市售水性基料的相容性不足,这是它们通常仅能产生非常黯淡的清漆膜的原因。此外,该公开文献中描述的多异氰酸酯交联剂包含大量的亲水性聚醚多元醇,这导致了涂层的永久亲水性,同时降低了硬度。
为了改善相容性,EP-A 0 680 983提出在与聚环氧乙烷聚醚醇的反应中使用包含TDI和1,6-二异氰酸根合己烷(六亚甲基二异氰酸酯,HDI)这两者的多异氰酸酯或多异氰酸酯混合物来替代纯芳族TDI多异氰酸酯。但是,这些混合的脂族-芳族非离子亲水化交联剂也不能克服与足够的乳化性所需的高聚醚含量相关联的缺点,这是这些产品也未能在市场上占据主导地位的原因。
CN 105949436的主题是通过使TDI/HDI混合物与聚乙二醇反应、将反应混合物催化三聚化并随后与二羟甲基丙酸和二甲基乙醇胺反应来制备亲水性HDI/TDI混合多异氰酸酯。以这种方式,获得了具有高异氰酸酯含量的无溶剂、相对低粘度的产物,然而该产物在单体方面并不低,并且由于固有存在的羧酸铵基团的已知催化效应而具有完全不足的储存稳定性。
US 5 652 300描述了更快干燥的水分散性多异氰酸酯,其通过使特定的多异氰酸酯混合物与非离子亲水性表面活性物质(例如甲氧基聚乙二醇)以及任选的附加疏水性NCO反应性脂族化合物或脂肪酸酯衍生物反应来制备,所述多异氰酸酯混合物由二醇改性的HDI多异氰酸酯和基于1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI)或TDI的聚异氰脲酸酯多异氰酸酯组成。这些产品也表现出由亲水性聚醚醇所导致的永久亲水性的主要缺点,永久亲水性的形式为所获得的涂层仅具有低耐水性和相对较低的硬度。
为了避免这一主要缺点,近年来已经开发了水乳化性多异氰酸酯,其通过并入离子基团(尤其是磺酸根基团)来亲水改性。
根据WO 2001/88006的教导,可以通过使脂族、脂环族、芳族或芳脂族多异氰酸酯与2-(环己基氨基)乙磺酸(CHES)或3-(环己基氨基)丙磺酸(CAPS)反应获得亲水化多异氰酸酯,其作为水性涂料体系中的交联剂,导致产生具有高硬度和优异的溶剂耐受性和化学品耐受性的涂层。这些离子亲水化多异氰酸酯在乳化之前可以任选与其它非亲水性多异氰酸酯混合,其中该混合物的磺酸根改性部分起到乳化剂的作用,即使对于随后混入的疏水性多异氰酸酯也如此。
这同样适用于WO 2015/035673,其描述了在氮上进一步被脂环族取代的氨基丙磺酸、氨基丁磺酸和/或氨基异丁磺酸作为脂族、脂环族、芳族或芳脂族多异氰酸酯的亲水化剂。这些氨基磺酸的使用需要两阶段制备过程,其中,初始仅有一部分量的多异氰酸酯发生反应,随后将其与其它多异氰酸酯混合。
因此,本发明的目的是提供具有芳脂族和/或芳族异氰酸酯基团的新型亲水改性多异氰酸酯,其适合作为许多不同应用中的水性基料的交联剂组分,并且尤其导致与现有技术的已知水乳化性多异氰酸酯相比更快的干燥。该新型多异氰酸酯应具有长的处理时间,尽管其具有高反应性,并应固化以形成具有高机械和化学品耐受性的透明、尽可能无混浊的涂膜。
在提供下文中更详细描述的多异氰酸酯混合物的情况下,令人惊讶地实现了这一目的。
本发明基于以下令人惊讶的观察结果:由具有限定的最小磺酸根基团含量的亲水性HDI 多异氰酸酯和不足量的芳脂族和/或芳族多异氰酸酯组成的多异氰酸酯混合物与常规水性涂料基料组合,得到与使用现有技术的多异氰酸酯制备的那些相比干燥明显更快并且同时就其它涂料性能而言在任何方面都不逊于这些的涂料。特别令人惊讶的是,由于芳脂族和/或芳族异氰酸酯基团对水的已知高反应性,与使用常规市售纯脂族多异氰酸酯交联剂相比,使用本发明的多异氰酸酯混合物可以完全预料不到地实现更高的无气泡层厚度。
本发明提供了多异氰酸酯混合物,其包含具有脂族和/或脂环族键合的异氰酸酯基团的多异氰酸酯组分A)和具有芳脂族和/或芳族键合的异氰酸酯基团的多异氰酸酯组分B),其特征在于多异氰酸酯组分A)包含至少0.85重量%的化学键合形式的磺酸根基团(以SO3计算;摩尔量 = 80 g/mol),并且多异氰酸酯组分B)的比例为组分A)和B)的总量的7至43重量%。
本发明还提供了制备这些亲水性多异氰酸酯混合物的方法及其在聚氨酯塑料的生产中用作起始组分的用途,特别是用作具有对异氰酸酯基团呈反应性的基团的水溶性或水分散性漆基料或漆基料组分的交联剂的用途。
根据本发明的表述“包含”或“含有”优选是指“基本由……组成”,特别优选是指“由……组成”。
用于制备根据本发明的多异氰酸酯混合物的多异氰酸酯组分A)是任何具有脂族和/或脂环族键合的异氰酸酯基团的多异氰酸酯,其包含至少0.85重量%、优选至少0.90重量%、更优选至少0.95重量%、甚至更优选1.00至3.00重量%和最优选1.10至1.80重量%的化学键合形式的磺酸根基团(以SO3计算;摩尔量 = 80 g/mol)。
这类包含磺酸根基团的多异氰酸酯组分A)是已知的。这些优选是至少一种多异氰酸酯C)与至少一种带有至少一个对异氰酸酯基团呈反应性的基团的具有磺酸和/或磺酸根基团的有机化合物D)和任选的非离子亲水性或疏水性化合物E)任选在其它助剂和添加剂F)的存在下的反应产物。
适于制备包含磺酸根基团的多异氰酸酯组分A)的多异氰酸酯C) 是任何具有脂族和/或脂环族键合的异氰酸酯基团的二异氰酸酯和/或多异氰酸酯。
合适的二异氰酸酯C)是可以以各种方式(例如通过在液相或气相中的光气化或通过无光气途径,例如通过氨基甲酸酯热裂解)获得的任何二异氰酸酯。优选的二异氰酸酯是具有脂族或脂环族键合的异氰酸酯基团的分子量为140至400的那些,实例是1,4-二异氰酸根合丁烷、1,5-二异氰酸根合戊烷(五亚甲基二异氰酸酯,PDI)、1,6-二异氰酸根合己烷(六亚甲基二异氰酸酯,HDI)、2-甲基-1,5-二异氰酸根合戊烷、1,5-二异氰酸根合-2,2-二甲基戊烷、2,2,4-或2,4,4-三甲基-1,6-二异氰酸根合己烷、1,10-二异氰酸根合癸烷、1,3-和1,4-二异氰酸根合环己烷、1,3-和1,4-双(异氰酸根合甲基)环己烷、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI)、2,4'-和4,4'-二异氰酸根合二环己基甲烷(H12-MDI)、1-异氰酸根合-1-甲基-4(3)异氰酸根合甲基环己烷、双(异氰酸根合甲基)降冰片烷或至少两种此类二异氰酸酯的混合物。
合适的多异氰酸酯C)是任何具有脲二酮、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多异氰酸酯,其通过简单的脂族和/或脂环族二异氰酸酯的改性来制备,例如上文提及的类型的那些,如例如在J. Prakt. Chem. 336 (1994)185 - 200、DE-A 1 670 666、DE-A 1 954 093、DE-A 2 414 413、DE-A 2 452 532、DE-A 2641 380、DE-A 3 700 209、DE-A 3 900 053和DE-A 3 928 503或EP-A 0 336 205、EP-A 0339 396和EP-A 0 798 299中所描述的,或通过至少两种此类多异氰酸酯的混合物来制备。在制备这些多异氰酸酯的过程中,在实际改性反应之后通常进行去除未反应的过量单体二异氰酸酯的进一步工艺步骤。单体通过本身已知的方法来去除,优选通过高真空下的薄膜蒸馏或通过用对异氰酸酯基团呈惰性的合适溶剂进行萃取,所述溶剂例如为脂族或脂环族烃类,如戊烷、己烷、庚烷、环戊烷或环己烷。
为了制备包含磺酸根基团的多异氰酸酯组分A),优选使用具有小于 1重量%、优选小于 0.5重量%、特别优选小于 0.3重量%的单体二异氰酸酯含量的所提及类型的多异氰酸酯作为起始组分C)。根据DIN EN ISO 10283:2007-11通过使用内标的气相色谱法测量残余单体含量。
用于制备包含磺酸根基团的多异氰酸酯组分A)的特别优选的多异氰酸酯C)是所提及的类型的包含异氰脲酸酯基团的多异氰酸酯。
非常特别优选的是基于PDI、HDI、IPDI和/或4,4'-二异氰酸根合二环己基甲烷的多异氰酸酯C),最优选的是基于PDI和/或HDI的多异氰酸酯C)。
上文提及为合适、优选、特别优选和非常特别优选的多异氰酸酯C)优选具有2.3至5.0、优选2.5至4.5的平均NCO官能度和6.0至26.0重量%、优选8.0至25.0重量%、特别优选10.0至24.0重量%的异氰酸酯基团含量。
用于制备包含磺酸根基团的多异氰酸酯组分A)的起始化合物D)是任何带有至少一个对异氰酸酯基团呈反应性的基团和至少一个磺酸或磺酸根基团的有机化合物。这些是本身已知的羟基-、巯基-或氨基-官能磺酸和/或其盐,或是至少两种此类化合物的混合物。
合适的起始化合物D)例如是通式(I)的羟基磺酸
其中R1是具有最多10个碳原子的烷基或芳基基团,其可以包含酯基、羰基、最多两个叔氨基和/或羟基,或是五元或六元脂环族基团,其可以任选包含氮或氧原子,并且还可以被其它羟基取代。
合适的羟基磺酸的实例包括:2-羟基乙磺酸、3-羟基丙磺酸、4-羟基丁磺酸、5-羟基戊磺酸、6-羟基己磺酸、异构的苯酚磺酸类,尤其是4-羟基苯磺酸、2-(羟甲基)苯磺酸、3,5-双(羟甲基)苯磺酸、4-(2-羟乙基)-1-哌嗪乙磺酸(HEPES)、4-(2-羟乙基)-1-哌嗪丙磺酸(HEPPS)和2-羟基-4-吗啉丙磺酸(MOPSO)。
合适的羟基磺酸还有特定的聚醚磺酸,如在例如EP-A 0 592 073、US 3 102 893和US 2 989 547中描述为去垢剂。
用于制备包含磺酸根基团的多异氰酸酯组分A)的优选的羟基磺酸D)是通式(I)的那些,其中R1是具有最多6个碳原子的烷基或具有6至10个碳原子的芳基。
特别优选的羟基磺酸D)是2-羟基乙磺酸、3-羟基丙磺酸、4-羟基苯磺酸和/或2-(羟甲基)苯磺酸。
合适的起始化合物D)还有巯基磺酸,如2-巯基乙磺酸和3-巯基丙-1-磺酸。
适合作为起始组分D)的氨基官能化合物是例如取代芳族磺酸,其可以带有最多三个磺酸基团并包含最多三个、优选最多两个、特别优选正好一个伯或仲氨基、优选正好一个伯氨基,其中在芳环上在氨基邻位处的位置未被取代。
这些优选是通式(II)的取代芳族磺酸
其中R2、R3和R4各自独立地是相同或不同的基团并且表示氢或饱和或不饱和、直链或支链、脂族、脂环族、芳脂族或芳族有机基团,其可以另外在链中包含杂原子,其中R3和R4也可以彼此组合一起形成环,优选稠合芳环,条件是基团R3和R4中的至少一者不是氢。
式(II)中的脂族或芳脂族基团R2、R3和R4优选是具有1至18个碳原子的那些,例如甲基、乙基、丙基、异丙基、N-丁基、仲丁基、叔丁基、戊基、己基、庚基、辛基、2-乙基己基、2,4,4-三甲基戊基、癸基、十二烷基、十四烷基、十六烷基、十八烷基、1,1-二甲基丙基、1,1-二甲基丁基、1,1,3,3-四甲基丁基、苄基、1-苯基乙基、2-苯基乙基、α,α-二甲基苄基、二苯甲基、对甲苯基甲基、1-(对丁基苯基)乙基、对氯苄基、2,4-二氯苄基、对甲氧基苄基、间乙氧基苄基、2-氰基乙基、2-氰基丙基、2-甲氧基羰基乙基、2-乙氧基羰基乙基、2-丁氧基羰基丙基、1,2-二(甲氧基羰基)乙基、2-甲氧基乙基、2-乙氧基乙基、2-丁氧基乙基、二乙氧基甲基、二乙氧基乙基、1,3-二氧杂环戊烷-2-基、1,3-二氧杂环己烷-2-基、2-甲基-1,3-二氧杂环戊烷-2-基、4-甲基-1,3-二氧杂环戊烷-2-基、2-异丙氧基乙基、2-丁氧基丙基、2-辛氧基乙基、氯甲基、2-氯乙基、三氯甲基、三氟甲基、1,1-二甲基-2-氯乙基、2-甲氧基异丙基、丁基硫基甲基、2-十二烷基硫基乙基、2-苯基硫基乙基、2,2,2-三氟乙基、2-苯氧基乙基、2-苯氧基丙基、3-苯氧基丙基、4-苯氧基丁基、6-苯氧基己基、2-甲氧基乙基、2-甲氧基丙基、3-甲氧基丙基、4-甲氧基丁基、6-甲氧基己基、2-乙氧基丙基、3-乙氧基丙基、4-乙氧基丁基或6-乙氧基己基基团。
式(II)中的脂环族基团R2、R3和R4优选是具有5至12个碳原子的那些,例如环戊基、环己基、环辛基、环十二烷基、甲基环戊基、二甲基环戊基、甲基环己基、二甲基环己基、二乙基环己基、丁基环己基、甲氧基环己基、二甲氧基环己基、二乙氧基环己基、丁基硫基环己基(butylthiocyclohexyl)、氯环己基、二氯环己基、二氯环戊基基团以及饱和或不饱和的双环体系,例如降冰片烷基或降冰片烯基基团。
式(II)中的芳族基团R2、R3和R4优选是具有6至12个碳原子的那些,例如苯基、甲苯基、二甲苯基、邻-萘基、β-萘基、4-联苯基、氯苯基、二氯苯基、三氯苯基、二氟苯基、甲基苯基、二甲基苯基、三甲基苯基、乙基苯基、二乙基苯基、异丙基苯基、叔丁基苯基、十二烷基苯基、甲氧基苯基、二甲氧基苯基、乙氧基苯基、己氧基苯基、甲基萘基、异丙基萘基、氯萘基、乙氧基萘基、2,6-二甲基苯基、2,4,6-三甲基苯基、2,6-二甲氧基苯基、2,6-二氯苯基、4-溴苯基、2-或4-硝基苯基、2,4-或2,6-二硝基苯基、4-二甲基氨基苯基、4-乙酰基苯基、甲氧基乙基苯基或乙氧基甲基苯基基团。
如果式(II)中的基团R3和R4一起形成环,则R3和R4优选是亚丁-1,4-基(butyl-1,4-ylene)链或特别优选1,3-亚丁二烯-1,4-基(1,3-butadien-1,4-ylene)链,这意味着芳族磺酸在这种情况下优选具有四氢化萘或特别优选萘结构。
基团R2特别优选是氢、甲基、乙基、正丙基、异丙基、叔丁基、环戊基或环己基基团,尤其优选是氢。
基团R3和R4特别优选各自独立地为氢、甲基、乙基、异丙基、叔丁基、己基、辛基、壬基、癸基、十二烷基、苯基或萘基基团,尤其优选氢和/或甲基。在这种情况下,优选地,基团R4和R5中的一者是氢,而另一者不是氢。
式(II)中的磺酸基团,以及取代基R3和R4,处于芳环上的基于伯或仲氨基的对位或间位,磺酸基团在这种情况下优选处于间位。
合适的通式(II)的芳族氨基磺酸是例如4-氨基甲苯-2-磺酸、5-氨基甲苯-2-磺酸或2-氨基萘-4-磺酸,特别优选的是4-氨基甲苯-2-磺酸。
用于制备包含磺酸根基团的多异氰酸酯组分A)的其它起始化合物D)最后还有通式(III)的氨基官能磺酸
其中R5和R6各自独立地是相同或不同的基团并且是氢或具有1至18个碳原子的饱和或不饱和、直链或支链、脂族或脂环族或芳族有机基团,其是取代或未取代的和/或在链中包含杂原子,其中R5和R6,与彼此和任选一个另外的氮原子或一个氧原子组合,可以形成具有3至8个碳原子的脂环族或杂环的环,其可以任选被进一步取代,并且R7是具有2至6个碳原子的直链或支链脂族基团。
在通式(III)中,R5和R6各自独立地优选是具有1至8个碳原子的饱和、直链或支链、脂族或脂环族有机基团,其也可以彼此组合形成脂环族环,并且R7是具有2至4个碳原子的直链或支链脂族基团。
合适的通式(III)的氨基磺酸是例如2-氨基乙磺酸、3-氨基丙-1-磺酸、4-氨基丁-1-磺酸、3-氨基丁-1-磺酸、3-氨基-2-甲基丙-1-磺酸、4-氨基丁-2-磺酸、2-甲基氨基乙-1-磺酸、2-乙基氨基乙-1-磺酸、2-丙基氨基乙-1-磺酸、2-异丙基氨基乙-1-磺酸、2-正丁基氨基乙-1-磺酸、2-(叔丁基)氨基乙-1-磺酸、2-戊基氨基乙-1-磺酸、2-己基氨基乙-1-磺酸、2-辛基氨基乙-1-磺酸、2-苯胺基乙-1-磺酸、2-环丙基氨基乙-1-磺酸、2-环丁基氨基乙-1-磺酸、2-环戊基氨基乙-1-磺酸、2-环己基氨基乙-1-磺酸、异构的2-(甲基环己基)氨基乙-1-磺酸、2-(2,3-二甲基环己基)氨基乙-1-磺酸、2-(3,3,5-三甲基环己基氨基乙-1-磺酸、2-(4-叔丁基环己基)氨基乙-1-磺酸、2-环庚基氨基乙-1-磺酸、2-环辛基氨基乙-1-磺酸、2-(2-降冰片烷基)氨基乙-1-磺酸、2-(1-金刚烷基)氨基乙-1-磺酸、2-(3,5-二甲基-1-金刚烷基)氨基乙-1-磺酸、3-甲基氨基丙-1-磺酸、3-乙基氨基丙-1-磺酸、3-丙基氨基丙-1-磺酸、3-异丙基氨基丙-1-磺酸、3-正丁基氨基丙-1-磺酸、3-(叔丁基)氨基丙-1-磺酸、3-戊基氨基丙-1-磺酸、3-己基氨基丙-1-磺酸、3-辛基氨基丙-1-磺酸、3-苯胺基丙-1-磺酸、3-环丙基氨基丙-1-磺酸、3-环丁基氨基丙-1-磺酸、3-环戊基氨基丙-1-磺酸、3-环己基氨基丙-1-磺酸、异构的3-(甲基环己基)氨基丙-1-磺酸、3-(2,3-二甲基环己基)氨基丙-1-磺酸、3-(3,3,5-三甲基环己基氨基丙-1-磺酸、3-(4-叔丁基环己基)氨基丙-1-磺酸、3-环庚基氨基丙-1-磺酸、3-环辛基氨基丙-1-磺酸、3-(2-降冰片烷基)氨基丙-1-磺酸、3-(1-金刚烷基)氨基丙-1-磺酸、3-(3,5-二甲基-1-金刚烷基)氨基丙-1-磺酸、3-甲基氨基丁-1-磺酸、3-乙基氨基丁-1-磺酸、3-丙基氨基丁-1-磺酸、3-异丙基氨基丁-1-磺酸、3-正丁基氨基丁-1-磺酸、3-(叔丁基)氨基丁-1-磺酸、3-戊基氨基丁-1-磺酸、3-己基氨基丁-1-磺酸、3-辛基氨基丁-1-磺酸、3-苯胺基丁-1-磺酸、3-环丙基氨基丁-1-磺酸、3-环丁基氨基丁-1-磺酸、3-环戊基氨基丁-1-磺酸、3-环己基氨基丁-1-磺酸、异构的3-(甲基环己基)氨基丁-1-磺酸、3-(2,3-二甲基环己基)氨基丁-1-磺酸、3-(3,3,5-三甲基环己基氨基丁-1-磺酸、3-(4-叔丁基环己基)氨基丁-1-磺酸、3-环庚基氨基丁-1-磺酸、3-环辛基氨基丁-1-磺酸、3-(2-降冰片烷基)氨基丁-1-磺酸、3-(1-金刚烷基)氨基丁-1-磺酸、3-(3,5-二甲基-1-金刚烷基)氨基丁-1-磺酸、4-甲基氨基丁-1-磺酸、4-乙基氨基丁-1-磺酸、4-丙基氨基丁-1-磺酸、4-异丙基氨基丁-1-磺酸、4-正丁基氨基丁-1-磺酸、4-(叔丁基)氨基丁-1-磺酸、4-戊基氨基丁-1-磺酸、4-己基氨基丁-1-磺酸、4-辛基氨基丁-1-磺酸、4-苯胺基丁-1-磺酸、4-环丙基氨基丁-1-磺酸、4-环丁基氨基丁-1-磺酸、4-环戊基氨基丁-1-磺酸、4-环己基氨基丁-1-磺酸、异构的4-(甲基环己基)氨基丁-1-磺酸、4-(2,3-二甲基环己基)氨基丁-1-磺酸、4-(3,3,5-三甲基环己基氨基丁-1-磺酸、4-(4-叔丁基环己基)氨基丁-1-磺酸、4-环庚基氨基丁-1-磺酸、4-环辛基氨基丁-1-磺酸、4-(2-降冰片烷基)氨基丁-1-磺酸、4-(1-金刚烷基)氨基丁-1-磺酸、4-(3,5-二甲基-1-金刚烷基)氨基丁-1-磺酸、3-甲基氨基-2-甲基丙-1-磺酸、3-乙基氨基-2-甲基丙-1-磺酸、3-丙基氨基-2-甲基丙-1-磺酸、3-异丙基氨基-2-甲基丙-1-磺酸、3-正丁基氨基-2-甲基丙-1-磺酸、3-(叔丁基)氨基-2-甲基丙-1-磺酸、3-戊基氨基-2-甲基丙-1-磺酸、3-己基氨基-2-甲基丙-1-磺酸、3-辛基氨基-2-甲基丙-1-磺酸、3-苯胺基-2-甲基丙-1-磺酸、3-环丙基氨基-2-甲基丙-1-磺酸、3-环丁基氨基-2-甲基丙-1-磺酸、3-环戊基氨基-2-甲基丙-1-磺酸、3-环己基氨基-2-甲基丙-1-磺酸、异构的3-(甲基环己基)氨基-2-甲基丙-1-磺酸、3-(2,3-二甲基环己基)氨基-2-甲基丙-1-磺酸、3-(3,3,5-三甲基环己基氨基-2-甲基丙-1-磺酸、3-(4-叔丁基环己基)氨基-2-甲基丙-1-磺酸、3-环庚基氨基-2-甲基丙-1-磺酸、3-环辛基氨基-2-甲基丙-1-磺酸、3-(2-降冰片烷基)氨基-2-甲基丙-1-磺酸、3-(1-金刚烷基)氨基-2-甲基丙-1-磺酸、3-(3,5-二甲基-1-金刚烷基)氨基-2-甲基丙-1-磺酸、3-甲基氨基丁-2-磺酸、3-乙基氨基丁-2-磺酸、3-丙基氨基丁-2-磺酸、3-异丙基氨基丁-2-磺酸、3-正丁基氨基丁-2-磺酸、3-(叔丁基)氨基丁-2-磺酸、3-戊基氨基丁-2-磺酸、3-己基氨基丁-2-磺酸、3-辛基氨基丁-2-磺酸、3-苯胺基丁-2-磺酸、3-环丙基氨基丁-2-磺酸、3-环丁基氨基丁-2-磺酸、3-环戊基氨基丁-2-磺酸、3-环己基氨基丁-2-磺酸、异构的3-(甲基环己基)氨基丁-2-磺酸、3-(2,3-二甲基环己基)氨基丁-2-磺酸、3-(3,3,5-三甲基环己基氨基丁-2-磺酸、3-(4-叔丁基环己基)氨基丁-2-磺酸、3-环庚基氨基丁-2-磺酸、3-环辛基氨基丁-2-磺酸、 3-(2-降冰片烷基)氨基丁-2-磺酸、3-(1-金刚烷基)氨基-2-磺酸和3-(3,5-二甲基-1-金刚烷基)氨基丁-2-磺酸。
用于制备包含磺酸根基团的多异氰酸酯组分A)的特别优选的氨基磺酸D)是通式(III)的那些,其中基团R5和R6均不为氢。
非常特别优选的氨基磺酸D)是2-异丙基氨基乙-1-磺酸、3-异丙基氨基丙-1-磺酸、4-异丙基氨基丁-1-磺酸、2-环己基氨基乙-1-磺酸、3-环己基氨基丙-1-磺酸和4-环己基氨基丁-1-磺酸。
为了制备包含磺酸根基团的多异氰酸酯组分A),使多异氰酸酯C)与至少一种带有至少一个对异氰酸酯基团呈反应性的基团的磺酸 D)以使得所得多异氰酸酯组分A)包含至少0.85重量%、优选至少0.90重量%、更优选至少0.95重量%、甚至更优选1.00至3.00重量%和最优选1.10至1.80重量%的化学键合形式的磺酸根基团(以SO3计算;摩尔量 = 80 g/mol)的量反应。
为了制备包含磺酸根基团的多异氰酸酯组分A),带有至少一个对异氰酸酯基团呈反应性的基团的磺酸D)在与多异氰酸酯组分C)反应之前、期间或之后被至少部分中和,并以这种方式转化为磺酸根基团。
合适的中和剂在这种情况下是任何碱,如碱金属氢氧化物或碱土金属氢氧化物,但优选为胺,尤其是一元叔胺,例如三甲胺、三乙胺、异构的三丙胺和三丁胺、N,N-二甲基乙胺、N,N-二甲基丙胺、N,N-二甲基异丙胺、N,N-二甲基丁胺、N,N-二甲基异丁胺、N,N-二甲基辛胺、N,N-二甲基-2-乙基己胺、N,N-二甲基月桂胺、N,N-二乙基甲胺、N,N-二乙基丙胺、N,N-二乙基丁胺、N,N-二乙基己胺、N,N-二乙基辛胺、N,N-二乙基-2-乙基己胺、N,N-二乙基月桂胺、N,N-二异丙基甲胺、N,N-二异丙基乙胺、N,N-二异丙基丁胺、N,N-二异丙基-2-乙基己胺、N,N-二辛基甲胺、N,N-二甲基烯丙胺、N,N-二甲基苄胺、N,N-二乙基苄胺、N,N-二苄基甲胺、三苄基胺、N,N-二甲基-4-甲基苄胺、N,N-二甲基环己胺、N,N-二乙基环己胺、N,N-二环己基甲胺、N,N-二环己基乙胺、三环己基胺、N-甲基吡咯烷、N-乙基吡咯烷、N-丙基吡咯烷、N-丁基吡咯烷、N-甲基哌啶、N-乙基哌啶、N-丙基哌啶、N-丁基哌啶、N-甲基吗啉、N-乙基吗啉、N-丙基吗啉、N-丁基吗啉、N-仲丁基吗啉、N-叔丁基吗啉、N-异丁基吗啉和奎宁环,或二元叔胺,例如1,3-双(二甲基氨基)丙烷、1,4-双(二甲基氨基)丁烷和N,N'-二甲基哌嗪,或至少两种此类叔胺的混合物。
合适但较不优选的中和胺另外还有带有对异氰酸酯基团呈反应性的基团的叔胺,例如链烷醇胺,如二甲基乙醇胺、甲基二乙醇胺或三乙醇胺。
优选用于磺酸D)的中和胺是N,N-二甲基丁胺、N,N-二甲基-2-乙基己胺、N,N-二乙基甲胺、N,N-二异丙基乙胺、N,N-二异丙基-2-乙基己胺、N,N-二甲基环己胺、N,N-二环己基甲胺、N-甲基吡咯烷、N-甲基哌啶、N-乙基哌啶、N-甲基吗啉、N-乙基吗啉、N-异丁基吗啉或其混合物。
特别优选的是N,N-二甲基丁胺、N,N-二乙基甲胺、N,N-二异丙基乙胺、N,N-二甲基环己胺、N-甲基哌啶、N-乙基吗啉或其混合物。
指定用于制备包含磺酸根基团的多异氰酸酯组分A)的中和剂以使得根据本发明的所得方法产物中起始化合物D)的磺酸基团被中和到至少20摩尔%的程度、优选中和到至少50摩尔%的程度、特别优选中和到至少90摩尔%的程度和尤其优选完全中和并以磺酸根基团形式存在的量添加。
用于制备包含磺酸根基团的多异氰酸酯组分A)的起始化合物E)是任何非离子亲水性或疏水性化合物,其包含至少一个对异氰酸酯呈反应性的基团。
合适的非离子亲水性化合物E)是例如可以以本身已知的方式通过合适的起始物分子的烷氧基化获得的具有每分子5至50个环氧乙烷单元的统计平均数的一元或多元聚环氧烷聚醚醇(例如参见Ullmanns Encyclopädie der technischen Chemie,第4版,第19卷,Verlag Chemie,Weinheim第31-38页)。这种类型的起始物分子可以是例如分子量为32至300的一元醇或多元醇,例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、异构的戊醇、己醇、辛醇和壬醇、正癸醇、正十二烷醇、正十四烷醇、正十六烷醇、正十八烷醇、环己醇、异构的甲基环己醇、羟甲基环己烷、3-甲基-3-羟甲基氧杂环丁烷、苄醇、苯酚、异构的甲酚、辛基苯酚、壬基苯酚和萘酚、糠醇、四氢糠醇、1,2-乙二醇、1,2-和1,3-丙二醇、异构的丁二醇、戊二醇、己二醇、庚二醇和辛二醇、1,2-和1,4-环己二醇、1,4-环己烷二甲醇、4,4'-(1-甲基乙叉基(ethylidene))双环己醇、1,2,3-丙三醇、1,1,1-三羟甲基乙烷、1,2,6-己三醇、1,1,1-三羟甲基丙烷、2,2-双(羟甲基)-1,3-丙二醇或1,3,5-三(2-羟乙基)异氰脲酸酯。
适用于烷氧基化反应的环氧烷尤其是环氧乙烷和环氧丙烷,这些可以以任何顺序或以混合物用于烷氧基化反应。合适的聚醚醇是纯聚环氧乙烷聚醚醇或混合的聚环氧烷聚醚,其环氧烷单元在至少70摩尔%的程度上、优选在至少80摩尔%的程度上由环氧乙烷单元组成。
优选的聚环氧烷聚醚醇E)是使用分子量为32至150的上述一元醇作为起始物分子制备的那些。特别优选的聚醚醇是具有5至50个、尤其优选5至25个环氧乙烷单元的统计平均数的纯聚乙二醇单甲醚醇。
如果使用的话,用于制备包含磺酸根基团的多异氰酸酯组分A)的非离子亲水性化合物E)以基于起始多异氰酸酯C)计最多30重量%、优选最多25重量%、更优选最多20重量%和最优选最多15重量%的程度上的量使用。
合适的疏水性化合物E)是例如在每种情况下具有至少8个碳原子的脂族醇或脂肪酸酯醇。
合适的脂族疏水性醇是例如1-辛醇、2-乙基-1-己醇、异构的壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇、十五烷醇、十六烷醇和3-苯基-2-丙烯醇(肉桂醇)以及以这些醇为起始物的疏水性聚环氧烷醇,其环氧烷单元在至少80摩尔%、优选至少90摩尔%的程度上,特别优选完全由环氧丙烷单元组成。
合适的脂肪酸酯醇E)是例如羟基官能脂肪酸(例如羟基乙酸、3-羟基丙酸、3-和4-羟基丁酸、2-羟基琥珀酸(苹果酸)、2,3-二羟基琥珀酸(酒石酸)、2-羟基-1,2,3-丙三甲酸(柠檬酸)、羟基硬脂酸、蓖麻油酸、水杨酸和扁桃酸)与醇(例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、异构的戊醇、己醇、辛醇和壬醇、正癸醇或正十二烷醇)的酯化产物,其中脂肪酸和酯化醇的碳原子总数为至少8。
如果使用的话,用于制备包含磺酸根基团的多异氰酸酯组分A)的疏水性化合物E)以基于起始多异氰酸酯C)计最多30重量%、优选最多20重量%、特别优选最多10重量%的程度上的量使用。
在包含磺酸根基团的多异氰酸酯组分A)的制备中,任选还可以使用其它助剂和添加剂F),如抗氧化剂和/或催化剂。
合适的抗氧化剂F)是例如本身由塑料化学已知的具有抗氧化作用的化合物,例如优选的位阻酚和/或二-或三取代的亚磷酸酯。
合适的位阻酚F)是例如2,6-二-叔丁基苯酚、2,4-二甲基-6-叔丁基苯酚、2,6-二-叔丁基-4-甲基苯酚、三乙二醇双(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、3-(3,5-二-叔丁基-4-羟基苯基)丙酸十八烷基酯、季戊四醇四(3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯)、3-(3,5-二-叔丁基-4-羟基苯基)丙酸与脂族支链C7-至C9-醇的酯,例如3-(3,5-二-叔丁基-4-羟基苯基)丙酸异庚酯、3-(3,5-二-叔丁基-4-羟基苯基)丙酸异辛酯或3-(3,5-二-叔丁基-4-羟基苯基)丙酸异壬酯、3-(3,5-二-叔丁基-4-羟基苯基)丙酸异十三烷基酯、硫代二乙基双[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、N,N'-六亚甲基双(3,5-二-叔丁基-4-羟基苯基)丙酰胺、1,2-双(3,5-二-叔丁基-4-羟基苯基丙酸)酰肼、4'-羟基-3',5'-二-叔丁基苯甲酸2,4-二-叔丁基苯基酯、(3,5-二-叔丁基-4-羟基苯基)甲基硫代乙酸与脂族支链C10-至C14-醇的酯、2,2'-硫代双(4-甲基-6-叔丁基苯酚)、2-甲基-4,6-双(辛基硫基甲基)苯酚、1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯、异氰脲酸三(3,5-二-叔丁基-4-羟基苄基)酯和2,5-二-叔戊基氢醌,其任选与3,3'-硫代二丙酸双十二烷基酯或3,3'-硫代二丙酸双十八烷基酯组合使用。
合适的亚磷酸酯F)是例如二取代或优选三取代的亚磷酸酯,例如亚磷酸二丁酯和亚磷酸二苄酯、亚磷酸三乙酯和亚磷酸三丁酯。亚磷酸酯类型的抗氧化剂F)优选是三取代的亚磷酸酯,其中至少一个取代基是具有6至18个碳原子的任选取代的芳族基团或具有9至18个碳原子的直链或支链脂族基团,例如亚磷酸芳基酯,例如亚磷酸三苯基酯、亚磷酸三(2,4-二-叔丁基苯基)酯或亚磷酸三(壬基苯基)酯,亚磷酸烷基-芳基酯,例如亚磷酸二苯基异辛基酯、亚磷酸二苯基异癸基酯、亚磷酸二异癸基苯基酯、亚磷酸二异辛基苯基酯、亚磷酸苯基新戊二醇酯或亚磷酸2,4,6-三-叔丁基苯基(2-丁基-2-乙基-1,3-丙二醇)酯,亚磷酸烷基酯,例如亚磷酸三异癸基酯、亚磷酸三月桂基酯或亚磷酸三(十三烷基)酯,或芳族或脂族取代的二亚磷酸酯,例如二异癸基季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯或四苯基二丙二醇二亚磷酸酯。
用于制备包含磺酸根基团的多异氰酸酯组分A)的优选的抗氧化剂F)是包含2,6-二-叔丁基-4-甲基苯酚结构的位阻酚,和带有至少一个具有10至16个碳原子的直链或支链脂族取代基或苯基基团的三取代亚磷酸酯。特别优选的抗氧化剂F)是2,6-二-叔丁基-4-甲基苯酚、3-(3,5-二-叔丁基-4-羟基苯基)丙酸与脂族支链C7-至C9-醇的酯、3-(3,5-二-叔丁基-4-羟基苯基)丙酸十八烷基酯、亚磷酸三异癸酯、亚磷酸苯基二异癸基酯和/或亚磷酸二苯基异癸基酯。
用于制备包含磺酸根基团的多异氰酸酯组分A)的非常特别优选的抗氧化剂F)是2,6-二-叔丁基-4-甲基苯酚和3-(3,5-二-叔丁基-4-羟基苯基)丙酸与脂族支链C7-至C9-醇的酯。
在包含磺酸根基团的多异氰酸酯组分A)的制备中,如果使用的话,抗氧化剂F)单独和以与彼此的任何所需组合以基于多异氰酸酯C)的量计0.001至3.0重量%、优选0.002至2.0重量%、特别优选0.005至1.0重量%、尤其优选0.01至0.5重量%(以所用抗氧化剂的总量计算)的量使用。
抗氧化剂F)在这种情况下可以在实际反应开始前以上文指定的量添加到反应参与物中的一种或多种之中、添加到多异氰酸酯C)中、添加到带有至少一个对异氰酸酯基团呈反应性的基团的磺酸D)中和/或添加到任选要使用的非离子亲水性或疏水性化合物E)中。但是,它们也可在反应参与物的计量添加过程中的任何所需时间点或此后,优选在计量添加开始时添加到反应混合物中。
如果使用的话,在反应开始前将抗氧化剂F)添加到多异氰酸酯C)中。
在包含磺酸根基团的多异氰酸酯组分A)的制备中,组分C)、D)和任选的E)的反应通常进行得足够快,但是为了加速该反应,也可以任选使用由聚氨酯化学已知的常规催化剂作为另外的助剂和添加剂F),例如另外的叔胺,如三乙胺、吡啶、甲基吡啶、苄基二甲基胺、N,N-内亚乙基哌嗪(N,N-endoethylene piperazine)、N-甲基哌啶、五甲基二亚乙基三胺、N,N-二甲基氨基环己烷、N,N'-二甲基哌嗪或金属盐,如氯化铁(III)、三(乙基乙酰乙酸)铝、氯化锌、正辛酸锌(II)、2-乙基-1-己酸锌(II)、2-乙基-1-己酸锌(II)、硬脂酸锌(II)、环烷酸锌(II)、乙酰丙酮锌(II)、正辛酸锡(II)、2-乙基-1-己酸锡(II)、乙基己酸锡(II)、月桂酸锡(II)、棕榈酸锡(II)、氧化二丁基锡(IV)、二丁基二氯化锡(IV)、二乙酸二丁基锡(IV)、二马来酸二丁基锡(IV)、二月桂酸二丁基锡(IV)、二乙酸二辛基锡(IV)、乙醇酸钼或至少两种此类催化剂的混合物。
如果使用的话,这些催化剂F)以基于反应参与物的总重量计0.001至2重量%、优选0.005至0.5重量%的量用于制备包含磺酸根基团的多异氰酸酯组分A)。
适于制备根据本发明的多异氰酸酯混合物的多异氰酸酯组分B)是任何具有芳脂族和/或芳族键合的异氰酸酯基团的二异氰酸酯、三异氰酸酯和/或多异氰酸酯。在本发明的背景下,芳脂族键合的异氰酸酯基团理解为是指经由任选支链的亚烷基基团、优选亚甲基基团与芳环键合的异氰酸酯基团,而芳族键合的异氰酸酯基团理解为是指直接与芳环键合的那些。
合适的二异氰酸酯和三异氰酸酯B)是可以以各种方式(例如通过在液相或气相中的光气化或通过无光气途径,例如通过氨基甲酸酯热裂解)获得的任何芳脂族和/或芳族二异氰酸酯和三异氰酸酯,优选分子量为160至600的那些,如1,3-和1,4-双(异氰酸根合甲基)苯(苯二亚甲基二异氰酸酯,XDI)、1,3-和1,4-双(2-异氰酸根合丙-2-基)苯(四甲基苯二亚甲基二异氰酸酯,TMXDI)、1,3-双(异氰酸根合甲基)-4-甲基苯、1,3-双(异氰酸根合甲基)-4-乙基苯、1,3-双(异氰酸根合甲基)-5-甲基苯、1,3-双(异氰酸根合甲基)-4,5-二甲基苯、1,4-双(异氰酸根合甲基)-2,5-二甲基苯、1,4-双(异氰酸根合甲基)-2,3,5,6-四甲基苯、1,3-双(异氰酸根合甲基)-5-叔丁基苯、1,3-双(异氰酸根合甲基)-4-氯苯、1,3-双(异氰酸根合甲基)-4,5-二氯苯、1,3-双(异氰酸根合甲基)-2,4,5,6-四氯苯、1,4-双(异氰酸根合甲基)-2,3,5,6-四氯苯、1,4-双(异氰酸根合甲基)-2,3,5,6-四溴苯、1,4-双(2-异氰酸根合乙基)苯和1,4-双(异氰酸根合甲基)萘、1,2-、1,3-和1,4-二异氰酸根合苯(苯二异氰酸酯)、2,4-和2,6-二异氰酸根合甲苯(甲苯二异氰酸酯,TDI)、2,3,5,6-四甲基-1,4-二异氰酸根合苯、异构的二乙基苯二异氰酸酯、二异丙基苯二异氰酸酯、二异十二烷基苯二异氰酸酯和联苯二异氰酸酯、3,3'-二甲氧基联苯-4,4'-二异氰酸酯、2,2'-、2,4'-和4,4'-二异氰酸根合二苯基甲烷(MDI)、3,3'-二甲基二苯基甲烷-4,4'-二异氰酸酯、4,4'-二异氰酸根合二苯基乙烷、1,5-二异氰酸根合萘(NDI)、二苯醚二异氰酸酯、乙二醇二苯醚二异氰酸酯、二乙二醇二苯醚二异氰酸酯、1,3-丙二醇二苯醚二异氰酸酯、二苯甲酮二异氰酸酯、三异氰酸根合苯、2,4,6-三异氰酸根合甲苯、三甲基苯三异氰酸酯、二苯基甲烷-2,4,4'-三异氰酸酯、3-甲基二苯基甲烷-4,6,4'-三异氰酸酯、异构的萘三异氰酸酯和甲基萘二异氰酸酯、三苯甲烷三异氰酸酯、2,4-二异氰酸根合-1-[(5-异氰酸根合-2-甲基苯基)甲基]苯、4-甲基-二苯甲烷-3,5,2',4',6'-五异氰酸酯或至少两种此类二异氰酸酯的混合物。
同样合适的多异氰酸酯组分B)还有称为“聚合物-MDI”的二异氰酸根合二苯甲烷的多核同系物。
特别合适的多异氰酸酯组分B)是具有氨基甲酸酯和/或异氰脲酸酯结构的多异氰酸酯,其可以由单体2,4-和/或2,6-TDI通过与多元醇的反应和/或低聚化(优选三聚化)获得,其可以通过任何已知方法(描述在例如DE-A 870 400、DE-A 953 012、DE-A 1 090 196、EP-A 0 546 399、CN 105218780、CN 103881050、CN 101717571、US 3 183 112、EP-A 0 416338、EP-A 0 751 163、EP-A 1 378 529、EP-A 1 378 530、EP-A 2 174 967、JP 63260915或JP 56059828中)获得,或者是至少两种此类多异氰酸酯的混合物。
最后,合适的多异氰酸酯组分B)还有带有芳族和脂族异氰酸酯基团二者的那些,例如DE-A 1 670 667、EP-A 0 078 991、EP-A 0 696 606和EP-A 0 807 623中描述的2,4-和/或2,6-TDI与HDI的混合三聚体或脲基甲酸酯。
为了制备根据本发明的多异氰酸酯混合物,优选使用具有氨基甲酸酯和/或异氰脲酸酯结构的基于2,4-和/或2,6-TDI的多异氰酸酯组分B),其包含基于多异氰酸酯的固含量计小于1.5重量%、优选小于1.0重量%、特别优选小于0.5重量%的单体二异氰酸酯含量。根据DIN EN ISO 10283:2007-11通过使用内标的气相色谱法测量残余单体含量。
用于制备根据本发明的多异氰酸酯混合物的特别优选的多异氰酸酯组分B)是所提及的类型的包含氨基甲酸酯基团的TDI多异氰酸酯,特别是2,4-和/或2,6-TDI与1,1,1-三羟甲基丙烷(TMP)和任选进一步优选的低分子量醇(如二乙二醇)的低单体反应产物。
用于制备根据本发明的多异氰酸酯混合物的多异氰酸酯组分B)优选为疏水形式。然而,当然也可以任选地亲水改性多异氰酸酯组分B),例如通过上文在多异氰酸酯组分A)的制备中描述的方法,通过与对异氰酸酯基团呈反应性的具有磺酸和/或磺酸根基团的有机化合物 D)和/或指定为化合物E)的非离子亲水性聚醚醇反应。如果使用的话,带有至少一个对异氰酸酯基团呈反应性的基团的磺酸D)在这种情况下以使得所得多异氰酸酯组分B)包含0.60至2.00重量%、优选0.80至1.80重量%、特别优选1.00至1.60重量%的化学键合形式的磺酸根基团(以SO3计算;摩尔量 = 80 g/mol)的量使用。如果使用的话,非离子亲水性化合物E)可以在这种情况下以基于多异氰酸酯组分B)计最多30重量%、优选最多25重量%、特别优选最多20重量%的程度上的量使用。
为了改善相容性,多异氰酸酯组分B)还可以任选通过与脂族醇或脂肪酸酯醇(如上文在多异氰酸酯组分A)的制备中描述为疏水性化合物E))反应来改性。如果使用的话,此类疏水性化合物E)在这种情况下以基于多异氰酸酯组分B)计最多30重量%、优选最多20重量%、特别优选最多10重量%的程度上的量使用。
为了制备根据本发明的多异氰酸酯混合物,包含磺酸根基团的多异氰酸酯组分A)和多异氰酸酯组分B)在优选20至200℃、特别优选30至160℃、尤其优选35至120℃的温度下借助于合适的混合设备来混合和均化,其中选择比率以使得多异氰酸酯组分B)的比例为组分A)和B)的总量的7至43重量%、优选10至40重量%、更优选15至35重量%和最特别优选20至30重量%。
多异氰酸酯组分A)和B)可以在无溶剂的情况下混合。优选在实际混合之前、期间或之后,将对起始组分的反应性基团、尤其对异氰酸酯基团呈惰性的合适的有机溶剂添加到多异氰酸酯组分A)和/或B)中,尤其是添加到多异氰酸酯组分B)中。合适的溶剂的实例是本身已知的常规漆溶剂,例如乙酸乙酯、乙酸丁酯、乙二醇单甲基或单乙基醚乙酸酯、乙酸1-甲氧基-2-丙酯(MPA)、乙酸3-甲氧基-正丁酯、丙酮、2-丁酮、4-甲基-2-戊酮、环己酮、甲苯、二甲苯、氯苯、石油溶剂、相对高度取代的芳烃,例如以溶剂石脑油(solvent naphtha)、Solvesso®、Isopar®、Nappar®(Deutsche EXXON CHEMICAL GmbH, Cologne, DE)和Shellsol®(Deutsche Shell Chemie GmbH, Eschborn, DE)为名商业化的种类的那些,碳酸酯,如碳酸二甲酯、碳酸二乙酯、碳酸1,2-亚乙酯和碳酸1,2-亚丙酯,内酯,如β-丙内酯、γ-丁内酯、ε-己内酯和ε-甲基己内酯,以及如丙二醇二乙酸酯、二乙二醇二甲基醚、二丙二醇二甲基醚、丁基乙二醇乙酸酯、丁基二乙二醇乙酸酯、1,3-二氧杂环戊烷、N-甲基吡咯烷酮和N-甲基己内酰胺之类的溶剂,或至少两种此类溶剂的混合物。
在根据本发明的多异氰酸酯混合物的制备中,如果使用的话,有机溶剂以使得所得方法产物优选具有40至95重量%、特别优选50至90重量%、尤其优选60至85重量%的固含量(非挥发性部分)的量使用。
根据本发明的方法产物是任选溶解在有机溶剂中的包含磺酸根基团的多异氰酸酯混合物,其可以在不使用高剪切力的情况下,仅通过搅拌到水中容易地转化为优选沉淀稳定的分散体。
任选地,在乳化之前,将任何另外的非亲水化多异氰酸酯添加到根据本发明的多异氰酸酯混合物中,例如指定为合适的多异氰酸酯C)和/或多异氰酸酯组分B)的类型的那些,由此获得同样是根据本发明的多异氰酸酯混合物的多异氰酸酯混合物,条件是遵守上文就磺酸根基团含量和具有芳脂族和/或芳族键合的异氰酸酯基团的多异氰酸酯组分的比例所作的规定,因为这些通常由以下的混合物组成:
(i)根据本发明的用磺酸根基团亲水改性的多异氰酸酯混合物,和
(ii)通过举例提及的类型的未改性的多异氰酸酯。
在此类混合物中,存在于根据本发明的多异氰酸酯混合物中的包含磺酸根基团的多异氰酸酯组分A)对于随后混入的非亲水性多异氰酸酯起到了乳化剂的作用。
根据本发明的多异氰酸酯混合物代表了用于通过异氰酸酯加聚方法生产聚氨酯塑料的有价值的起始材料。
为此目的,所述多异氰酸酯混合物优选以水性乳液的形式使用,其在水性双组分体系的情况下可以与分散在水中的多羟基化合物组合反应。
在使用基于溶解或分散在水中的具有对异氰酸酯基团呈反应性的基团、尤其是醇羟基的漆基料或漆基料组分的水性涂料组合物的涂层制备中,根据本发明的包含磺酸根基团的多异氰酸酯混合物特别优选用作此类基料或基料组分的交联剂。交联剂(任选为乳化形式)在这里可以在处理涂料组合物之前通过以任何方法进行的简单搅拌或甚至通过使用双组分喷枪与基料或基料组分组合。
在此背景下可以提及的漆基料或漆基料组分包括:包含羟基的聚丙烯酸酯,其溶解或分散在水中,尤其是分子量为1000至20 000的那些,其是以有机多异氰酸酯作为交联剂的有价值的双组分基料,或任选的由聚酯和醇酸树脂化学已知类型的分散在水中的包含羟基的氨基甲酸酯改性聚酯树脂。原则上,任何溶解或分散在水中的包含对异氰酸酯呈反应性的基团的基料均适合作为根据本发明的多异氰酸酯混合物的反应参与物。这些还包括例如分散在水中的聚氨酯或聚脲,由于氨基甲酸酯或脲基团中存在的活性氢原子,其可以与多异氰酸酯交联。
本发明进一步提供了一种涂料组合物,其包含至少一种根据本发明的多异氰酸酯混合物。
在根据本发明用作水性漆基料的交联剂组分的情况下,根据本发明的包含磺酸根基团的多异氰酸酯混合物通常以使得对应于0.5:1至2:1的NCO基团与对NCO基团呈反应性的基团(尤其是醇羟基)的当量比的量使用。
然而,出于实现非常特殊的性能的目的,例如作为改善粘附性的添加剂,根据本发明的多异氰酸酯混合物可以任选地以次要量与非官能水性漆基料混合。
根据本发明的多异氰酸酯混合物当然也可以以用本身由聚氨酯化学已知的封闭剂封闭的形式,与上述水性漆基料或漆基料组分组合用作水性单组分PUR烤漆体系。合适的封闭剂是例如丙二酸二乙酯、乙酰乙酸乙酯、丙酮肟、丁酮肟、ε-己内酰胺、3,5-二甲基吡唑、1,2,4-三唑、二甲基-1,2,4-三唑、咪唑或这些封闭剂中的至少两种的混合物。
使用本发明的包含磺酸根基团的多异氰酸酯混合物配制的水性涂料的预期基底包括任何所需基底,例如金属、木材、玻璃、石材、陶瓷材料、混凝土、硬质和软质塑料、纺织品、皮革和纸,在涂布前也可以任选为其提供常规底漆。根据本发明的包含磺酸根基团的多异氰酸酯混合物的优选应用领域是用于为木材和家具上清漆的水性双组分清漆。
通常,用根据本发明的多异氰酸酯混合物配制的水性涂料组合物(任选可以向所述组合物中并入涂料行业中常规的助剂和添加剂,例如流动控制辅助剂、染料、彩色颜料、填料、消光剂或乳化剂,尤其是不与异氰酸酯基团呈反应性的所谓的外部乳化剂,如例如EP-A 0 486 881和WO 97/31960中所述)具有甚至在室温干燥的情况下也良好的涂层技术性能。
当然,它们可以替代地在强制条件下在升高的温度下干燥或通过在最高260℃的温度下烘烤干燥。
本发明还提供了用根据本发明的涂料组合物涂布的基底,所述涂料组合物任选通过热的作用固化。
作为水性涂料组合物中的交联剂组分,与来自现有技术的迄今为止已知的包含磺酸根基团的多异氰酸酯相比,根据本发明的多异氰酸酯混合物提供了在同样长的实际活化期下明显更快干燥的优点。由于它们优异的水乳化性(这使得能够实现在水性漆基料中均匀、特别是细散的分布),它们提供了具有优异的光学性能(特别是高表面光泽度)、流动性和高透明度的涂层,并且甚至还使得能够以与采用市售纯脂族多异氰酸酯交联剂可能实现的相比更大的层厚度来实现无气泡施加。
根据本发明的涂料组合物甚至在室温下也表现出令人惊讶地快速干燥,使得它们尤其推荐用于木材和家具行业,在所述行业中,诸如短循环时间和尽可能快速的打磨性能(sandability)之类的性能是合意的。
除了用作水性2K-PUR涂料的交联剂组分的优选用途之外,根据本发明的包含磺酸根基团的多异氰酸酯混合物还非常适合作为水性分散胶粘剂、皮革和纺织品涂料或纺织品印花浆的交联剂、作为无AOX纸助剂或甚至作为矿物建筑材料(例如混凝土或砂浆)的添加剂。
指定为对于根据本发明的多异氰酸酯混合物优选的特征对于本发明的其它主题也是优选的。
下面的实施例用于例示本发明,但决不应被理解为对保护范围施加任何限制。
实施例
除非另行指明,否则所有百分比基于重量计。
根据DIN EN ISO 11909:2007-05通过滴定法测定NCO含量。
用来自Anton Paar Germany GmbH (DE)的Physica MCR 51流变仪根据DIN ENISO 3219:1994-10在250 s-1的剪切速率下取得所有粘度测量结果。
根据DIN EN ISO 10283:2007-11通过使用内标的气相色谱法测量残余单体含量。
使用来自Methrom的Titrando 841自动滴定装置根据DIN 53715(基于DIN 51777第1部分(1973版本)创建)通过Karl Fischer体积滴定法测定水含量。这种方法的测量范围是0.01至99重量%。
根据DIN EN ISO 2813:2015-02在60°和20°角度下通过反射测定法获得所得涂层的光泽度。测量值越高,光泽度越高。
根据DIN EN ISO 13803:2015-02在20°角度下测得雾度。雾度值越低,涂层越不混浊。
根据DIN EN ISO 1522; 2007-04在玻璃板上测定根据König的摆杆阻尼。
根据DIN 53 150:2002-09测定涂料体系的干燥性能。
根据DIN EN ISO 4628-2:2016-07测定最大无气泡层厚度(起泡程度)。
通过DIN EN 12720:2014-02中描述的方法使用咖啡、红酒、水、芥末和乙醇作为测试液体测定化学品耐受性。
起始化合物
多异氰酸酯C)
多异氰酸酯C1
基于EP-A 330 966的实施例11通过HDI的催化三聚化制备的包含异氰脲酸酯基团的HDI多异氰酸酯,其中修改之处在于在粗混合物的NCO含量为40%时通过添加磷酸二丁酯终止反应。随后,通过薄膜蒸馏在130℃的温度和0.2 mbar的压力下除去未转化的HDI。
NCO含量: 21.7%
NCO官能度: 3.4
单体HDI: 0.1%
粘度(23℃): 3080 mPas
色值(Hazen): 18。
多异氰酸酯C2
通过WO 2016/146579中对于多异氰酸酯组分A2)所描述的方法通过PDI的催化三聚化制备的包含异氰脲酸酯基团的PDI多异氰酸酯。在粗混合物的NCO含量为36.7%时通过添加等摩尔量的磷酸二丁酯(基于所用催化剂的量计)使反应失活,并在80℃下进一步搅拌30分钟。随后,通过薄膜蒸馏在140℃的温度和0.5 mbar的压力下除去未转化的PDI。
NCO含量: 21.8%
NCO官能度: 3.5
单体PDI: 0.09%
粘度(23℃): 9850 mPas
色值(Hazen): 34。
氨基磺酸D)
3-(环己基氨基)丙磺酸(Sigma-Aldrich Chemie Gmbh, Munich, DE)用作氨基磺酸,其在真空(100℃/约0.5 mbar)下干燥3小时后具有0.4%的水含量。
多异氰酸酯组分A1)
将943.9克(4.88 val)的含有异氰脲酸酯基团的起始多异氰酸酯C1)与36.0克(0.16 val)的3-(环己基氨基)丙磺酸(CAPS)、20.1克(0.16摩尔)的二甲基环己胺和0.05克(50 ppm)的2,6-二-叔丁基-4-甲基苯酚在干燥氮气下在100℃下一起搅拌4:00小时,直到主要形成基本透明的包含磺酸根基团的多异氰酸酯混合物。在冷却到室温并经T 5500滤层(Seitz)过滤后,测定下列特征数据:
NCO含量: 19.8%
NCO官能度: 3.3
粘度(23℃): 8210 mPas
色值(Hazen): 18
磺酸根基团含量: 1.30%(以SO3计算;摩尔量% = 80 g/mol)。
多异氰酸酯组分A2)
将960.7克(4.92 val)的含有异氰脲酸酯基团的起始多异氰酸酯C1)与25.0克(0.11 val)的3-(环己基氨基)丙磺酸(CAPS)、14.3克(0.11摩尔)的二甲基环己胺和0.05克(50 ppm)的2,6-二-叔丁基-4-甲基苯酚在干燥氮气下在100℃下一起搅拌3:30小时,直到主要形成基本透明的包含磺酸根基团的多异氰酸酯混合物。在冷却到室温并经T 5500滤层(Seitz)过滤后,测定下列特征数据:
NCO含量: 20.2%
NCO官能度: 3.3
粘度(23℃): 4050 mPas
色值(Hazen): 18
磺酸根基团含量: 0.90%(以SO3计算;摩尔量% = 80 g/mol)。
多异氰酸酯组分A3)
将965.3克(4.99 val)的含有异氰脲酸酯基团的起始多异氰酸酯C1)与22.1克(0.10 val)的3-(环己基氨基)丙磺酸(CAPS)、12.6克(0.10摩尔)的二甲基环己胺和0.05克(50 ppm)的2,6-二-叔丁基-4-甲基苯酚在干燥氮气下在100℃下一起搅拌3:30小时,直到主要形成基本透明的包含磺酸根基团的多异氰酸酯混合物。在冷却到室温并经T 5500滤层(Seitz)过滤后,测定下列特征数据:
NCO含量: 20.5%
NCO官能度: 3.3
粘度(23℃): 3740 mPas
色值(Hazen): 20
磺酸根基团含量: 0.80%(以SO3计算;摩尔量% = 80 g/mol)。
多异氰酸酯组分A4)
将937.2克(4.86 val)的含有异氰脲酸酯基团的起始多异氰酸酯C2)与40.0克(0.18 val)的3-(环己基氨基)丙磺酸(CAPS)、22.8克(0.18摩尔)的二甲基环己胺、0.05克(50 ppm)的2,6-二-叔丁基-4-甲基苯酚和250克的MPA在干燥氮气下在100℃下一起搅拌3:15小时,直到主要形成基本透明的包含磺酸根基团的多异氰酸酯混合物。在冷却到室温并经T 5500滤层(Seitz)过滤后,测定下列特征数据:
NCO含量: 15.7%
NCO官能度: 3.4
固含量: 80%
粘度(23℃): 3420 mPas
色值(Hazen): 17
磺酸根基团含量: 1.45%(以SO3计算;摩尔量% = 80 g/mol,基于固体)。
多异氰酸酯组分B1)
基于EP-A 0 546 399的实施例4制备的含有氨基甲酸酯基团的TDI多异氰酸酯,其中修改之处在于使用80% 2,4-TDI和20% 2,6-TDI的混合物,并且所得浅黄色树脂以60%浓度溶解在乙酸1-甲氧基-2-丙基酯(MPA)中。
NCO含量: 10.6%
NCO官能度: 3.3
单体2,4-TDI: 0.13%
单体2,6-TDI: 0.14%
粘度(23℃): 370 mPas
色值(Hazen): 34。
实施例1至10(本发明和对比)
将多异氰酸酯组分A1)、A2)和A3)与多异氰酸酯组分B1)在30℃下以不同比率混合,并通过搅拌均化30分钟。随后在每种情况下用MPA将多异氰酸酯混合物的固含量调节至70%。
下表1显示了所获得的多异氰酸酯混合物的相应组成和特征数据。
实施例11至20(本发明和对比)
将100重量份的市售羟基官能聚丙烯酸酯水性分散体(固含量为40%且OH含量为3.0%,基于树脂固体,可以商品名Bayhydrol A 2651 (Covestro AG, Leverkusen)获得)与2.6重量份的市售非离子润湿剂(Surfynol AD01, Evonik Materials Netherlands BV,Utrecht)、0.16重量份的市售流动控制添加剂(TEGO Flow 425, Evonik Resource EmbH,Essen)和0.16重量份的市售增稠剂(OPTIFLO-TVS VF, BYK-Chemie GmbH, Wesel)混合。向该透明涂料材料中添加实施例1至10的多异氰酸酯混合物,在每种情况下添加量如表2中所规定(在每种情况下对应于1.5:1的异氰酸酯基团与醇羟基的当量比),并通过以1000 rpm搅拌5分钟使混合物均化。随后通过添加水将透明涂料的固含量调节至45%。
为了比较,使用相同的方法,同样由100重量份的Bayhydrol A 2651和32.12重量份的多异氰酸酯组分A1)在MPA或32.4重量份的多异氰酸酯组分A4)的70%溶液中制备透明涂料(在每种情况下对应于1.5: 1的异氰酸酯基团与醇羟基的当量比)。
借助于拉膜框(film drawing frame),将涂料以200 μm的湿膜层厚度(干膜层厚度约90 μm)施加到玻璃板和黑色有机玻璃片材上,并在每种情况下在室温(约25℃)和50%相对空气湿度下干燥。表2显示了所获得的涂层的漆相关性能。
在所有情况下,施加备用(application-ready)混合物的处理时间>6小时。
实施例13至16和20表明,使用来自实施例2至5和9的根据本发明的多异氰酸酯混合物与水性基料组合,得到有光泽、透明、几乎无混浊的涂膜,与使用纯脂族多异氰酸酯A1)的交联涂层(实施例11)和使用实施例1的仅含5重量%的芳族多异氰酸酯的多异氰酸酯混合物的交联涂层(实施例12)相比,其优点为在>6小时的不变的长活化期下明显更快的干燥(T4)。对比例17表明,具有45重量%的芳族多异氰酸酯B1)比例的多异氰酸酯混合物与水性基料分散体不相容,并得到可通过低光泽度识别的高度混浊的涂膜。
实施例18和19的比较表明,为了获得透明、无混浊的涂膜,需要特定最小量的多异氰酸酯组分A)中的磺酸根基团。
实施例21和对比例22通过含有异氰脲酸酯的PDI多异氰酸酯的实施例显示了根据本发明的多异氰酸酯混合物的更快干燥的优点。
实施例23和24(对比)
为了测定最大无气泡层厚度,借助于步进式间隙涂膜机(step gap filmapplicator)将来自实施例20和对比例11的透明涂料施加到黑色有机玻璃片材上,并在每种情况下在室温(约25℃)和55%的相对空气湿度下干燥。下表显示了对于各种施加的层厚度根据DIN EN ISO 4628-2:2016-07目测评价的起泡程度(0=最佳等级;5=最差等级)。
表3:
比较表明,用来自实施例9的根据本发明的多异氰酸酯混合物交联的涂膜(实施例20),尽管其具有一定比例的对水呈高度反应性的芳族异氰酸酯基团,但在300 μm的施加层厚度下仍然能够完全无气泡地干燥,并且甚至在更高的施加厚度下,与来自实施例11的用纯脂族多异氰酸酯组分A1)交联的涂层相比,显示出明显较低的气泡形成。
实施例25和26(本发明和对比)
将100重量份的市售羟基官能聚丙烯酸酯水性分散体(固含量为40%且OH含量为3.0%,基于树脂固体,可以商品名Bayhydrol A 2651(Covestro AG, Leverkusen)获得)与2.8重量份的市售非离子润湿剂(Surfynol AD01, Evonik Materials Netherlands BV,Utrecht)、38.2重量份的市售白色颜料水性分散体(White Aquamac 6, Proquimac PFC,S.A, Barcelona, Spain)、2.0重量份的市售增稠剂(OPTIFLO-TVS VF, BYK-Chemie GmbH,Wesel)和29.8重量份的去离子水混合,得到白色涂料。向该储备混合物中添加37.4重量份的来自实施例9的多异氰酸酯混合物(对应于1.7:1的异氰酸酯基团与醇羟基的当量比),并通过以1000 rpm搅拌5分钟使混合物均化。
为了比较,使用相同的方法,由100重量份的Bayhydrol A 2651和36.3重量份的多异氰酸酯组分A1)在MPA中的70%溶液(对应于1.7:1的异氰酸酯基团与醇羟基的当量比)制备白色涂料。
借助于拉膜框将涂料以200 μm的湿膜层厚度(干膜层厚度约90 μm)施加在玻璃板上,并在每种情况下在50℃下干燥16小时。在23℃下再过24小时后,根据DIN EN 12720:2014-02测试由此获得的白色涂层的化学品耐受性。下表4显示了在不同测试时间段之后的测试结果。
表4:
a) 根据DIN EN 12720:2014-02的方法,评价0至5 (0 = 最差等级,5 = 最佳等级)
b) 作为48%的水溶液。
实施例表明,用来自实施例9的本发明的多异氰酸酯混合物交联的涂膜(实施例25)具有与用纯脂族多异氰酸酯组分A1)交联的涂层一样好的家用化学品耐受性。
Claims (21)
1.多异氰酸酯混合物,其包含具有脂族和/或脂环族键合的异氰酸酯基团的多异氰酸酯组分A)和具有芳脂族和/或芳族键合的异氰酸酯基团的多异氰酸酯组分B),其特征在于所述多异氰酸酯组分A)包含至少0.85重量%的化学键合形式的磺酸根基团,以SO3计算,摩尔量 = 80 g/mol,并且所述多异氰酸酯组分B)的比例为组分A)和B)的总量的7至43重量%。
2.根据权利要求1所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分A)是至少一种脂族和/或脂环族多异氰酸酯C)与至少一种带有至少一个对异氰酸酯基团呈反应性的基团且包含一个或多个磺酸和/或磺酸根基团的有机化合物D)、和任选至少一种包含至少一个对异氰酸酯基团呈反应性的基团的非离子亲水性或疏水性化合物E)的反应产物,其已任选在其它助剂和添加剂F)的存在下制备。
3.根据权利要求2所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯C)是任何具有脂族和/或脂环族键合的异氰酸酯基团的二异氰酸酯和/或多异氰酸酯。
4.根据权利要求2或3所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯C)是基于PDI、HDI、IPDI和/或4,4'-二异氰酸根合二环己基甲烷的那些。
5.根据权利要求2或3所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯C)是基于PDI和/或HDI的那些。
6.根据权利要求2或3所述的多异氰酸酯混合物,其特征在于所述有机化合物D)是羟基-、巯基-和/或氨基-官能磺酸和/或其盐。
8.根据权利要求2或3所述的多异氰酸酯混合物,其特征在于所述有机化合物D)是2-异丙基氨基乙-1-磺酸、3-异丙基氨基丙-1-磺酸、4-异丙基氨基丁-1-磺酸、2-环己基氨基乙-1-磺酸、3-环己基氨基丙-1-磺酸和/或4-环己基氨基丁-1-磺酸和/或其盐。
9.根据权利要求2或3所述的多异氰酸酯混合物,其特征在于所述有机化合物D)在至少20摩尔%的程度上以用N,N-二甲基丁胺、N,N-二乙基甲胺、N,N-二异丙基乙胺、N,N-二甲基环己胺、N-甲基哌啶、N-乙基吗啉中和的磺酸根基团形式存在。
10.根据权利要求2或3所述的多异氰酸酯混合物,其特征在于所述非离子亲水性或疏水性有机化合物E)是纯聚环氧乙烷聚醚醇和/或混合的聚环氧烷聚醚醇,其环氧烷单元在至少70摩尔%的程度上由环氧乙烷单元组成,和/或在每种情况下包含至少8个碳原子的脂族醇或脂肪酸酯醇。
11.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分A)包含至少0.90重量%的化学键合形式的磺酸根基团,以SO3计算,摩尔量 = 80 g/mol。
12.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分A)包含至少0.95重量%的化学键合形式的磺酸根基团,以SO3计算,摩尔量 = 80 g/mol。
13.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分A)包含1.00至3.00重量%的化学键合形式的磺酸根基团,以SO3计算,摩尔量 = 80 g/mol。
14.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分A)包含1.10至1.80重量%的化学键合形式的磺酸根基团,以SO3计算,摩尔量 = 80 g/mol。
15.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分B)是具有氨基甲酸酯和/或异氰酸酯结构的多异氰酸酯,其由单体2,4-和/或2,6-TDI通过与多元醇反应和/或低聚化获得。
16.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分B)的比例为组分A)和B)的总量的10至40重量%。
17.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分B)的比例为组分A)和B)的总量的15至35重量%。
18.根据权利要求1至3任一项所述的多异氰酸酯混合物,其特征在于所述多异氰酸酯组分B)的比例为组分A)和B)的总量的20至30重量%。
19.至少一种根据权利要求1至18任一项所述的多异氰酸酯混合物在聚氨酯塑料的生产中作为起始组分的用途。
20.包含至少一种根据权利要求1至18任一项所述的多异氰酸酯混合物的涂料组合物。
21.基底,其涂布有根据权利要求20所述的涂料组合物,所述涂料组合物任选通过热的作用来固化。
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