CN101277988A - 用于制备柔性涂层的双组分体系 - Google Patents
用于制备柔性涂层的双组分体系 Download PDFInfo
- Publication number
- CN101277988A CN101277988A CNA200680036690XA CN200680036690A CN101277988A CN 101277988 A CN101277988 A CN 101277988A CN A200680036690X A CNA200680036690X A CN A200680036690XA CN 200680036690 A CN200680036690 A CN 200680036690A CN 101277988 A CN101277988 A CN 101277988A
- Authority
- CN
- China
- Prior art keywords
- coating system
- component coating
- groups
- zinc
- component
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 9
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 29
- 229920001228 polyisocyanate Polymers 0.000 claims description 29
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- 238000000034 method Methods 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- -1 zinc (II) compound Chemical class 0.000 claims description 4
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229920002396 Polyurea Polymers 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 3
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000608 Polyaspartic Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000005700 Putrescine Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 description 1
- VKLNMSFSTCXMSB-UHFFFAOYSA-N 1,1-diisocyanatopentane Chemical compound CCCCC(N=C=O)N=C=O VKLNMSFSTCXMSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- JWTVQZQPKHXGFM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diamine Chemical compound CC(C)(N)CCC(C)(C)N JWTVQZQPKHXGFM-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 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
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 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
Classifications
-
- 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
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Abstract
本发明涉及用于制备柔性涂层的双组分涂料体系。该涂料体系包括具有脲基甲酸酯结构的聚氨酯预聚物以及作为固化剂的氨基官能的聚天冬氨酸酯。
Description
本发明涉及用于制备柔性涂层的双组分涂料体系。该涂料体系包括具有脲基甲酸酯结构的聚氨酯预聚物以及作为固化剂的氨基官能的聚天冬氨酸酯。
基于聚氨酯和聚脲的双组分涂料体系是已知的并已经应用在工业中。通常,其含液态多异氰酸酯组分和液态异氰酸酯反应性组分。通过让多异氰酸酯和作为异氰酸酯反应性组分的胺进行反应产生了强烈交联的聚脲涂料。但是伯胺和异氰酸酯在大多数情况下非常快地相互反应。典型的贮存期(Topfzeit)或胶凝时间通常仅为数秒到少数几分钟。因此,这类聚脲涂料不能手工施加,而只能借助特殊喷涂设备施加。然而,这类涂料具有优异的物理性能。
由文献已知的降低反应性的方法之一是使用低NCO含量的预聚物。通过使用NCO官能的预聚物和胺的组合,可以制备柔性的聚脲涂层。
US-A 3 428 610和US-A 4 463 126公开了通过借助芳族二胺固化NCO官能的预聚物来制备聚氨酯/聚脲弹性体。优选的芳族二胺是芳族二伯胺(di-aromatische Diamine),其中在每个氨基的邻位含有至少一个具有2-3个碳原子的烷基取代基和视需要在该氨基的另一个邻位含有甲基取代基,例如二乙基甲苯二胺(DETDA)。
US-A 4 463 126记载了一种用于制备不含溶剂的弹性涂层的方法,其中基于异佛尔酮二异氰酸酯(IPDI)和聚酯多元醇的NCO预聚物在室温下借助空间位阻芳族二伯胺进行固化。
这类体系的缺陷在于芳族二胺往往易于强烈泛黄。
另一种延迟多异氰酸酯和胺之间反应的可行方案是使用仲胺。EP-A 403 921和US-A 5 126 170公开了通过让聚天冬氨酸酯与多异氰酸酯反应形成聚脲涂层。聚天冬氨酸酯具有低的粘度和降低的对多异氰酸酯的反应性,并因此可以用于制备具有延长的贮存期的无溶剂涂覆剂。聚天冬氨酸酯的另一优点是产品是无色的。
与此不同的是,基于聚酯多元醇的无色脂族多异氰酸酯预聚物被聚天冬氨酸酯固化得非常慢,和涂层常常具有发粘的表面。
因此,现本发明的任务在于提供用于制备聚脲涂层的双组分涂覆剂,其具有足够长的贮存期,以便还允许手工施加和借助该双组分涂覆剂使得可以制备具有优异的工业使用数据如弹性和硬度的无色柔性涂层。
该任务现通过特定的脲基甲酸酯多异氰酸酯和聚天冬氨酸酯的组合来解决。
因此,本发明的主题是双组分涂料体系,其至少含有:
A)多异氰酸酯预聚物,其具有经脲基甲酸酯基团连接的聚醚基团,和
B)通式(I)的氨基官能的聚天冬氨酸酯
其中
X表示n价有机基团,其通过脱除n元多胺的伯氨基获得,
R1、R2表示相同或不同的有机基团,其在反应条件下对异氰酸酯基团呈惰性,和
n表示至少2的整数。
在组分A)中使用的脲基甲酸酯可通过如下方法获得,其中
A1)一种或多种脂族和/或脂环族多异氰酸酯与
B1)一种或多种多羟基化合物,其中至少一种为聚醚多元醇,
反应成NCO官能的聚氨酯预聚物,然后这样形成的氨基甲酸酯基团在添加下列组分条件下部分或者全部脲基甲酸酯化
A3)多异氰酸酯,其可以与来自A1)的不同,和
A4)催化剂,和
A5)视需要的稳定剂。
对于合适的脂族和脂环族多异氰酸酯A1)的实例是二异氰酸酯或三异氰酸酯,例如丁烷二异氰酸酯、戊烷二异氰酸酯、己烷二异氰酸酯(六亚甲基二异氰酸酯,HDI)、4-异氰酸根合甲基-1,8-辛烷二异氰酸酯(三异氰酸根合壬烷,TIN)或环状体系,例如4,4’-亚甲基双(环己基异氰酸酯)、3,5,5-三甲基-1-异氰酸根合-3-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI)以及ω,ω’-二异氰酸根合-1,3-二甲基环己烷(H6XDI)。
在组分A1)和A3)中优选使用己烷二异氰酸酯(六亚甲基二异氰酸酯,HDI)、4,4’-亚甲基双(环己基异氰酸酯)和/或3,5,5-三甲基-1-异氰酸根合-3-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI)作为多异氰酸酯。非常特别优选的多异氰酸酯是HDI。
优选在A1)和A3)中使用相同类型的多异氰酸酯。
作为组分A2)的多羟基化合物可以使用所有本领域技术人员已知的多羟基化合物,其优选具有大于或等于1.5的平均OH官能度,其中在A2)中所含的化合物的至少一种必须是聚醚多元醇。
适合在A2)中使用的多羟基化合物是低分子量二醇(例如1,2-乙二醇、1,3-丙二醇或1,2-丙二醇、1,4-丁二醇),三醇(例如甘油、三羟甲基丙烷)和四醇(例如季戊四醇),聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇以及聚硫醚多元醇。优选地,在A2)中仅使用上述类型的基于聚醚的物质作为多羟基化合物。
优选在A2)中使用的聚醚多元醇具有300-20000g/mol,特别优选1000-12000g/mol,非常特别优选2000-6000g/mol的数均分子量Mn。
此外,其优选具有≥1.9,特别优选≥1.95的平均OH官能度。
这类聚醚多元醇以已知的方式通过在碱催化剂或使用双金属氰化物化合物(DMC化合物)的条件下使合适的起始物分子烷氧基化获得。
特别合适的组分A2)的聚醚多元醇是不饱和端基含量小于或等于0.02毫当量/克多元醇(meq/g),优选小于或等于0.015meq/g,特别优选小于或等于0.01meq/g的上述类型的那些(测量方法:ASTMD2849-69)。
这类聚醚多元醇以本身已知的方式可通过使合适的起始物分子烷氧基化制备,特别是在使用双金属氰化物催化剂(DMC催化)条件下制备。这例如记载在US-A 5 158 922(例如实施例30)和EP-A 0 654 302(第5页,26行-第6页32行)中。
对于制备聚醚多元醇合适的起始物分子例如是简单的低分子量多元醇、水、具有至少两个N-H键的有机多胺或者这类起始物分子的任意混合物。适合于烷氧基化的环氧烷特别是环氧乙烷和/或环氧丙烷,在烷氧基化过程中它们可以以任意顺序或者以混合物形式使用。
优选的用于通过烷氧基化(特别是按照DMC方法)制备聚醚多元醇的起始物分子是特别简单的多元醇,例如乙二醇、1,3-丙二醇和1,4-丁二醇、1,6-己二醇、新戊基二醇、2-乙基-1,3-己二醇、甘油、三羟甲基丙烷、季戊四醇以及这类多元醇与下面示例性提及类型的二羧酸的低分子量的含羟基酯,或者这类简单多元醇的低分子量乙氧基化产物或丙氧基化产物,或者这类改性或未改性醇的任意混合物。
作为中间体的含异氰酸酯基团的聚氨酯预聚物的制备通过组分A2)的多羟基化合物与过量的来自A1)的多异氰酸酯反应进行。该反应通常在20-140℃,优选40-100℃温度,视需要在使用聚氨酯化学中本身已知的催化剂例如锡皂如二月桂基二丁基锡或叔胺例如三乙胺或二氮杂二环辛烷的条件下进行。
然后,通过让含异氰酸酯基团的聚氨酯预聚物与多异氰酸酯A3)反应进行脲基甲酸酯化,多异氰酸酯A3)可以与组分A1)的多异氰酸酯相同或不同,其中添加用于脲基甲酸酯化的合适催化剂A4)。典型地,随后为了稳定化添加组分A5)的酸性添加剂和例如通过薄层蒸馏或者萃取从产物中除去过量的多异氰酸酯。
组分A2)的化合物的OH基团对来自A1)和A3)的多异氰酸酯的NCO基团的摩尔比优选为1∶1.5-1∶20,特别优选1∶2-1∶15,非常特别优选1∶2-1∶10。
优选地,使用锌(II)化合物作为在A4)中的催化剂,其中该催化剂特别优选是长链、支化或者未支化、脂族羧酸的锌皂。优选的锌(II)皂是基于2-乙基己酸以及线型脂族C4-C30羧酸的那些。非常特别优选的组分A4)的化合物是双(2-乙基己酸)锌(II)、双(正辛酸)锌、双硬脂酸锌或它们的混合物。
这些脲基甲酸酯化催化剂通常以5ppm直至5重量%的量使用,基于总的反应混合物。优选使用5-500ppm的催化剂,特别优选使用20-200ppm的催化剂。
视需要,可以在脲基甲酸酯化之前、期间、之后还使用起稳定作用的添加剂。其可以是酸性添加剂例如路易斯酸(缺电子化合物)或布朗斯塔特酸(质子酸)或者在与水反应时释放出这类酸的那些化合物。
起稳定作用的添加剂例如是无机酸或有机酸或与水反应成相应酸的中性化合物如酰卤或酯。在此提及的特别有盐酸、磷酸、磷酸酯、苯甲酰氯、间苯二甲酰氯、对甲苯磺酸、甲酸、乙酸、二氯乙酸和2-氯丙酸。
上述酸性添加剂也可以用于让脲基甲酸酯化催化剂失活。此外,其改善了本发明制备的脲基甲酸酯的稳定性,例如对在薄层蒸馏期间或者在制备后在产物存储期间的热负载的稳定性。
所述酸性添加剂通常至少以如下量添加,也即酸性添加剂的酸性中心和催化剂的摩尔比为至少1∶1。但是,优选添加过量的酸性添加剂。
如果使用酸性添加剂,那么其优选是有机酸例如羧酸或酰卤例如苯甲酰氯或间苯二甲酰氯。
如果要分离掉过量的二异氰酸酯,那么薄层蒸馏是优选的方法,且其优选在100-160℃温度和0.01-3毫巴压力进行。然后的残留单体含量优选低于1重量%,特别优选低于0.5重量%(二异氰酸酯)。
整个方法步骤可以视需要在存在惰性溶剂条件下进行。在本文中惰性溶剂理解为在给出反应条件下不与进料物反应的那些。实例是乙酸乙酯、乙酸丁酯、甲氧基丙基乙酸酯、甲基乙基酮、甲基异丁基酮、甲苯、二甲苯、芳族或脂(环)族烃混合物或者上述溶剂的任意混合物。然而,本发明的反应优选无溶剂地进行。
相关组分的添加既可以在含异氰酸酯基团的预聚物的制备过程中也可以在脲基甲酸酯化过程中以任意顺序进行。但是,优选地,向预先放置的组分A1)和A3)的多异氰酸酯添加聚醚多元醇A2),最后添加脲基甲酸酯化催化剂A4)。
在本发明的一个优选实施方案中,组分A1)和A3)的多异氰酸酯被预先放置在合适的反应容器中,视需要进行搅拌,温热到40-100℃。然后,在达到理想温度后在搅拌条件下添加组分A2)的多羟基化合物,并搅拌直到达到或者略低于根据所选择的化学计量比所期望的聚氨酯预聚物的理论NCO含量。现在添加A4)的脲基甲酸酯化催化剂,并将反应混合物在50℃和100℃温热,直到达到或者略低于所需的NCO含量。在添加作为稳定剂的酸性添加剂之后,冷却反应混合物或者直接送入薄层蒸馏。在此处在100-160℃温度和0.01-3毫巴压力下除去过量多异氰酸酯直到残余单体含量低于1%,优选低于0.5%。在薄层蒸馏后可以视需要添加其它的稳定剂。
这种要求保护的双组分涂料体系所用的脲基甲酸酯通常对应于通式(II)
其中
Q1和Q2彼此独立地为上述类型的链状和/或环状脂族二异氰酸酯,优选是-(CH2)6-,
R3和R4彼此独立地为氢或C1-C4烷基,其中R3和R4优选为氢和/或甲基,和在每个重复单元k中R3和R4的意义可以不同,
Y是具有2-6个官能度的上述类型的起始物分子的残基,和
z是2-6的数,由于使用不同的起始物分子其当然不一定是整数,以及
k优选对应于这么多单体单元,使得基于该结构的聚醚的数均分子量为300-20000g/mol,和
m为1或3。
优选获得对应于通式(III)的脲基甲酸酯
其中,
Q表示上述类型的链状和/或环状脂族二异氰酸酯,优选-(CH2)6-,
R3和R4彼此独立地为氢或C1-C4烷基,其中R3和R4优选为氢和/或甲基,和在每个重复单元m中R3和R4的意义可以不同,
Y是上述类型的二官能起始物分子的残基,和
k优选对应于这么多单体单元,使得基于该结构的聚醚的数均分子量为300-20000g/mol,和
m等于1或3。
因为为了制备式(II)和(III)的脲基甲酸酯通常使用基于经聚合环氧乙烷、环氧丙烷或四氢呋喃的多元醇,那么式(II)和(III)在m=1的情况下,特别优选R3和R4的至少一个基团是氢;在m=3的情况下,R3和R4是氢。
根据本发明在A)中使用的脲基甲酸酯通常具有700-50000g/mol,优选1500-8000g/mol,特别优选1500-4000g/mol的数均分子量。
根据本发明在A)中使用的脲基甲酸酯通常在23℃具有500-100000mPas,优选500-50000mPas和特别优选1000-7500mPas、非常特别优选1000-3500mPas的粘度。
组分B)的聚天冬氨酸酯在式(I)中的基团X优选基于选自下列的n元多胺:乙二胺、1,2-二氨基丙烷、1,4-二氨基丁烷、1,6-二氨基己烷、2,5-二氨基-2,5-二甲基己烷、2,2,4-和/或2,4,4-三甲基-1,6-二氨基己烷、1,11-二氨基十一烷、1,12-二氨基十二烷、1-氨基-3,3,5-三甲基-5-氨基甲基环己烷、2,4-和/或2,6-六氢甲代苯二胺、2,4’-和/或4,4’-二氨基二环己基甲烷、3,3’-二甲基-4,4’-二氨基二环己基甲烷、2,4,4’-三氨基-5-甲基二环己基甲烷和具有脂族结合的伯氨基团的数均分子量Mn为148-6000g/mol的聚醚多胺。
特别优选地,基团X基于1,4-二氨基丁烷、1,6-二氨基己烷、2,2,4-和/或2,4,4-三甲基-1,6-二氨基己烷、1-氨基-3,3,5-三甲基-5-氨基甲基环己烷、4,4’-二氨基二环己基甲烷或3,3’-二甲基-4,4’-二氨基二环己基甲烷。
就基团R1和R2而言,“在反应条件下对异氰酸酯基团呈惰性”是指这些基团不含Zerewitinoff活性氢的基团(CH酸性化合物;参见Chemie Lexikon,Georg Thieme Verlag Stuttgart)例如OH、NH或SH。
优选地,R1和R2彼此独立地为C1-C10烷基,特别优选甲基或乙基。
对于X基于2,4,4’-三氨基-5-甲基二环己基甲烷的情况下,优选R1=R2=乙基。
优选地,在式(I)中n是2-6,特别优选2-4的整数。
氨基官能的聚天冬氨酸酯B)的制备以已知的方式通过让下式的相应伯胺
X-[NH2]n
与下面通式的马来酸酯或富马酸酯反应而进行。
R1OOC-CH=CH-COOR2
合适的多胺是上文中作为基团X的基础提及的二胺。
合适的马来酸酯和富马酸酯的实例是马来酸二甲酯、马来酸二乙酯、马来酸二丁酯和相应的富马酸酯。
由上述起始材料制备氨基官能的聚天冬氨酸酯B)优选在0-100℃温度范围内进行,其中起始材料以这样的数量比使用,使得每个伯氨基团分摊至少一个、优选刚好一个烯属双键,在反应之后可以蒸馏除去视需要以过量使用的起始材料。反应可以在本体形式或者在存在合适的溶剂例如甲醇、乙醇、丙醇或二噁烷或上述溶剂的混合物条件下进行。
在本发明的双组分涂料体系中,游离或嵌段的氨基对游离NCO基团的比优选为0.5∶1-1.5∶1,特别优选为1∶1-1.5∶1。
为了制备本发明的双组分涂料体系,将各组分彼此混合。
上述涂覆剂可以借助本身已知的技术例如喷涂、浸涂、流涂、辊涂、涂抹或浇注施加在表面上。在急骤馏掉(Ablüften)视需要存在的溶剂后,然后在环境条件下或者在例如40-200℃的较高温度固化涂层。
上述涂覆剂可以被施加到例如金属、塑料、陶瓷、玻璃或天然物质上,其中上述基材可以视需要预先经历必要的预处理。
实施例
NCO含量的测定通过用盐酸返滴定过量添加的二正丁胺进行。粘度借助Haake公司的旋转粘度计在23℃测定。
若非另行指出,所有百分比数据均基于重量。
制备预聚物1
首先向2520.7g 1,6-己烷二异氰酸酯添加90mg间苯二甲酰氯,然后在搅拌条件下将该混合物温热到100℃。现在在3小时内添加1978.5g聚丙二醇,其借助DMC催化剂(不含碱)制备(不饱和基团含量<0.01meq/g,摩尔重量为2000g/mol,OH值为56,理论官能度为2)。然后在100℃温热该反应混合物,直到达到26.1%的NCO含量。现将温度降低到90℃,在添加360mg双(2-乙基己酸)锌(II)后搅拌该反应混合物,直到NCO含量为24.3%。在添加360mg间苯二甲酰氯后,在0.5mbar和140℃借助薄层蒸馏除去过量的1,6-己烷二异氰酸酯。
得到NCO含量为5.9%、粘度为2070mPas(23℃)和游离HDI残余含量<0.03%的澄清无色产物。
制备预聚物2
首先向1003.4g 1,6-己烷二异氰酸酯添加40mg间苯二甲酰氯,然后在搅拌条件下将该混合物温热到100℃。现在在3小时内添加796.3g聚四亚甲基二醇(=聚四氢呋喃,分子量2000g/mol,OH值为56,理论官能度为2)。然后在100℃温热该反应混合物,直到达到26.0%的NCO含量。现将温度降低到90℃,在添加140mg双(2-乙基己酸)锌(II)后搅拌该反应混合物,直到NCO含量为24.2%。在添加140mg间苯二甲酰氯后,在0.5mbar和140℃借助薄层蒸馏除去过量的1,6-己烷二异氰酸酯。
得到NCO含量为5.9%、粘度为17300mPas(23℃)和游离HDI残余含量为0.06%的澄清无色产物。
制备预聚物3
先向77.3g 1,6-己烷二异氰酸酯添加4mg间苯二甲酰氯,然后在搅拌条件下将该混合物温热到100℃。现在在3小时内添加122.7g聚丙二醇,其借助DMC催化(不含碱)制备(不饱和基团含量<0.01meq/g,摩尔重量为4000g/mol,OH值为28,理论官能度为2)。然后在100℃温热该反应混合物,直到达到18.0%的NCO含量。现将温度降低到90℃,在添加20mg双(2-乙基己酸)锌(II)后搅拌该反应混合物,直到NCO含量为16.7%。在添加20mg间苯二甲酰氯后,在0.7mbar和140℃借助薄层蒸馏除去过量的1,6-己烷二异氰酸酯。
得到NCO含量为3.2%、粘度为3189mPas(23℃)和游离HDI残余含量<0.03%的澄清无色产物。
制备预聚物4(对比例)
在100℃在搅拌条件下在5小时内向321.4g 1,6-己烷二异氰酸酯添加378.4g聚丙二醇,其借助DMC催化(不含碱)制备(不饱和基团含量<0.01meq/g,摩尔重量为2000g/mol,OH值为56,理论官能度为2)。然后在搅拌条件下于100℃温热该混合物,直到达到20.7%的NCO含量。最后,在添加140mg磷酸二丁酯之后,在0.5mbar和140℃借助薄层蒸馏除去过量的1,6-己烷二异氰酸酯。
得到NCO含量为3.15%、粘度为1596mPas(23℃)和游离HDI残余含量<0.03%的澄清无色产物。
脲基甲酸酯1(对比例)
使用由伯醇开始制备的基于HDI的脲基甲酸酯,其具有19.7%的NCO含量并具有415mPas(23℃)的粘度。
制备聚天冬氨酸酯1
在搅拌条件下于50℃将344g(2mol)马来酸二乙酯滴加到210g(2当量)的4,4’-二氨基二环己基甲烷中。添加结束后在60℃于N2气氛继续搅拌90小时并在最后两小时内于1mbar脱水。得到当量重量为277g的液态产物。
制备聚天冬氨酸酯2
在搅拌条件下于50℃将344g(2mol)马来酸二乙酯滴加到238g(2当量)的3,3’-二甲基-4,4’-二氨基二环己基甲烷中。添加结束后在60℃于N2气氛继续搅拌90小时并在最后两小时内于1mbar脱水。得到当量重量为291g的液态产物。
制备涂料
将预聚物1和2以及脲基甲酸酯1(对比例)在室温下分别与氨基官能的聚天冬氨酸酯1和2混合,其中NCO/NH比保持为1.05∶1。然后,借助150μm刮刀在玻璃板上施加相应的膜。涂层的组成和性质总结在表1中。
表1:实施例1-6-膜的组成和性质
n.b.未测量;贮存期是指所述组合物仍能被加工成膜的时间。
含脲基甲酸酯基团的预聚物1和2基于原则上相同的单元。由于它们好的相溶性、高的官能度和好的柔化性能,因而在24小时内得到不发粘的柔性、韧性和澄清膜。
与此不同,借助脲基甲酸酯1,尽管固化得非常快,但是得到脆性膜,以致不能测定机械性能。
固化试验
预聚物1、3和4(对比实施例)在室温下与氨基官能的聚天冬氨酸酯1混合,其中NCO/NH比例保持在1.05∶1。在混合后,最终将澄清组合物浇注成3mm厚膜。膜的组成和固化性质总结在表2中。
表2:实施例7-9
含脲基甲酸酯基团的预聚物1和3在24小时后得到澄清、柔性和不发粘的膜,而预聚物4(不含脲基甲酸酯基团)没有表现出完全固化(和预聚物3相同的NCO含量)。
Claims (11)
2.根据权利要求1的双组分涂料体系,其特征在于,在A)中使用的脲基甲酸酯可通过如下方法获得,其中
A1)一种或多种脂族和/或脂环族多异氰酸酯与
B1)一种或多种多羟基化合物,其中至少一种为聚醚多元醇,
反应生成NCO官能的聚氨酯预聚物,然后这样形成的氨基甲酸酯基团在添加下列组分条件下部分或者全部脲基甲酸酯化
A3)多异氰酸酯,其可以与来自A1)的不同,和
A4)催化剂,和
A5)视需要的稳定剂。
3.根据权利要求2的双组分涂料体系,其特征在于,在A)中使用的脲基甲酸酯的制备时在组分A1)和A3)中使用己烷二异氰酸酯(六亚甲基二异氰酸酯,HDI)、4,4’-亚甲基双(环己基异氰酸酯)和/或3,5,5-三甲基-1-异氰酸根合-3-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯,IPDI)作为多异氰酸酯。
4.权利要求2或3的双组分涂料体系,其特征在于,在A1)和A3)中使用相同类型的多异氰酸酯。
5.权利要求2-4之一的双组分涂料体系,其特征在于,为了脲基甲酸酯化在A4)中作为催化剂使用锌(II)化合物。
6.权利要求5的双组分涂料体系,其特征在于,作为锌(II)化合物使用双(2-乙基己酸)锌(II)、双(正辛酸)锌、双硬脂酸锌或它们的混合物。
7.权利要求2-6之一的双组分涂料体系,其特征在于,在A2)中仅使用聚醚多元醇,其中该聚醚多元醇具有2000-6000g/mol的数均分子量Mn,≥1.95的平均OH官能度和根据ASTM D2849-69小于或等于0.01meq/g的不饱和端基程度。
8.权利要求2-7之一的双组分涂料体系,其特征在于,组分A2)的化合物的OH基团对来自A1)和A3)的多异氰酸酯的NCO基团的摩尔比为1∶2-1∶10。
9.权利要求2-8之一的双组分涂料体系,其特征在于,在A5)中作为稳定剂使用无机酸或有机酸、酰卤或酯。
10.涂料,其可以根据权利要求1-9之一的双组分涂料体系获得。
11.基材,其用根据权利要求10的涂料涂覆。
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-
2005
- 2005-10-04 DE DE102005047562A patent/DE102005047562A1/de not_active Withdrawn
-
2006
- 2006-09-20 US US11/524,001 patent/US7927704B2/en active Active
- 2006-09-22 ES ES06777194T patent/ES2383224T3/es active Active
- 2006-09-22 EP EP06777194A patent/EP1937742B1/de not_active Not-in-force
- 2006-09-22 PL PL06777194T patent/PL1937742T3/pl unknown
- 2006-09-22 JP JP2008533896A patent/JP5275032B2/ja not_active Expired - Fee Related
- 2006-09-22 WO PCT/EP2006/009203 patent/WO2007039133A1/de active Application Filing
- 2006-09-22 BR BRPI0616849-3A patent/BRPI0616849A2/pt not_active IP Right Cessation
- 2006-09-22 CN CNA200680036690XA patent/CN101277988A/zh active Pending
- 2006-09-22 CA CA 2624312 patent/CA2624312C/en not_active Expired - Fee Related
- 2006-09-22 AU AU2006299127A patent/AU2006299127B2/en not_active Ceased
- 2006-09-22 AT AT06777194T patent/ATE554117T1/de active
- 2006-09-22 KR KR1020087008051A patent/KR20080064822A/ko not_active Application Discontinuation
-
2008
- 2008-03-11 IL IL190075A patent/IL190075A0/en unknown
- 2008-04-21 NO NO20081898A patent/NO20081898L/no not_active Application Discontinuation
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102300893A (zh) * | 2009-02-03 | 2011-12-28 | 拜尔材料科学股份公司 | 基于含有脲基甲酸酯基团的多异氰酸酯的涂料 |
CN102300894A (zh) * | 2009-02-03 | 2011-12-28 | 拜尔材料科学股份公司 | 用于柔性涂层的双组分涂料组合物 |
CN102300894B (zh) * | 2009-02-03 | 2014-06-25 | 拜尔材料科学股份公司 | 用于柔性涂层的双组分涂料组合物 |
WO2012000944A1 (en) | 2010-06-29 | 2012-01-05 | Bayer Materialscience Ag | Aliphatic polyurea coating, the method for preparing the same and the use thereof |
CN106029728A (zh) * | 2014-02-25 | 2016-10-12 | 涂层国外知识产权有限公司 | 包含二异氰酸酯扩链的二天冬氨酸酯的涂料组合物 |
CN106029729A (zh) * | 2014-02-25 | 2016-10-12 | 涂层国外知识产权有限公司 | 包含二异氰酸酯扩链的二天冬氨酸酯的涂料组合物 |
CN106029728B (zh) * | 2014-02-25 | 2019-08-06 | 涂层国外知识产权有限公司 | 包含二异氰酸酯扩链的二天冬氨酸酯的涂料组合物 |
CN106029729B (zh) * | 2014-02-25 | 2019-11-08 | 涂层国外知识产权有限公司 | 包含二异氰酸酯扩链的二天冬氨酸酯的涂料组合物 |
Also Published As
Publication number | Publication date |
---|---|
CA2624312A1 (en) | 2007-04-12 |
EP1937742A1 (de) | 2008-07-02 |
JP5275032B2 (ja) | 2013-08-28 |
CA2624312C (en) | 2014-03-25 |
JP2009510238A (ja) | 2009-03-12 |
IL190075A0 (en) | 2008-08-07 |
US20070078255A1 (en) | 2007-04-05 |
AU2006299127B2 (en) | 2011-12-01 |
NO20081898L (no) | 2008-04-21 |
KR20080064822A (ko) | 2008-07-09 |
PL1937742T3 (pl) | 2012-09-28 |
US7927704B2 (en) | 2011-04-19 |
BRPI0616849A2 (pt) | 2011-07-05 |
EP1937742B1 (de) | 2012-04-18 |
WO2007039133A1 (de) | 2007-04-12 |
ATE554117T1 (de) | 2012-05-15 |
DE102005047562A1 (de) | 2007-04-05 |
AU2006299127A1 (en) | 2007-04-12 |
ES2383224T3 (es) | 2012-06-19 |
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