CN114479565A - Coating composition and method for controlling the rate of crosslinking reaction thereof - Google Patents
Coating composition and method for controlling the rate of crosslinking reaction thereof Download PDFInfo
- Publication number
- CN114479565A CN114479565A CN202011145807.6A CN202011145807A CN114479565A CN 114479565 A CN114479565 A CN 114479565A CN 202011145807 A CN202011145807 A CN 202011145807A CN 114479565 A CN114479565 A CN 114479565A
- Authority
- CN
- China
- Prior art keywords
- coating composition
- group
- crosslinking
- isocyanate
- metal catalyst
- 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
- 239000008199 coating composition Substances 0.000 title claims abstract description 107
- 238000004132 cross linking Methods 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 51
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- 239000012948 isocyanate Substances 0.000 claims description 27
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004971 Cross linker Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000002981 blocking agent Substances 0.000 claims description 12
- 230000000536 complexating effect Effects 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- -1 acetobutanone Chemical compound 0.000 claims description 6
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- PRRBQHNMYJRHFW-UHFFFAOYSA-M 3-oxoheptanoate Chemical compound CCCCC(=O)CC([O-])=O PRRBQHNMYJRHFW-UHFFFAOYSA-M 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 description 23
- 239000003973 paint Substances 0.000 description 21
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 16
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- PSCJODZIMUSFCK-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole-2-carboxylic acid Chemical compound OC(=O)C1=NCCO1 PSCJODZIMUSFCK-UHFFFAOYSA-N 0.000 description 1
- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001125671 Eretmochelys imbricata Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UCXRDUYATJAIQG-UHFFFAOYSA-N OC(=O)N=C=N Chemical compound OC(=O)N=C=N UCXRDUYATJAIQG-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000000232 haloalkynyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- VGPBPWRBXBKGRE-UHFFFAOYSA-N n-(oxomethylidene)hydroxylamine Chemical compound ON=C=O VGPBPWRBXBKGRE-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- RPDJEKMSFIRVII-UHFFFAOYSA-N oxomethylidenehydrazine Chemical compound NN=C=O RPDJEKMSFIRVII-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- RUUOPSRRIKJHNH-UHFFFAOYSA-N pyridazine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=N1 RUUOPSRRIKJHNH-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012384 transportation and delivery Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a coating composition and a method for controlling the speed of a crosslinking reaction of the coating composition, and the composition and the method provide a single-component crosslinking system suitable for a coating, and the composition and the method can particularly provide excellent storage stability while meeting the requirement of low-temperature crosslinking of the coating, meet the storage requirement of the single-component system, and solve the problems that the construction time limit is short after the traditional two-component system is mixed and the traditional single-component system needs high-temperature baking crosslinking.
Description
Technical Field
The invention relates to the field of coatings. In particular, the present invention relates to a coating composition and a method of controlling the rate of a crosslinking reaction thereof.
Background
Coatings can be generally divided into two-component systems and one-component systems, depending on the packaging composition. Typically, one component of a two-component system comprises a curable resin and the other component comprises a cross-linking agent for the curable resin, and the resin (host) and cross-linking agent are thoroughly mixed and applied at the time of use. However, the two-component system has several problems in that the imprecision of the content of each component or the excessively fast reaction rate leads to incomplete or excessively fast curing, a crosslinking reaction of the main agent and the crosslinking agent may occur upon mixing, the storage cannot be prolonged, and the pot life is very short. Therefore, the two-component system requires that the prepared coating is used up as soon as possible during the use process; while the two-component systems themselves are generally sensitive to moisture and humidity, storage and recycling requires extra care to prevent deterioration of the crosslinking agent.
Typical one-component systems can be divided into non-crosslinking one-component systems and crosslinking one-component systems. Wherein, the non-crosslinking single-component system mainly relies on the resin component to carry out drying and physical film forming, thereby achieving certain mechanical property and strength. However, since the resin is physically formed into a film only by itself, the crosslinking density is insufficient, and good resistance cannot be provided, particularly, the solvent resistance is poor, so that the range of use is narrow, and the resin is widely used in the civil field such as exterior wall paints and emulsion paints. The crosslinking type single component system needs to bake the coated paint at high temperature to initiate the crosslinking reaction of the crosslinking agent, so that the coated film has good crosslinking density and the resistance are improved. However, the activation energy of the traditional cross-linking type single-component system is higher, and the reaction can only be carried out at the temperature of between 120 and 140 ℃ generally. Especially for the automotive and coil coating industries, it is advantageous to reduce the number of high temperature steps and processing time.
In view of the advantages of natural stability (no deterioration after 6 months of storage at room temperature) and environmental protection (baking temperature less than or equal to 120 ℃), if the balance between the crosslinking effect and the stability of the crosslinking type single-component system at low temperature can be realized, the rate of the crosslinking reaction is controlled by adopting a specific steric hindrance group and/or a catalyst and/or a solvent, the stability of the single-component system and the degree of the low-temperature crosslinking reaction are improved, and the industrial field range of the single-component system can be greatly expanded.
Disclosure of Invention
The object of the present invention is to achieve storage-stable one-component coating compositions which can be cured at temperatures of from 60 ℃ to 120 ℃ in a curing time of 600 minutes or less. These low temperature curable coating compositions may include a functional resin having a steric group, and/or a crosslinkable agent that may be blocked, and/or a metal catalyst, and/or a complexing solvent. The coating composition is storage stable in that any one or more of the combination of a functional resin with a sterically hindered group, a cross-linking agent that can be blocked, a catalyst, and a solvent, controls the cross-linking reaction between the functional resin and the cross-linking agent.
In a first aspect of the present invention, there is provided a low temperature curable coating composition comprising a functional resin containing hydroxyl, amino or isocyanate groups, and/or a crosslinkable agent which may be blocked, and/or a metal catalyst, and/or a complexing solvent.
Further wherein the structure of the functional resin comprises the following group I:
further, the crosslinking agent is a blocked isocyanate resin.
Further, the central metal ion of the metal catalyst is selected from tin, iron, cobalt, nickel, zinc, zirconium, titanium or aluminum;
further, the complexing solvent and the central metal ion M of the metal catalyst are subjected to a complexing reaction to form a structure shown as a formula II:
Further, the coating composition is cured at a temperature of 60 ℃ to 120 ℃ (preferably 80 ℃ to 100 ℃) in 1 minute to 600 minutes (preferably 3 minutes to 300 minutes, more preferably 10 minutes to 150 minutes).
Further, the functional group X is a hydroxyl group.
Further, said R0Is a straight chain or branched chain alkyl of C1-C6, preferably methyl or n-pentyl.
Further, the crosslinking agent is selected from polyisocyanates blocked with at least one of methyl ethyl ketoxime, acetoxime, 3, 5-dimethylpyrazole, 2-methylimidazole, acetylacetone, ethyl acetoacetate, diethyl malonate, caprolactam, phenol, catechol, tert-butanol, isopropanol, ethanol, methanol and sodium sulfite.
Further, the crosslinking agent is triisocyanate blocked by methyl ethyl ketoxime or acetone oxime.
Further, the metal catalyst is selected from dibutyltin dilaurate, zinc acetate, zirconium n-butoxide, cobalt chloride, nickel chloride, ferrous acetate, ferric acetate, nickel oxide, aluminum isopropoxide, or aluminum oxide.
Further, the boiling point of the complexing solvent ranges from 120 ℃ to 180 ℃.
Further, the complexing solvent is selected from acetylacetone, acetyl butanone, ethyl acetoacetate, propyl acetoacetate or ethyl malonyl acetate.
Further, the low temperature cured coating composition comprises, based on the total weight of the composition: 30.0 to 70.0 wt.% of a functional resin, and/or 20.0 to 50.0 wt.% of a crosslinkable agent that can be blocked, and/or 0.01 to 5.0 wt.% of a catalyst, and/or 5.0 to 30.0 wt.% of a solvent.
Further, the low temperature cured coating composition has a viscosity change of no more than 30% when stored at 0 ℃ to 50 ℃ for at least 90 days.
Further, the low temperature cured coating composition has a viscosity change of no more than 20% when stored at 10 ℃ to 40 ℃ for at least 30 days.
Further, the low temperature cured coating composition has a viscosity change of no more than 10% when stored at 10 ℃ to 30 ℃ for at least 10 days.
In a second aspect of the invention, there is provided a low temperature coating obtained by curing the coating composition of the first aspect of the invention at a temperature of 60 ℃ to 120 ℃ for 1 minute to 600 minutes.
In a third aspect of the invention, there is provided a kit comprising a coating composition according to the first aspect of the invention and an adjuvant.
In a fourth aspect of the invention, there is provided a method of curing a coating composition according to the first aspect of the invention, said method comprising curing the coating composition at a temperature of from 60 ℃ to 120 ℃.
In a fifth aspect of the present invention, there is provided a method of controlling the rate of a crosslinking reaction of a coating composition comprising a functional resin, said method comprising the steps of: preparing a functional resin containing sterically hindered groups, the structure of said functional resin comprising the following group I:
In a sixth aspect of the present invention, there is provided a method of controlling the rate of a crosslinking reaction of a coating composition, the method comprising the steps of:
providing a blocking agent and a polyisocyanate, wherein the molar ratio of hydroxyl groups to isocyanate NCO groups in the blocking agent is 1:1 to 3:1, the blocking agent is selected from methyl ethyl ketoxime, acetoxime, 3, 5-dimethylpyrazole, 2-methylimidazole, acetylacetone, ethyl acetoacetate, diethyl malonate, caprolactam, phenol, catechol, tert-butanol, isopropanol, ethanol or methanol and sodium sulfite;
a metal catalyst is provided in which the central metal ion is selected from tin, iron, cobalt, nickel, zinc, zirconium, titanium or aluminum.
The temperature stability and pot life of the coating composition are further improved by blocking or protecting the reactive groups of the crosslinker. The blocking of the reactive groups of the crosslinker results in a higher cure initiation temperature, which makes it possible to provide a one-component system in which the functional resin, the blocked crosslinker and the catalyst are all contained prior to application of the one-component system.
In blocked isocyanate resins, when the blocking group itself is removed from the isocyanate resin (i.e., deblocked) thereby leaving a free isocyanate group, it reacts with the hydroxyl group of the hydroxy-functional resin. The free NCO groups react with the hydroxyl groups to form carbamate linkages (-NH-CO-O-), thereby forming crosslinked carbamates. In the absence of metal catalysts, the blocked isocyanate crosslinker remains blocked and only slowly deblocks the isocyanate resin even at elevated temperatures. The blocked isocyanate resin is also less susceptible to crosslinking with the hydroxy-functional resin, and even less self-crosslinking, at temperatures of 60 ℃ to 120 ℃. Blocked isocyanate resins mean that more than 90% of the NCO groups are blocked, even more than 95% or 99% of the groups are blocked. The blocked isocyanate may be any isocyanate suitable for crosslinking, typically a polyisocyanate, preferably a diisocyanate or triisocyanate. The blocking agents may be used alone or in combination.
The higher the temperature at which the blocking group is deblocked, the less likely the crosslinking agent is to be able to undergo the necessary crosslinking reaction in the presence of a metal catalyst at 60 ℃ to 120 ℃, and it is preferred that the blocking group is deblocked from the isocyanate resin at a temperature of 40 ℃ to 70 ℃.
Further, under the control of a catalyst, the reaction activation temperature of 60-120 ℃ is one or more of carboxyl-carbodiimide crosslinking reaction, carboxyl-hydroxyl crosslinking reaction, carboxyl-oxazoline crosslinking reaction, carboxyl-azapyridine crosslinking reaction, epoxy-dicyandiamide, epoxy-carboxyl, hydroxyl-isocyanate, amino-isocyanate and other crosslinking reactions with arbitrary activation temperature of 60-120 ℃.
In a seventh aspect of the present invention, there is provided a method of controlling the rate of a crosslinking reaction of a coating composition, the method comprising the steps of: providing a metal catalyst and a solvent, and carrying out a complex reaction to form a structure shown as a formula II:
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1. the low-temperature curing coating composition provided by the invention is used as a single-component low-temperature crosslinking system, gives consideration to the low-temperature crosslinking requirement of the coating composition, can provide excellent storage stability, overcomes the defect that the construction working hours are short after the traditional two-component coating is mixed, and also overcomes the defect that the traditional single-component coating needs high-temperature baking for crosslinking reaction.
2. The low-temperature curing coating composition provided by the invention greatly expands the application range of a single-component low-temperature crosslinking system, and can be used for vehicles, engineering machinery, anticorrosive materials, terraces, wood, coiled materials and the like.
Detailed Description
Specific examples of the present invention are described in detail below. However, the present invention should be understood not to be limited to such an embodiment described below, and the technical idea of the present invention may be implemented in combination with other known techniques or other techniques having the same functions as those of the known techniques.
In the following description of the embodiments, the present invention will be described with reference to various directional terms in order to clearly illustrate the structure and operation of the invention, but the terms "front", "rear", "left", "right", "outer", "inner", "outer", "inward", "axial", "radial", and the like should be construed as words of convenience and should not be construed as limiting terms.
Description of the terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "about" when used in reference to a specifically recited value means that the value may vary by no more than 1% from the recited value. For example, as used herein, the expression "about 100" includes 99 and 101 and all values in between (e.g., 99.1, 99.2, 99.3, 99.4, etc.).
As used herein, the term "comprising" or "includes" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the subject matter claimed. In this application, the use of the singular also includes the plural unless specifically stated otherwise. It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It should also be noted that the use of "or", "or" means "and/or" unless stated otherwise. Furthermore, the terms "comprising" or "including" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
As used herein, "low temperature" in the term "low temperature cured coating composition" and the like may be understood as not exceeding 120 ℃, further may be understood as 60 ℃ to 120 ℃.
As used herein, the level of cure can also be assessed by measuring gel content, which directly indicates the degree of cure due to crosslinking.
As used herein, the term "two-component system" has its ordinary meaning in the art and can be understood as a system of separately packaged curable resin and crosslinker.
Definitions for the terms of the standardization sector can be found in the literature references including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4TH ED." Vols.A (2000) and B (2001), Plenum Press, New York. Unless otherwise indicated, conventional methods within the skill of the art are employed, such as mass spectrometry, NMR, IR and UV/VIS spectroscopy, and pharmacological methods. Unless a specific definition is set forth, the terms used herein in the context of analytical chemistry, organic synthetic chemistry, and the relevant description of pharmaceutical and pharmaceutical chemistry are known in the art. Standard techniques can be used in chemical synthesis, chemical analysis, pharmaceutical preparation, formulation and delivery, and treatment of patients. For example, the reaction and purification can be carried out using the instructions of the kit from the manufacturer, or according to the methods known in the art or the instructions of the present invention. The techniques and methods described above can generally be practiced according to conventional methods well known in the art, as described in various general and more specific documents referred to and discussed in this specification. In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds.
When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when the formula is written from right to left. For example, -CH2O-is equivalent to-OCH2-。
The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including but not limited to patents, patent applications, articles, books, operating manuals, and papers, are hereby incorporated by reference in their entirety.
Certain chemical groups defined herein are preceded by a shorthand notation to indicate the total number of carbon atoms present in the group. For example, C1-C6 alkyl refers to an alkyl group as defined below having a total of 1 to 6 carbon atoms. The total number of carbon atoms in the shorthand notation excludes carbons that may be present in a substituent of the group.
In addition to the foregoing, the following terms, when used in the specification and claims of this application, have the meanings indicated below, unless otherwise specifically indicated.
"hydroxy" means an-OH group.
In this application, the term "alkyl" as a group or as part of another group (e.g., as used in halo-substituted alkyl and the like groups) refers to a fully saturated straight or branched hydrocarbon chain radical consisting only of carbon and hydrogen atoms, having, for example, 1 to 7 carbon atoms, and attached to the rest of the molecule by a single bond, including, but not limited to, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 2-dimethylpropyl, n-hexyl, heptyl, and the like.
In this application, "optionally" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. For example, "optionally substituted aryl" means that the aryl group is substituted or unsubstituted, and the description includes both substituted and unsubstituted aryl groups. The "optionally" substituents described in the claims and the description section of the present invention are selected from alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, cyano, nitro, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl.
The terms "moiety," "structural moiety," "chemical moiety," "group," "chemical group" as used herein refer to a specific segment or functional group in a molecule. Chemical moieties are generally considered to be chemical entities that are embedded in or attached to a molecule.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically stated otherwise.
Unless clearly indicated to the contrary, each aspect or embodiment defined herein may be combined with any other aspect or embodiments. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature indicated as being preferred or advantageous.
Reagent and apparatus
The following reagents were used as received:
setalux 1774-SS-65 (from Nuplex);
BL3370 isocyanate (from Coverstro);
butyl acetate (purchased from shanghai Lingfeng chemical);
BYK-306 (from BYK);
DBTDL (available from shanghai Lingfeng chemical);
isocyanate Desmodur N3300 (from Coverstro);
comparative example 1 preparation of coating composition C1
A coating composition C1 was prepared by mixing 63.0g of Setalux 1774-SS-65 resin, 21.6g of BL3370 isocyanate, 17.4g of butyl acetate, 0.2g of BYK-306, and 0.5g of DBTDL at room temperature for 30 minutes. The coating composition C1 was a one-component system.
Coating composition C1 was applied to a substrate using a 150um drawdown bar and baked at 80 ℃ for 30 minutes to give a paint film of coating composition C1.
Comparative example 2 preparation of coating composition C2
A coating composition C2 was prepared by mixing 63.0g of Setalux 1774-SS-65 resin, 23.0g of the crosslinker isocyanate Desmodur N3300, 14.7g of butyl acetate, 0.2g of BYK-306, and 0.5g of DBTDL for 30 minutes at room temperature. The coating composition C2 was a one-component system.
Coating composition C2 was applied to a substrate using a 150um drawdown bar and baked at 80 ℃ for 30 minutes to give a paint film of coating composition C2.
Comparative example 3 preparation of coating composition C3
Firstly, synthesizing a main resin PE-1000: 25.75g of epsilon-caprolactone, 0.64g of stannous isooctanoate, 1.60g of ethylene glycol and 25.00g of dimethylbenzene are reacted in an oil bath at 140 ℃ for 24 hours, and after the residual acid value is tested to be less than 5, the PE-1000 resin is obtained by cooling.
A coating composition C3 was prepared by mixing 63.0g of PE-1000 resin, 23.0g of the crosslinker isocyanate Desmodur N3300, 13.3g of butyl acetate, 0.2g of BYK-306, 0.5g of DBTDL for 30 minutes at room temperature. The coating composition C3 was a two-component system.
Coating composition C3 was applied to a substrate using a 150um drawdown bar and baked at 80 ℃ for 30 minutes to give a paint film of coating composition C3.
Example 4 preparation of coating composition 4
The host resin PE-1001 was first synthesized. 25.75g of epsilon-caprolactone, 0.64g of stannous isooctanoate, 1.96g of 1, 2-propylene glycol and 25.00g of dimethylbenzene are reacted in an oil bath at 140 ℃ for 24 hours, and after the residual acid value is tested to be less than 5, the PE-1001 resin is obtained by cooling. The ortho position of the hydroxyl group of the host resin PE1001 has methyl steric hindrance.
A coating composition 4 was prepared by mixing 63.0g of PE-1001 resin, 23.0g of the crosslinker isocyanate Desmodur N3300, 13.3g of butyl acetate, 0.2g of BYK-306, and 0.5g of DBTDL at room temperature for 30 minutes. The coating composition 4 is a two-component system.
The coating composition 4 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 4.
EXAMPLE 5 preparation of coating composition 5
The host resin PE-1005 was first synthesized. 25.75g of epsilon-caprolactone, 0.64g of stannous isooctanoate, 3.05g of 1,2 hexanediol and 25.00g of dimethylbenzene are reacted in an oil bath at 140 ℃ for 24 hours, and after the residual acid value is tested to be less than 5, the PE-1005 resin is obtained by cooling. The hydroxyl group of the main body resin PE1005 has n-amyl steric hindrance in the ortho-position.
A coating composition 5 was prepared by mixing 63.0g of PE-1005 resin, 23.0g of the crosslinker isocyanate Desmodur N3300, 13.3g of butyl acetate, 0.2g of BYK-306, and 0.5g of DBTDL at room temperature for 30 minutes. The coating composition 5 is a two-component system.
The coating composition 5 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 5.
Example 6 preparation of coating composition 6
First, a blocked crosslinker BIT-50 was prepared by the following steps:
(1) 50g of isocyanate trimer, 18g of cyclohexanone, 20g of xylene, 25g of butanone, 0.3g of DBTDL were added to produce an isocyanate solution. Wherein, the isocyanate-containing trimer can be one or more selected from HDI trimer, TDI trimer, MDI trimer and IPDI trimer.
(2) Heating the isocyanate solution to 45 ℃, gradually dripping the sealant at the rotating speed of 500-800 rpm, keeping the ratio of the hydroxyl group of the sealant to the NCO group of the isocyanate within the range of 1: 1-3: 1, finishing dripping the sealant for 2 hours, keeping the temperature for 0.5 hour, and slowly heating to 70-75 ℃;
wherein, the blocking agent can be one or more of methyl ethyl ketoxime, acetoxime, 3, 5-dimethylpyrazole, 2-methylimidazole, acetylacetone, ethyl acetoacetate, diethyl malonate, caprolactam, phenol, catechol, tert-butyl alcohol, isopropanol, ethanol, methanol and sodium sulfite.
(3) Until the characteristic peak of isocyanate in the solution is detected by infrared ray at 2250cm-1Disappearance, as end point of reaction, obtaining the blocked crosslinker BIT-50.
40g of Setalux 1774-SS-65, 40g of crosslinker BIT-50, 17.2g of butyl acetate, 0.2g of BYK-306 and 0.5g of DBTDL were mixed at room temperature for 30 minutes to prepare coating composition 6.
The coating composition 6 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 6.
Example 7 preparation of coating composition 7
Firstly, preparing a solvent complex catalyst-1: a mixture of 5.0g DBTDL, 93.4g butyl acetate and a complexing solvent (i.e., 1.6g acetylacetone) was stirred at 500rpm for 30min to prepare solvent complex catalyst-1.
A coating composition 7 was prepared by mixing 63.0g of Setalux 1774-SS-65, 23.0g of the crosslinking agent Desmodur N3300, 13.3g of butyl acetate, 0.2g of BYK-306, and 0.5g of the solvent complex catalyst-1 at room temperature for 30 minutes.
The coating composition 7 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 7.
Example 8 preparation of coating composition 8
Firstly, preparing a solvent complex catalyst-2, and stirring a mixture of 5.0g of DBTDL, 93.4g of butyl acetate and a complex solvent (namely 2.1g of ethyl acetoacetate) at the rotating speed of 500rpm for 30min to prepare the solvent complex catalyst-2.
A coating composition 8 was prepared by mixing 63.0g of Setalux 1774-SS-65, 23.0g of the crosslinking agent Desmodur N3300, 13.3g of butyl acetate, 0.2g of BYK-306, and 0.5g of the solvent complex catalyst-2 at room temperature for 30 minutes.
The coating composition 8 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 8.
Example 9 preparation of coating composition 9
Firstly, preparing a solvent complex catalyst-3, and stirring a mixture of 1.5g of anhydrous zinc acetate, 93.4g of butyl acetate and 2.1g of a complex solvent (namely ethyl acetoacetate) at the rotating speed of 500rpm for 30min to prepare the solvent complex catalyst-3.
A coating composition 9 was prepared by mixing 63.0g of Setalux 1774-SS-65, 23.0g of the crosslinking agent Desmodur N3300, 13.3g of butyl acetate, 0.2g of BYK-306, and 0.5g of the solvent complex catalyst-3 at room temperature for 30 minutes.
The coating composition 9 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 9.
Comparative example 4 preparation of coating composition C4
40.0g of Setalux 1774-SS-65 resin, 40.0g of crosslinking agent BIT-50, 17.2g of butyl acetate and 0.2g of BYK-306 were mixed at room temperature for 30 minutes to prepare a coating composition C4.
Coating composition C4 was applied to a substrate using a 150um drawdown bar and baked at 80 ℃ for 30 minutes to give a paint film of coating composition C4.
Example 11 preparation of coating composition 11
40.0g of Setalux 1774-SS-65 resin, 40.0g of a crosslinking agent BIT-50, 17.2g of butyl acetate, 0.2g of BYK-306 and 0.5g of anhydrous zinc acetate were mixed at room temperature for 30 minutes to prepare a coating composition 11. Wherein anhydrous zinc acetate is used as a catalyst for the low-temperature deblocking reaction.
The coating composition 11 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 11.
EXAMPLE 12 preparation of coating composition 12
40.0g of Setalux 1774-SS-65 resin, 40.0g of a crosslinking agent BIT-50, 17.2g of butyl acetate, 0.2g of BYK-306 and 0.5g of zirconium n-butoxide were mixed at room temperature for 30 minutes to prepare a coating composition 12. Wherein the n-butyl zirconium is used as a catalyst for the low-temperature deblocking reaction.
The coating composition 12 was applied to a substrate using a 150um draw down bar and baked at 80 ℃ for 30 minutes to give a paint film of the coating composition 12.
Performance testing
Testing the service life at room temperature:
the coating bleeding time was measured by leaving it at 23. + -. 2 ℃ for a certain time interval according to GB 6753.4-1986 measurement of the bleeding time of coating. When the flowing-out time is increased to 2 times of the initial flowing-out time, the time interval is the using time limit of the coating at room temperature.
And (4) testing the storage stability:
the storage stability of the coatings was tested according to GB-T6753.3-1986 test method for the storage stability of coatings.
MEK rub resistance test:
according to the MEK resistance of a paint film tested by GB-T23989-2009 paint solvent wiping resistance test method, the more times of resistance indicate that the crosslinking density is higher.
The test results are shown in table 1 below:
first, with respect to table 1 above, it should be noted that: the test of the MEK resistance of the paint film is a precondition for judging the 'service life at room temperature' and the 'viscosity change after storage'.
The MEK resistance times shown in the coating compositions C1 and C4 as comparative examples above were 0 and 20 times, respectively, and thus they could not satisfy the requirements of the coating composition of the present invention, wherein the "room temperature service life" and "viscosity change after storage" are shown only for reference.
As can be seen from Table 1 above, the coating composition C1 as a control was a conventional one-component system, which required high temperature conditions to perform the crosslinking reaction and failed to perform at a low temperature of 80 ℃; the coating composition C2 as a control was a conventional two-component system which allowed crosslinking reaction at a low temperature of 80 ℃ but had a short pot life at room temperature (4 hours) and poor storage stability.
The comparative coating compositions C1, C2 and 6, 11, 12, which contain blocked cross-linking agents and metal catalysts, and 6, 11, 12, utilize reactive group blocking techniques, have good shelf life and storage stability at room temperature, are essentially equivalent to conventional one-component systems, and are much higher than conventional two-component coatings. Meanwhile, under the low-temperature baking condition of 80 ℃, the reactivity of the modified polyurethane is basically equal to that of the traditional two-component system and is far higher than that of the traditional one-component system.
In comparison with coating composition C3, coating composition 4 and coating composition 5, coating compositions 4 and 5 exhibited increased steric hindrance due to the inclusion of the hindered group that controls the rate of the crosslinking reaction, i.e., the group ortho to the hydroxyl group was replaced with a methyl group and a pentyl group, respectively, from a hydrogen atom, thereby successfully increasing the pot life of the coating from 4 hours to 5.5 hours and 8.2 hours at room temperature, and achieving the goal of controlling the crosslinking reaction of the one-component system.
Meanwhile, in comparison with coating compositions C2, 7, 8 and 9, coating compositions 7, 8 and 9 successfully reduced the room temperature activity of the synergistically used metal catalysts by using a solvent complexation technique with complexing agents of specific structures (acetylacetone and ethyl acetoacetate), so that the room temperature lifetime of the coatings was extended from 4 hours to 12 hours, 14 hours and 13 hours, respectively, and the final crosslink density was not affected, achieving the purpose of controlling the crosslinking reaction.
In addition, as a control coating composition C4, coating compositions 6, 11, and 12 used a catalyst control technique, compared to coating compositions 6, 11, and 12, to successfully increase the MEK-resistance of the final crosslinked paint film from 20 to 50 times by selecting different catalysts, and achieved the goal of crosslinking reaction control without affecting the room temperature pot life and storage stability of the paint.
Therefore, the coating composition provided by the invention realizes the controllable crosslinking reaction rate at low temperature, ensures longer room-temperature service life, excellent storage stability and paint film performance, and thus provides technical feasibility for a single-component low-temperature crosslinking coating system.
The use of a qualifier such as "a" or "an" in the present context does not imply a limitation on the number, but rather describes a technical feature not previously present, unless otherwise specified. Similarly, modifiers similar to "about", "approximately" or "approximately" that occur before a numerical term herein typically include the same number, and their specific meaning should be read in conjunction with the context. Similarly, unless a specific number of a claim recitation is intended to cover both the singular and the plural, and embodiments may include a single feature or a plurality of features.
The embodiments described in the specification are only preferred embodiments of the present invention, and the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the present invention. Those skilled in the art can make various technical solutions based on the present invention by logical analysis, reasoning, or limited experiments, and all such solutions are within the scope of the present invention.
Claims (11)
1. A low temperature-curable coating composition comprising:
a functional resin having a steric hindrance group; or
A metal catalyst and a crosslinker blocked by a blocking agent; or
A metal catalyst and a complexing solvent;
wherein the content of the first and second substances,
the cross-linking agent is isocyanate resin blocked by a blocking agent;
the complexing solvent and the central metal ion M of the metal catalyst are subjected to a complexing reaction to form a structure shown as a formula II:
2. The coating composition of claim 1, wherein:
the structure of the functional resin includes the following group I:
wherein X is a functional group, is a hydroxyl group, an amino group or an isocyanate group, R0、R1、R2、R3、R4Are respectively a straight chain or branched chain alkyl of C1-C12 or hydrogen, and are not simultaneously hydrogen.
3. The coating composition of claim 1 or 2, wherein the central metal ion of the metal catalyst is selected from tin, iron, cobalt, nickel, zinc, zirconium, titanium, or aluminum.
4. The coating composition according to any one of claims 1 to 3, wherein the crosslinking agent is selected from polyisocyanates blocked with at least one blocking agent selected from the group consisting of methyl ethyl ketoxime, acetoxime, 3, 5-dimethylpyrazole, 2-methylimidazole, acetylacetone, ethyl acetoacetate, diethyl malonate, caprolactam, phenol, catechol, t-butanol, isopropanol, ethanol, methanol and sodium sulfite; preferably, the molar ratio of hydroxyl groups to isocyanate NCO groups in the blocking agent is from 1:1 to 3: 1.
5. The coating composition of any of claims 1-4, wherein the metal catalyst is selected from the group consisting of dibutyltin dilaurate, zinc acetate, zirconium n-butoxide, cobalt chloride, nickel chloride, ferrous acetate, ferric acetate, nickel oxide, aluminum isopropoxide, and aluminum oxide.
6. The coating composition of any one of claims 1-5, wherein the complexing solvent is selected from the group consisting of acetylacetone, acetobutanone, ethyl acetoacetate, propyl acetoacetate, and ethyl propionylacetate.
7. A low temperature coating obtained by curing the coating composition of any one of claims 1-6 at a temperature of 60 ℃ to 120 ℃ for 1 minute to 600 minutes.
8. A method of curing the coating composition of any one of claims 1-6, the method comprising curing the coating composition at a temperature of 60 ℃ to 120 ℃.
9. A method of controlling the rate of a crosslinking reaction of a coating composition comprising a functional resin, said method comprising the steps of: preparing a functional resin containing sterically hindered groups, the structure of said functional resin comprising the following group I:
10. A method of controlling the rate of a crosslinking reaction of a coating composition, the method comprising the steps of:
(1) providing a blocking agent and a polyisocyanate, wherein the molar ratio of hydroxyl groups to isocyanate NCO groups in the blocking agent is 1:1 to 3:1, the blocking agent is selected from methyl ethyl ketoxime, acetoxime, 3, 5-dimethylpyrazole, 2-methylimidazole, acetylacetone, ethyl acetoacetate, diethyl malonate, caprolactam, phenol, catechol, tert-butyl alcohol, isopropanol, ethanol, methanol or sodium sulfite;
(2) a metal catalyst is provided in which the central metal ion is selected from tin, iron, cobalt, nickel, zinc, zirconium, titanium or aluminum.
11. A method of controlling the rate of a crosslinking reaction of a coating composition, the method comprising the steps of: providing a metal catalyst and a solvent, and carrying out a complex reaction to form a structure shown as a formula II:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011145807.6A CN114479565A (en) | 2020-10-23 | 2020-10-23 | Coating composition and method for controlling the rate of crosslinking reaction thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011145807.6A CN114479565A (en) | 2020-10-23 | 2020-10-23 | Coating composition and method for controlling the rate of crosslinking reaction thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114479565A true CN114479565A (en) | 2022-05-13 |
Family
ID=81470629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011145807.6A Pending CN114479565A (en) | 2020-10-23 | 2020-10-23 | Coating composition and method for controlling the rate of crosslinking reaction thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114479565A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4395528A (en) * | 1981-03-02 | 1983-07-26 | M&T Chemicals Inc. | Catalyst composition and curable polymer compositions containing same |
| EP0810245A1 (en) * | 1996-05-28 | 1997-12-03 | Elf Atochem North America, Inc. | Catalyst for low temperature cure of blocked isocyanates |
| US20020068171A1 (en) * | 1997-10-21 | 2002-06-06 | Martin Melchiors | One-component stoving composition and use thereof |
| WO2012044509A1 (en) * | 2010-10-01 | 2012-04-05 | E. I. Du Pont De Nemours And Company | Two-component coating compositions |
| CN109476811A (en) * | 2016-07-26 | 2019-03-15 | 巴斯夫涂料有限公司 | The single-component low temperature curing coating formed via the double-deck curing mechanism |
-
2020
- 2020-10-23 CN CN202011145807.6A patent/CN114479565A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4395528A (en) * | 1981-03-02 | 1983-07-26 | M&T Chemicals Inc. | Catalyst composition and curable polymer compositions containing same |
| EP0810245A1 (en) * | 1996-05-28 | 1997-12-03 | Elf Atochem North America, Inc. | Catalyst for low temperature cure of blocked isocyanates |
| US20020068171A1 (en) * | 1997-10-21 | 2002-06-06 | Martin Melchiors | One-component stoving composition and use thereof |
| WO2012044509A1 (en) * | 2010-10-01 | 2012-04-05 | E. I. Du Pont De Nemours And Company | Two-component coating compositions |
| CN109476811A (en) * | 2016-07-26 | 2019-03-15 | 巴斯夫涂料有限公司 | The single-component low temperature curing coating formed via the double-deck curing mechanism |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4180119B2 (en) | New zirconium urethane catalyst | |
| ZA200209576B (en) | Photoactivatable coating composition. | |
| AU2001260325A1 (en) | Photoactivatable coating composition | |
| EP1778778A2 (en) | Organometallic compositions and coating compositions | |
| JP4421841B2 (en) | Block polyisocyanate | |
| JPH039948B2 (en) | ||
| EP0351873B1 (en) | Process for the preparation of polyisocyanate | |
| EP4144780A1 (en) | Sulfonic acid-modified polyisocyanate and preparation method therefor | |
| CN100467511C (en) | Cyclic ketones as blocking agents | |
| CN108368225B (en) | Acrylic polyurethane coatings comprising polyether polyols | |
| JP3616996B2 (en) | Hydroxy functional urethane with tertiary carbamate linkage | |
| CN114479565A (en) | Coating composition and method for controlling the rate of crosslinking reaction thereof | |
| JP4130583B2 (en) | HDI block polyisocyanate | |
| MXPA05011282A (en) | Blocked biuretized isocyanates. | |
| JP2012107091A (en) | Blocked polyisocyanate composition | |
| US6677424B2 (en) | Coating composition | |
| EP2438103B1 (en) | Two-component coating compositions | |
| AU2006201579A1 (en) | Compounds containing allophanate, isocyanate and ortho ester groups and their use as binders | |
| CN114736351A (en) | Blocked isocyanate curing agent, preparation method thereof and baking type coating | |
| JPH11310753A (en) | One-component bakable composition and use thereof | |
| NO20023535L (en) | Alcohol-blocked polyisocyanates for band coating | |
| CA2270675A1 (en) | Coating composition | |
| CN114805746B (en) | Carbodiimide group-containing polyisocyanate crosslinking agent and preparation method thereof | |
| JP2775291B2 (en) | Aqueous block polyisocyanate composition and thermosetting aqueous composition containing the same | |
| US20060100361A1 (en) | Delayed crosslinking polycondensable composition, use thereof for producing coatings and resulting coatings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |