CN115044013B - Bio-based air-curing type water-based polyurethane urea resin and preparation method thereof - Google Patents
Bio-based air-curing type water-based polyurethane urea resin and preparation method thereof Download PDFInfo
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- CN115044013B CN115044013B CN202210800538.5A CN202210800538A CN115044013B CN 115044013 B CN115044013 B CN 115044013B CN 202210800538 A CN202210800538 A CN 202210800538A CN 115044013 B CN115044013 B CN 115044013B
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- Prior art keywords
- acid
- polyurethane urea
- bio
- resin
- urea resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229920000180 alkyd Polymers 0.000 claims abstract description 81
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 150000001412 amines Chemical group 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 12
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000013638 trimer Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 6
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 6
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000013557 residual solvent Substances 0.000 claims description 5
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims description 4
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 4
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 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 4
- 229960004488 linolenic acid Drugs 0.000 claims description 4
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 4
- 235000021313 oleic acid Nutrition 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012973 diazabicyclooctane Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000005338 heat storage Methods 0.000 abstract 1
- 238000009472 formulation Methods 0.000 description 29
- 239000003973 paint Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000002023 wood 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/3243—Polyamines aromatic containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
The invention relates to the technical field of high-performance environment-friendly coatings, in particular to a bio-based air-curing type water-based polyurethane urea resin and a preparation method thereof. The raw materials of the water-based polyurethane urea resin comprise alkyd resin, polyether polyol, diisocyanate, dimethylolpropionic acid/dimethylolbutyric acid, aniline oligomer, amine chain extender, solvent, neutralizer and water. The bio-based air-curing water-based polyurethane urea resin prepared by the invention has the advantages of solid content of not less than 35%, solvent content of not more than 6%, long heat storage time of 6 months at 50 ℃, low viscosity, quick drying, high hardness, excellent corrosion resistance and the like.
Description
Technical Field
The invention relates to the technical field of high-performance environment-friendly coatings, in particular to a bio-based air-curing type water-based polyurethane urea resin and a preparation method thereof.
Background
With the development of industry, the problem of environmental pollution is increasingly plagued by human beings, so the development of environment-friendly paint is a great trend. The fundamental approach to solve the problem of environmental pollution of paints is to develop solvent-free paints, water-based paints, powder paints and high-solids paints. With the enhancement of environmental awareness and the increasingly strict environmental regulations, the water-based paint has become one of the main development directions of the environmental protection paint, and the water-based paint reduces the pollution to the environment because all or most of water is used for replacing the organic solvent.
Alkyd resin is an important resin for paint, and has the advantages of abundant monomer sources, low price, multiple varieties, large formula change, convenience for chemical modification and good performance; alkyd resins can be formulated either as one-component self-drying lacquers or as two-component self-drying (e.g.polyurethane lacquers) or amino baking lacquers. Alkyd resins have therefore been of great importance in the coatings industry since their development.
However, like other solvent borne coatings, solvent borne alkyd coatings contain large amounts of solvent (> 25%) and thus are a serious hazard to the atmosphere and to operator health during production and construction. In addition, the water resistance of the alkyd resin is poor due to easy hydrolysis of ester groups in the molecular structure of the alkyd resin, and meanwhile, the self-dried water-based alkyd resin has the defect of softer paint film, so that the application range and development space of the water-based alkyd resin are limited.
Disclosure of Invention
The invention aims to provide a bio-based air-curing type water-based polyurethane urea resin and a preparation method thereof, which are used for solving the defects in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a bio-based air-curing type water-based polyurethane urea resin, which is prepared from the following raw materials in parts by weight:
15 to 25 parts of alkyd resin, 6 to 15 parts of isocyanate monomer, 0 to 4 parts of polyether polyol, 1.5 to 3 parts of dimethylolpropionic acid or dimethylolbutyric acid, 4 to 6 parts of solvent, 0.01 to 0.1 part of catalyst, 0.05 to 0.25 part of aniline oligomer, 0.6 to 3 parts of amine chain extender, 0.8 to 2 parts of neutralizer and 50 to 60 parts of water.
Preferably, the fatty acid contained in the alkyd resin is unsaturated fatty acid, and the unsaturated fatty acid is one or more of soybean oil fatty acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid and coconut oleic acid; and the alkyd resin has an alkyd constant of not less than 1.08, an alcohol-acid ratio of not more than 1.3 and an acid value of not less than 3mg KOH/g.
Preferably, the isocyanate monomer is one or more of toluene diisocyanate, diphenylmethane diisocyanate, terephthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
Preferably, the polyether polyol is one or more of N204, N210, N220, N230, N240.
Preferably, the solvent is one or more of acetone, N-methylpyrrolidone, methyl isobutyl ketone, N-dimethylformamide and dimethyl sulfoxide; the catalyst is one or more of diazabicyclooctane, dibutyltin dilaurate and stannous octoate.
Preferably, the neutralizing agent is triethylamine.
Preferably, the aniline oligomer is one or more of aniline trimer, aniline tetramer, aniline pentamer and sulfonated aniline trimer; the amine chain extender is one or more of ethylenediamine, isophorone diamine and diethylenetriamine.
The invention also provides a preparation method of the bio-based air-curing water-based polyurethane urea resin, which comprises the following steps:
(1) Mixing alkyd resin, polyether polyol, a catalyst and isocyanate monomer, and heating to 90-95 ℃ for reaction;
or mixing alkyd resin, a catalyst and isocyanate monomer, and heating to 90-95 ℃ for reaction;
(2) When the NCO content is remained by 8-10%, cooling to 70-80 ℃, adding dimethylolpropionic acid/dimethylolbutyric acid and a solvent, and heating to 90-95 ℃ for continuous reaction;
(3) When the NCO content is 3-5%, cooling to 50-60 ℃, adding the residual solvent and the aniline oligomer for one-time chain extension, continuously cooling to 45-50 ℃, adding the neutralizer for neutralization for 0.5-1 h, and obtaining a resin solution;
(4) Pouring the resin solution into ice water for dispersion, adding an amine chain extender for secondary chain extension, and obtaining the bio-based air-curing type water-based polyurethane urea resin.
Preferably, the solvent added in the step (2) accounts for 75-85% of the total solvent.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The bio-based air-curing type water-based polyurethane urea resin prepared by the invention does not contain a surfactant, is dispersed in water after being neutralized by carboxyl carried by the resin, and has excellent thermal storage stability.
(2) The bio-based air-curing type water-based polyurethane urea resin prepared by the invention contains a large number of urethane bonds and urea bonds, and can form a certain amount of hydrogen bonds, so that the drying rate, the hardness and other performances of the alkyd resin are improved.
(3) The oxygen crosslinked alkyd resin is introduced into the bio-based air-curing type water-based polyurethane urea resin, so that the hardness, the drying speed and the corrosion resistance of the bio-based air-curing type water-based polyurethane urea resin are improved.
(4) The aniline oligomer with metal passivation capability is introduced into the bio-based air-curing type water-based polyurethane urea resin prepared by the invention as a chain extender, which is beneficial to improving the corrosion resistance and hardness of the bio-based air-curing type water-based polyurethane urea resin.
(5) The coating prepared from the bio-based air-curable aqueous polyurethane urea resin is suitable for the large-scale civil coating field and the industrial coating field, for example: steel structure coating, agricultural machinery coating, metal mechanical part coating, wood coating, indoor water pipe coating and the like.
Detailed Description
The invention provides a bio-based air-curing type water-based polyurethane urea resin, which is prepared from the following raw materials in parts by weight:
15 to 25 parts of alkyd resin, 6 to 15 parts of isocyanate monomer, 0 to 4 parts of polyether polyol, 1.5 to 3 parts of dimethylolpropionic acid or dimethylolbutyric acid, 4 to 6 parts of solvent, 0.01 to 0.1 part of catalyst, 0.05 to 0.25 part of aniline oligomer, 0.6 to 3 parts of amine chain extender, 0.8 to 2 parts of neutralizer, 50 to 60 parts of water, preferably 18 to 22 parts of alkyd resin, 8 to 13 parts of isocyanate monomer, 0.2 to 3 parts of polyether polyol, 1.8 to 2.8 parts of dimethylolpropionic acid or dimethylolbutyric acid, 4.5 to 5.5 parts of solvent, 0.04 to 0.08 part of catalyst, 0.08 to 0.22 part of aniline oligomer, 0.9 to 2.5 parts of amine chain extender, 1 to 1.5 parts of neutralizer and 52 to 56 parts of water.
In the invention, the fatty acid contained in the alkyd resin is unsaturated fatty acid, and the unsaturated fatty acid is one or more of soybean oil fatty acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid and coconut oleic acid, preferably one or more of soybean oil fatty acid, oleic acid, linoleic acid, linolenic acid and eleostearic acid; and the alkyd resin has an alkyd constant of not less than 1.08, preferably not less than 1.1, an alkyd ratio of not more than 1.3, preferably not more than 1.2, an acid number of not less than 3mg KOH/g, preferably not less than 3.2mg KOH/g.
In the invention, the preparation method of the alkyd resin comprises the following steps:
mixing fatty acid, polybasic acid, polyhydric alcohol, antioxidant, catalyst and solvent according to the mass ratio of 50-55:20-23:24-28:0.05-0.15:0.1-0.3:3-7, heating to 180-185 ℃ under nitrogen atmosphere, reacting at constant temperature for 0.8-1.2 h, continuously heating to 220-225 ℃, reacting at constant temperature until the acid value is less than 6mgKOH/g, cooling, vacuum extracting xylene solvent, discharging to obtain basic alkyd resin, preferably mixing fatty acid, polybasic acid, polyhydric alcohol, antioxidant, catalyst and solvent according to the mass ratio of 51-53:21-22:25-27:0.08-0.12:0.15-0.25:4-6, heating to 182-183 ℃ under nitrogen atmosphere, reacting at constant temperature for 0.9-1.1 h, continuously heating to 222-224 ℃, reacting at constant temperature until the acid value is less than 5mgKOH/g, cooling, vacuum extracting xylene solvent, and discharging;
the polybasic acid is one or more of phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride and isophthalic acid, preferably one or more of phthalic anhydride, hexahydrophthalic anhydride and tetrahydrophthalic anhydride;
the polyol is one or more of neopentyl glycol, trimethylolpropane, pentaerythritol and ethylene glycol, preferably one or more of neopentyl glycol, trimethylolpropane and ethylene glycol;
the antioxidant is hypophosphorous acid;
the catalyst is triphenylphosphine;
the solvent is one of xylene and methyl isobutyl ketone, preferably xylene.
In the invention, the preparation method of the aniline oligomer comprises the following steps:
mixing p-phenylenediamine, hydrochloric acid solution, ethanol, ammonium persulfate and aniline, stirring, reacting for 0.5-1 h, preferably 0.6-0.8 h, filtering the product, and adding NH 4 The OH reaction is carried out for 1 to 2 hours, preferably 1.2 to 1.8 hours. Then the mixture is decompressed and filtered, washed to be neutral by distilled water, and dried in vacuum at the temperature of 35-45 ℃ to obtain aniline trimer, preferably at the temperature of 38-42 ℃;
wherein, the mass ratio of the p-phenylenediamine to the hydrochloric acid solution to the ethanol to the ammonium persulfate to the aniline is 2-2.3:15-25:15-25:4-5: 3.5 to 4, preferably 2.1 to 2.2:18 to 22:18 to 22:4.2 to 4.6:3.6 to 3.9;
the concentration of the hydrochloric acid solution is 0.8 to 1.2mol/L, preferably 0.9 to 1mol/L.
In the present invention, the isocyanate monomer is one or more of toluene diisocyanate, diphenylmethane diisocyanate, terephthalylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, terephthalylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate.
In the present invention, the polyether polyol is one or more of N204, N210, N220, N230, N240, preferably one or more of N210, N220, N230, N240.
In the invention, the solvent is one or more of acetone, N-methyl pyrrolidone, methyl isobutyl ketone, N-dimethylformamide and dimethyl sulfoxide, preferably one or more of acetone, N-methyl pyrrolidone, methyl isobutyl ketone and dimethyl sulfoxide.
In the invention, the catalyst is one or more of diazabicyclooctane, dibutyl tin dilaurate and stannous octoate, preferably dibutyl tin dilaurate and/or stannous octoate.
In the present invention, the neutralizing agent is triethylamine.
In the invention, the aniline oligomer is one or more of aniline trimer, aniline tetramer, aniline pentamer and sulfonated aniline trimer, preferably one or more of aniline trimer, aniline tetramer and aniline pentamer.
The amine chain extender in the invention is one or more of ethylenediamine, isophorone diamine and diethylenetriamine, preferably ethylenediamine and/or isophorone diamine.
The invention also provides a preparation method of the bio-based air-curing water-based polyurethane urea resin, which comprises the following steps:
(1) Mixing alkyd resin, polyether polyol and isocyanate monomer, heating to 90-95 ℃ for reaction, preferably heating to 91-93 ℃ for reaction;
or mixing alkyd resin, a catalyst and isocyanate monomer, and heating to 90-95 ℃ for reaction, preferably 91-93 ℃;
(2) When the NCO content is 8-10%, cooling to 70-80 ℃, adding dimethylolpropionic acid/dimethylolbutyric acid and a solvent, heating to 90-95 ℃ for continuous reaction, preferably cooling to 72-78 ℃ when the NCO content is 8.5-9.5%, adding dimethylolpropionic acid/dimethylolbutyric acid and a solvent, heating to 91-93 ℃ for continuous reaction;
(3) When the NCO content is 3-5%, cooling to 50-60 ℃ and adding the residual solvent and the aniline oligomer for chain extension once, continuously cooling to 45-50 ℃, adding the neutralizer for neutralization for 0.5-1 h to obtain a resin solution, preferably when the NCO content is 3.5-4.5%, cooling to 52-56 ℃ and adding the residual solvent and the aniline oligomer for chain extension once, continuously cooling to 46-48 ℃, and adding the neutralizer for neutralization for 0.6-0.9 h to obtain the resin solution;
(4) Pouring the resin solution into ice water for dispersion, adding an amine chain extender for secondary chain extension, and obtaining the bio-based air-curing type water-based polyurethane urea resin.
In the invention, the solvent added in the step (2) accounts for 75-85% of the total solvent.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of bio-based air-curing type water-based polyurethane urea resin comprises the following steps:
(1) The basic alkyd resin is prepared, and the raw material composition and the proportion are shown in table 1.
The preparation method comprises the following steps: raw materials are added into a clean reaction kettle, the temperature is raised to 180 ℃ under the nitrogen atmosphere, the temperature is kept for 1h, and meanwhile, condensed water azeotroped with dimethylbenzene is collected. Continuously heating to 225 ℃, keeping the temperature until the acid value of the alkyd resin is 4mg KOH/g, cooling, removing xylene in vacuum, and discharging to obtain the basic alkyd resin, wherein the oil length of the alkyd resin is 50.2%, the K value is 1.12, and the R value is 1.22.
Table 1 raw material composition and formulation of basic alkyd resin
(2) Preparation of aniline trimer: 2.1g of p-phenylenediamine was dissolved in a mixed solution of 20g of HCl and 20g of ethanol, then, 4.6g of ammonium persulfate was added to the solution and stirred with 3.8g of aniline for reaction for 0.8 hours, then, the product was filtered and reacted with 1mol/L of aqueous ammonia for 1.5 hours, then, the mixture was filtered under reduced pressure, washed with distilled water and then with water to neutrality, and vacuum-dried at 40℃to obtain aniline trimer.
(3) The preparation of the bio-based air-curing aqueous polyurethane urea resin comprises the following raw materials in the composition and proportion shown in table 2.
The preparation method comprises the following steps: mixing the prepared basic alkyd resin, polyether polyol, catalyst and isocyanate monomer, heating to 92 ℃ for reaction, ending the reaction when the NCO content remains 9%, cooling to 75 ℃, adding dimethylolpropionic acid and solvent, and heating to 93 ℃. And when the NCO content is remained by 4%, cooling to 55 ℃, adding a solvent, continuously cooling to 48 ℃, adding a neutralizing agent, and neutralizing for 0.7h to obtain a resin solution. And then pouring the resin solution into ice water for dispersion, and adding an amine chain extender for chain extension to obtain the bio-based air-curing type water-based polyurethane urea resin. Wherein the solid mass of the bio-based air-curing aqueous polyurethane urea resin is 40%, the solvent content is 5.6%, and the viscosity is 4800mPa s.
TABLE 2 raw material composition and formulation of biobased air-curing aqueous polyurethane urea resin
Example 2
A preparation method of bio-based air-curing type water-based polyurethane urea resin comprises the following steps:
(1) The basic alkyd resin is prepared, and the raw material composition and the proportion are shown in table 3;
the preparation method is the same as that of the alkyd resin in the example 1, wherein the oil length of the alkyd resin is 58.4%, the K value is 1.09, and the R value is 1.16.
TABLE 3 raw material composition and formulation of basic alkyd resin
(2) The preparation of the bio-based air-curable aqueous polyurethane urea resin was the same as that of table 2 except that the basic alkyd resin was replaced with the basic alkyd resin prepared in table 3, and the preparation method was the same as that of the bio-based air-curable aqueous polyurethane urea resin of example 1. Wherein the solid mass of the bio-based air-curing aqueous polyurethane urea resin is 38%, the solvent content is 5.7%, and the viscosity is 4902mPa s.
Example 3
The invention provides a preparation method of bio-based air-curing water-based polyurethane urea resin, which comprises the following steps:
(1) The basic alkyd resin is prepared, and the raw material composition and the proportion are shown in table 4;
the preparation method is the same as that of the alkyd resin in the example 1, wherein the oil length of the alkyd resin is 69.9%, the K value is 1.17, and the R value is 1.23.
Table 4 raw material composition and formulation of base alkyd resin
(2) The preparation of the bio-based air-curing type aqueous polyurethane urea resin is shown in Table 5, and the basic alkyd resin is replaced by the basic alkyd resin prepared in Table 4, and the preparation method is the same as that of the bio-based air-curing type aqueous polyurethane urea resin in example 1. Wherein the solid mass of the bio-based air-curing aqueous polyurethane urea resin is 45%, the solvent content is 5.9%, and the viscosity is 4965mPa s.
TABLE 5 raw material composition and formulation of biobased air-curing aqueous polyurethane urea resin
Example 4
(1) The basic alkyd resin was prepared as in example 2.
(2) The aniline trimer is prepared, and the raw material composition and the proportion are shown in table 6;
the preparation method comprises the following steps: dissolving p-phenylenediamine in a mixed solution of HCl and ethanol, then adding ammonium persulfate to the solution and stirring with aniline for reaction for 0.8h, and then filtering the product and adding NH 4 OH was reacted for 1.5h, then the mixture was filtered under reduced pressure, washed with distilled water, added with water to neutrality, and dried in vacuo at 40℃to give aniline trimer.
TABLE 6 raw material composition and formulation of Aniline trimer
(3) The preparation method of the bio-based air-curing type water-based polyurethane urea resin comprises the following raw materials in the composition and proportion shown in table 7.
The preparation method comprises the following steps: the alkyd resin prepared in example 2, polyether polyol, catalyst and isocyanate monomer were mixed, heated to 90 ℃ to react, when the NCO content remained 8%, the reaction was ended, cooled to 70 ℃ to add dimethylolpropionic acid and solvent, and heated to 95 ℃. When the NCO content is remained by 5%, cooling to 60 ℃, adding the solvent and the aniline trimer for one-time chain extension, continuously cooling to 45 ℃, adding the neutralizer for neutralization for 0.5h, and obtaining the resin solution. And then pouring the resin solution into ice water for high-speed dispersion, and adding an amine chain extender for secondary chain extension to obtain the bio-based air-curing type water-based polyurethane urea resin. Wherein the solid mass of the bio-based air-curing type water-based polyurethane urea resin is 43%, the solvent content is 5.4%, the viscosity is 4893mPa s, and the aniline trimer accounts for 5% of the mole fraction of the amine chain extender.
TABLE 7 raw material composition and formulation of biobased air-curing aqueous polyurethane urea resin
Example 5
(1) The basic alkyd resin was prepared as in example 2.
(2) The aniline trimer was produced in the same manner as in example 4.
(3) The preparation method of the bio-based air-curing type water-based polyurethane urea resin and the composition and proportion of raw materials are shown in table 8.
The preparation method is the same as that of the bio-based air-curing aqueous polyurethane urea resin in example 7. Wherein the solid mass of the bio-based air-curing type water-based polyurethane urea resin is 44%, the solvent content is 5.2%, the viscosity is 4935mPa s, and the aniline trimer accounts for 10% of the mole fraction of the amine chain extender.
Table 8 raw material composition and ratio of biobased air-curing type aqueous polyurethane urea resin
Comparative example 1
The self-emulsifying aqueous alkyd resin formulation is shown in Table 9, and is prepared as follows: linoleic acid, trimethylolpropane, phthalic anhydride, and benzoic acid were added to a 1000mL four-necked flask equipped with an oil-water separator, a stirrer, a thermometer, and a spherical condenser, and after introducing nitrogen gas, stirring was started to raise the temperature. Heating to 180 ℃, keeping the temperature for 1h, heating to 225 ℃ again, keeping the temperature to react until the acid value is 50mgKOH/g, and cooling to 180 ℃. Adding 1,2, 4-trimellitic anhydride in the formula amount, maintaining 180 ℃ until the acid value of the product reaches 49mgKOH/g, vacuumizing to extract dimethylbenzene, cooling to 80 ℃, adding a proper amount of ethylene glycol butyl ether for dilution, adding a proper amount of neutralizer at 50 ℃ for neutralization, regulating the solid content to 40%, and discharging.
Table 9 self-emulsifying waterborne alkyd formulations
Comparative example 2
The formulation of the aqueous polyurethaneurea resin was as in Table 2 of example 1, except that the basic alkyd resin of Table 2 was replaced with N210, and the remainder of the formulation and process was as in example 1.
Comparative example 3
The basic alkyd resin was prepared in the same formulation and process as the basic alkyd resin of example 2, except that the acid number of the basic alkyd resin was reacted to 2mgKOH/g. The formulation of the bio-based air-curable aqueous polyurethaneurea resin was the same as in Table 2 of example 1, except that the basic alkyd resin of Table 2 was replaced with the basic alkyd resin of comparative example 3, and the remaining formulation and process were the same as in example 1. The reaction gelled after addition of the aniline trimer.
Comparative example 4
In the preparation formula of the basic alkyd resin, linoleic acid is changed into coconut oleic acid, the dosage is changed from 208g to 158.6g, other raw materials, dosage and process are the same as those of the preparation formula and process of the basic alkyd resin in the example 2, and the acid value of the basic alkyd resin is reduced to 1.6mgKOH/g and then discharged. The formulation of the biobased air-curable aqueous polyurethaneurea resin was the same as in Table 2 of example 1, except that the basic alkyd resin of Table 2 was replaced with the basic alkyd resin of comparative example 4 (50.4% oil length, and K and R values of 1.09 and 1.16, respectively), and the remaining formulation and process were the same as in example 1. The reaction gelled after addition of the aniline trimer.
Comparative example 5
In the preparation formulation of the basic alkyd resin, other raw materials, amounts and processes were the same as those of the preparation formulation and process of the basic alkyd resin in example 2, except that the amount of phthalic anhydride was changed from 87.2g to 107.2 g. The formulation of the biobased air-curable aqueous polyurethaneurea resin was the same as in Table 2 of example 1, except that the basic alkyd resin of Table 2 was replaced with the basic alkyd resin of comparative example 5 (oil length 54.8%, K and R values 1.05 and 1.08, respectively), and the rest of the formulation and process were the same as in example 1. The reaction gelled after addition of the aniline trimer.
Comparative example 6
In the formulation of the base alkyd resin, the formulation and process of the base alkyd resin of example 2 were the same except that the amount of trimethylolpropane was changed from 93.2g to 107.2 g. The formulation of the biobased air-curable aqueous polyurethaneurea resin was the same as in Table 2 of example 1, except that the basic alkyd resin of Table 2 was replaced with the basic alkyd resin of comparative example 5 (oil length 55.3%, K and R values 1.19 and 1.40, respectively), and the remaining formulation and process were the same as in example 1. The reaction gelled after addition of the aniline trimer.
Comparative example 7
The formulation and process for preparing the base alkyd resin were the same as that of the base alkyd resin of example 2. The formulation of the bio-based air-curable aqueous polyurethaneurea resin was the same as in Table 8 of example 5, except that the amount of aniline trimer in Table 8 was increased from 2.46g to 3.69g, and the other formulation and process were the same as in example 5. The reaction gelled after addition of the aniline trimer.
Experimental example 1
The aqueous resins prepared in examples 1 to 5, comparative examples 1 to 2 and 3AK0211Y (used by dilution to 40% in guangdong new materials limited) were prepared into aqueous paints according to the formulation of table 10, and the prepared aqueous paints were sprayed on the surface of clean tinplate, and after the spraying, they were maintained in a constant temperature and humidity room (temperature 23±2 ℃ and humidity 50% ±5%) for 7 days, and then subjected to performance test.
Table 10 Water-based paint formulation
Test items and methods are referenced below, and test results are shown in Table 11:
(1) Real drying time: according to the cotton ball pressing method in GB/T1728-2020 paint film and putty film drying time determination method;
(2) Adhesion force: according to GB/T9286-2021, cross-cut test of paint and varnish;
(3) Hardness: the paint film hardness is measured according to GB/T6739-2006 paint film hardness measured by a colored paint and varnish pencil method;
(4) Impact resistance: according to GB/T1732-2020, paint film impact resistance determination method; (5) flexibility: according to GB/T1731-1993 paint film flexibility determination method;
(6) Salt water resistance: according to the normal temperature brine-resistant method in GB 1763-79 (89) paint film chemical resistance determination method
TABLE 11 Performance test results for different examples and comparative examples
From the above test results, it is clear that the thermal storage stability, the paint film drying time and the paint hardness of the aqueous resin are greatly improved when the isocyanate modified alkyd resin is used, which is derived from the contribution of the hydrogen bond in the urethane bond or the urea bond or the double bond on the fatty acid chain in the alkyd resin. In addition, when the aniline oligomer is added in the form of a chain extender, not only the thermal storage stability of the aqueous resin is not affected, but also the real drying time, hardness and corrosion resistance of a paint film are further improved, which is derived from the rigid benzene ring structure in the aniline oligomer and the passivation effect of the aniline oligomer on a metal substrate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The bio-based air-curing type water-based polyurethane urea resin is characterized by being prepared from the following raw materials in parts by weight: 15 to 25 parts of alkyd resin, 6 to 15 parts of isocyanate monomer, 0 to 4 parts of polyether polyol, 1.5 to 3 parts of dimethylolpropionic acid or dimethylolbutyric acid, 4 to 6 parts of solvent, 0.01 to 0.1 part of catalyst, 0.08 to 0.22 part of aniline oligomer, 0.6 to 3 parts of amine chain extender, 0.8 to 2 parts of neutralizer and 50 to 60 parts of water;
the alkyd resin has an alkyd constant of not less than 1.08, an alcohol-acid ratio of not more than 1.3 and an acid value of not less than 3mg KOH/g;
the preparation method of the aniline oligomer comprises the following steps:
mixing p-phenylenediamine, hydrochloric acid solution, ethanol, ammonium persulfate and aniline, stirring, reacting for 0.5-1 h, filtering the product, and adding NH 4 Reacting OH for 1-2 h, then decompressing and filtering the mixture, washing the mixture to be neutral by distilled water, and vacuum drying the mixture at 35-45 ℃ to obtain aniline trimer;
the preparation method of the bio-based air-curing type water-based polyurethane urea resin comprises the following steps:
(1) Mixing alkyd resin, polyether polyol, a catalyst and isocyanate monomer, and heating to 90-95 ℃ for reaction;
or mixing alkyd resin, a catalyst and isocyanate monomer, and heating to 90-95 ℃ for reaction;
(2) When the NCO content is remained by 8-10%, cooling to 70-80 ℃, adding dimethylolpropionic acid/dimethylolbutyric acid and a solvent, and heating to 90-95 ℃ for continuous reaction;
(3) When the NCO content is 3-5%, cooling to 50-60 ℃, adding the residual solvent and the aniline oligomer for one-time chain extension, continuously cooling to 45-50 ℃, adding the neutralizer for neutralization for 0.5-1 h, and obtaining a resin solution;
(4) Pouring the resin solution into ice water for dispersion, adding an amine chain extender for secondary chain extension, and obtaining the bio-based air-curing type water-based polyurethane urea resin.
2. The bio-based air-curable aqueous polyurethane urea resin according to claim 1, wherein the fatty acid contained in the alkyd resin is an unsaturated fatty acid, and the unsaturated fatty acid is one or more of soybean oil fatty acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, and coconut oleic acid.
3. The biobased air-curable aqueous polyurethane urea resin according to claim 1 or 2, wherein the isocyanate monomer is one or more of toluene diisocyanate, diphenylmethane diisocyanate, terephthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate.
4. A biobased air curable aqueous polyurethaneurea resin according to claim 3, wherein the polyether polyol is one or more of N204, N210, N220, N230, N240.
5. The bio-based air-curable aqueous polyurethane urea resin according to claim 1,2 or 4, wherein the solvent is one or more of acetone, N-methylpyrrolidone, methyl isobutyl ketone, N-dimethylformamide, dimethyl sulfoxide; the catalyst is one or more of diazabicyclooctane, dibutyltin dilaurate and stannous octoate.
6. The bio-based air curable aqueous polyurethane urea resin of claim 5, wherein the neutralizing agent is triethylamine.
7. The bio-based air-curable aqueous polyurethane urea resin of claim 6, wherein the amine chain extender is one or more of ethylenediamine, isophorone diamine, and diethylenetriamine.
8. The method for producing a biobased air-curable aqueous polyurethane urea resin according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing alkyd resin, polyether polyol, a catalyst and isocyanate monomer, and heating to 90-95 ℃ for reaction;
or mixing alkyd resin, a catalyst and isocyanate monomer, and heating to 90-95 ℃ for reaction;
(2) When the NCO content is remained by 8-10%, cooling to 70-80 ℃, adding dimethylolpropionic acid/dimethylolbutyric acid and a solvent, and heating to 90-95 ℃ for continuous reaction;
(3) When the NCO content is 3-5%, cooling to 50-60 ℃, adding the residual solvent and the aniline oligomer for one-time chain extension, continuously cooling to 45-50 ℃, adding the neutralizer for neutralization for 0.5-1 h, and obtaining a resin solution;
(4) Pouring the resin solution into ice water for dispersion, adding an amine chain extender for secondary chain extension, and obtaining the bio-based air-curing type water-based polyurethane urea resin.
9. The method for preparing a bio-based air-curable aqueous polyurethane urea resin according to claim 8, wherein the solvent added in the step (2) is 75-85% of the total amount of the solvent.
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| KR20090072491A (en) * | 2007-12-28 | 2009-07-02 | (주)디피아이 홀딩스 | Polyurethane alkyd resin and water-dispersion enamel paint composition |
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| CN112940218A (en) * | 2021-02-04 | 2021-06-11 | 四川大学 | Degradable electroactive polyurethane material and preparation method and application thereof |
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| US11028215B2 (en) * | 2016-02-15 | 2021-06-08 | Board Of Regents, The University Of Texas System | Dopant-free conductive bioelastomers |
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| KR20090072491A (en) * | 2007-12-28 | 2009-07-02 | (주)디피아이 홀딩스 | Polyurethane alkyd resin and water-dispersion enamel paint composition |
| CN102432797A (en) * | 2011-08-18 | 2012-05-02 | 山东圣光化工集团有限公司 | Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof |
| CN104311775A (en) * | 2014-09-23 | 2015-01-28 | 李本明 | Polyaniline modified self-cross-linking waterborne polyurethane preparation method |
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