CN117165169A - Corrosion-resistant water-based paint for automobiles and preparation process thereof - Google Patents
Corrosion-resistant water-based paint for automobiles and preparation process thereof Download PDFInfo
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- CN117165169A CN117165169A CN202311262545.5A CN202311262545A CN117165169A CN 117165169 A CN117165169 A CN 117165169A CN 202311262545 A CN202311262545 A CN 202311262545A CN 117165169 A CN117165169 A CN 117165169A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000003973 paint Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000005260 corrosion Methods 0.000 title claims abstract description 38
- 230000007797 corrosion Effects 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 229920000180 alkyd Polymers 0.000 claims abstract description 40
- 229920005862 polyol Polymers 0.000 claims abstract description 39
- 150000003077 polyols Chemical class 0.000 claims abstract description 39
- -1 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid Chemical compound 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 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 abstract description 24
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 229960004488 linolenic acid Drugs 0.000 claims abstract description 24
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 14
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 83
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 66
- 235000010215 titanium dioxide Nutrition 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 39
- 239000004408 titanium dioxide Substances 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 23
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 229920013822 aminosilicone Polymers 0.000 claims description 15
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 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 12
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 238000005406 washing Methods 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 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000004970 Chain extender Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 230000002335 preservative effect Effects 0.000 description 5
- 239000006254 rheological additive Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 241000726094 Aristolochia Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BBFQZRXNYIEMAW-UHFFFAOYSA-N aristolochic acid I Chemical compound C1=C([N+]([O-])=O)C2=C(C(O)=O)C=C3OCOC3=C2C2=C1C(OC)=CC=C2 BBFQZRXNYIEMAW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of automobile coatings, in particular to an automobile corrosion-resistant water-based coating and a preparation process thereof, wherein the preparation process comprises the following steps: taking linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride, maleic anhydride, epoxy resin and ethylene glycol monobutyl ether as components, and reacting at high temperature to obtain modified alkyd polyol; reacting modified alkyd polyol with diisocyanate to obtain water-based resin; mixing deionized water, aqueous resin and an auxiliary agent by stirring, and dispersing at a high speed for 30-60 min to obtain a component A; and (3) adding the component B to obtain the water-based paint. According to the invention, the modified alkyd polyol is obtained through the reaction, reacts with diisocyanate and a chain extender, and is copolymerized with an acrylic monomer to obtain the water-based resin, and the 2-hydroxyethyl methacrylate phosphate is introduced to improve the stability and the corrosion resistance and the adhesive force of a film layer prepared by the water-based paint.
Description
Technical Field
The invention relates to the technical field of automobile coatings, in particular to an automobile corrosion-resistant water-based coating and a preparation process thereof.
Background
With the development of economic construction and industrial technology, china becomes the first automobile in the world and the large country for producing and selling paint, and has sufficient market demands, so that the automobile paint has wide prospects and promotes innovation in quality, yield and variety. Because of the characteristics of multiple varieties, large consumption, higher performance requirements and the like, the special paint has been developed, and is used as a paint variety with high technical content and high added value, and the automobile paint represents the highest level of the paint industry. Industrial production of automotive coatings is becoming a highly polluting industry, and as market demands increase year by year, environmental pollution is becoming an increasingly important issue. The solvent of the water-based paint is mainly water, is nontoxic, pollution-free and low in VOCs, has good environmental protection property and rich types, and can be widely applied in the field of automobile coating. Among the aqueous coating components, aqueous polyurethane is often used as a resin component, but has poor water resistance and corrosion resistance and also has a room for improvement. Therefore, we propose a corrosion-resistant water-based paint for automobiles and a preparation process thereof.
Disclosure of Invention
The invention aims to provide an automotive corrosion-resistant water-based paint and a preparation process thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 1, preparation of aqueous resin:
taking linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride, maleic anhydride, epoxy resin and ethylene glycol monobutyl ether as components, and reacting at high temperature to obtain modified alkyd polyol;
reacting modified alkyd polyol with diisocyanate to obtain water-based resin;
step 2, preparation of water-based paint:
mixing deionized water, aqueous resin and an auxiliary agent by stirring, and dispersing at a high speed for 30-60 min to obtain a component A; titanium dioxide and a curing agent are taken as a component B; before use, component B is added to obtain the water-based paint.
In step 2, the stirring speed is 600-700 rpm, and the high-speed dispersion speed is 1500-2000 rpm.
Further, in the step 2, the water-based paint comprises the following components in mass percent: 40-60 parts of water-based resin, 20-25 parts of titanium dioxide, 42-64 parts of curing agent and 1.5-4.0 parts of auxiliary agent;
the solid content of the water-based paint is 35-38%.
Further, the auxiliary agent comprises the following components in parts by mass: 0.1 to 0.3 part of wetting agent, 0.3 to 0.5 part of dispersing agent, 0.02 to 0.04 part of defoaming agent, 0.02 to 0.05 part of rheological additive, 0.03 to 0.05 part of flatting agent, 1 to 3 parts of film forming additive and 0.05 to 0.10 part of preservative;
wetting agent: TEGO-270, from Pick chemical technologies consultation (Shanghai);
dispersing agent: TEG0-755W, derived from german dihomo;
defoaming agent: TEGO-810, from Germany Digao;
rheology aid: BYK410, from the company pick chemical technologies consultation (Shanghai);
leveling agent: BYK-320, from German diGao;
film forming auxiliary agent: DPM, from Dow chemical (China) Co., ltd;
titanium white powder: r706 is from Dongguan chemical industry Co., ltd;
curing agent: SV-4655 is derived from Sortv.
Further, the aqueous resin is prepared by the following process:
step 1, preparing modified alkyd polyol:
mixing linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride accounting for 48-56% of the components in mass and maleic anhydride, adding solvent dimethylbenzene, heating to 120-130 ℃, stirring for 20-40 min, heating to 220-240 ℃ at a heating rate of 20 ℃/h, and carrying out heat preservation reflux reaction for 100-150 min;
cooling to 180-200 ℃, adding epoxy resin and phthalic anhydride with the mass of the rest components, and carrying out heat preservation reaction until the acid value of the system is 40-60 mgKOH/g; cooling to 115-125 ℃, adding ethylene glycol monobutyl ether, reacting for 90-120 min, cooling to 60-70 ℃, adding triethylamine for reaction neutralization, and distilling under reduced pressure to obtain modified alkyd polyol;
step 2, preparation of aqueous resin:
mixing modified alkyd polyol and isophorone diisocyanate, adding a catalyst under the protection of nitrogen atmosphere, and heating to 70-80 ℃ for reaction for 4-5 h; regulating the temperature of the system to 60-70 ℃, adding 2-bis (hydroxymethyl) propionic acid, hydroxyl-terminated polysiloxane and 1, 4-butanediol, and reacting for 160-200 min; cooling to 50-60 ℃, adding 2-hydroxyethyl methacrylate phosphate, and reacting for 5-6 h; adding triethylamine, reacting for 20-40 min and neutralizing;
adding butyl acrylate, styrene, diacetone acrylamide and adipic dihydrazide, mixing, adding an emulsifying agent and deionized water, and stirring and dispersing for 25-35 min at a rotating speed of 180-220 rpm; and adding an initiator, and reacting for 4-5 hours to obtain the water-based resin.
Further, the modified alkyd polyol comprises the following components in parts by mass: 133 to 145 parts of linolenic acid, 34 to 40 parts of pentaerythritol, 10 to 13 parts of 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, 18 to 30 parts of phthalic anhydride, 7.7 to 14 parts of maleic anhydride, 20 to 40 parts of epoxy resin, 7 to 12 parts of ethylene glycol monobutyl ether and 10 to 20 parts of triethylamine;
the ratio of linolenic acid to dimethylbenzene is 5g/100mL.
Further, the aqueous resin comprises the following components in parts by mass: 30 to 40 parts of modified alkyd polyol, 20 to 24 parts of isophorone diisocyanate, 0.1 to 0.2 part of catalyst dibutyltin dilaurate, 3 to 4 parts of 2-bis (hydroxymethyl) propionic acid, 2 to 4 parts of hydroxyl-terminated polysiloxane, 0.5 to 1.0 part of 1, 4-butanediol, 1.8 to 2.5 parts of 2-hydroxyethyl methacrylate phosphate, 3 to 6 parts of triethylamine, 5 to 8 parts of butyl acrylate, 4.5 to 6.5 parts of styrene, 0.2 to 0.3 part of diacetone acrylamide, 0.1 to 0.2 part of adipic dihydrazide, 0.5 to 0.7 part of emulsifier and 0.3 to 0.4 part of initiator ammonium persulfate;
the emulsifier is the mixture of dodecyl sodium sulfate SDS and octyl phenol polyoxyethylene ether OP-10, and the mass ratio is 2:1;
the solid content of the aqueous resin is 45-50%.
Linseed oil (l.o.): from HonNuo chemical Co., ltd
Hydroxy polysiloxane: number average molecular weight 2000, from Guangdong Aristolochia (Buddha chemical materials Co., ltd.)
Further, the component B is a titanium dioxide modified curing agent, and is specifically prepared by the following process:
mixing ethanol solution and secondary aminosilicone, regulating the pH of the system to 3-4 by glacial acetic acid, and stirring and hydrolyzing at room temperature for 55-75 min; adding titanium dioxide, heating to 70-85 ℃, and reacting for 4-6 hours to obtain sol; centrifuging for 8-15 min, filtering, washing, and vacuum drying at 80-90 ℃ for 8-12 h to obtain modified titanium dioxide;
mixing the HDI trimer and the modified titanium dioxide, stirring and dispersing for 10-15 min, slowly heating to 75-85 ℃, adding a catalyst, and reacting until the system is transparent; cooling, suction filtering, washing and drying to obtain the titanium white modified solidifying agent.
Further, the proportion of the titanium dioxide, the secondary aminosilicone and the ethanol solution is 25g (5.3-8.0 g) to 100mL;
the concentration of the ethanol solution was 75v%.
Further, the secondary aminosilicone is prepared by the process of:
mixing 3- (cyclohexane) -1-propanesulfonic acid, gamma-aminopropyl triethoxysilane and acetone, and reacting for 5-10 min under the protection of nitrogen atmosphere.
Further, the molar ratio of 3- (cyclohexylamine) -1-propanesulfonic acid to gamma-aminopropyl triethoxysilane is (1.01-1.05): 1.
Further, the titanium dioxide modified curing agent is prepared from the following components in parts by mass: 42 to 64 parts of HDI trimer, 20 to 25 parts of modified titanium dioxide, 0.05 to 0.10 part of catalyst dibutyl tin dilaurate.
HDI trimer 168: HDI-100 was obtained from Wanhua chemical group Co., ltd.
Compared with the prior art, the invention has the following beneficial effects:
in the technical scheme, linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride and maleic anhydride are used as raw materials to synthesize alkyd resin, then carboxyl groups in the molecular structure of the alkyd resin react with epoxy resin to obtain epoxy ester with hydroxyl groups, ethylene glycol monobutyl ether is introduced to obtain modified alkyd polyol which has good flexibility, and the modified alkyd polyol is used as polyol in a preparation component of water-based resin, has higher crosslinking density, can improve the dryness of the prepared water-based paint, and improves the hardness, mechanical property, adhesive force, water resistance, solvent resistance, corrosion resistance and other properties of a coating film after drying; the introduction of phenyl and carbazole structures can enhance the interaction between the metal substrate and the film layer prepared by the water-based paint, effectively inhibit the occurrence of electrochemical corrosion and improve the corrosion resistance; meanwhile, the interaction between the hydrogen bond and pi-pi bond can be enhanced, and the mechanical property of the film layer is improved.
The aqueous resin is obtained by reacting modified alkyd polyol, diisocyanate, a chain extender (2-bis (hydroxymethyl) propionic acid, hydroxyl-terminated polysiloxane, 1, 4-butanediol and 2-hydroxyethyl methacrylate phosphate) and copolymerizing with acrylic monomers (butyl acrylate and styrene), wherein the 2-hydroxyethyl methacrylate phosphate introduces a phosphate structure, can perform phosphating with metal to generate phosphate, and forms a compact passivation layer as a protective film to prevent water molecules and other ions from contacting with the metal; the phosphate has chelating effect with metal ions, and the covalent bond is utilized to bond the metal with the film layer prepared by the water-based paint, so that the stability of the prepared water-based resin is improved, and the corrosion resistance and the adhesive force of the film layer prepared by the water-based paint are improved. Under the action of an initiator, the styrene-acrylic resin is introduced by copolymerization with an acrylic monomer, so that the adhesive force, water resistance, heat resistance and corrosion resistance of a film layer prepared by the water-based paint can be further improved. The introduction of polysiloxane can improve the dryness, solvent resistance and corrosion resistance of a coating film prepared from the water-based resin, so that the prepared water-based coating can obtain good water resistance and corrosion resistance after the coating film is dried.
In the technical scheme, the 3- (cyclohexane) -1-propane sulfonic acid and the gamma-aminopropyl triethoxy silane are mixed for reaction, so that the primary amino group in the gamma-aminopropyl triethoxy silane and the sulfonic acid group of the 3- (cyclohexane) -1-propane sulfonic acid react, and the primary amino group in the siloxane is converted into the secondary amino group to obtain the secondary amino siloxane, thereby being more beneficial to the formation and utilization of a subsequent curing agent. And then carrying out surface coupling modification on the inorganic titanium dioxide by utilizing secondary aminosilicone to obtain modified titanium dioxide. The secondary amino group introduced on the surface of the modified titanium dioxide reacts with the-NCO group in the HDI trimer to obtain the titanium dioxide modified curing agent, wherein the sulfamic acid group in the secondary aminosiloxane can improve the water dispersion capacity of the curing agent and the titanium dioxide, realize the water dispersion property and the storage stability of the curing agent and the titanium dioxide in the aqueous resin, enhance the crosslinking between inorganic matters and organic polymers and improve the capacity of the prepared aqueous coating in the aspects of curing strength, water resistance, chemical resistance and heat resistance. The preparation process can enable the curing agent to keep higher reactivity.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following description of the embodiments of the present invention,
linseed oil (l.o.): from HonNuo chemical Co., ltd
Hydroxy polysiloxane: number average molecular weight 2000, from guangdong ark (berga) chemical materials limited;
HDI trimer 168: HDI-100, from Wanhua chemical group Co., ltd;
wetting agent: TEGO-270, from Pick chemical technologies consultation (Shanghai);
dispersing agent: TEG0-755W, derived from german dihomo;
defoaming agent: TEGO-810, from Germany Digao;
rheology aid: BYK410, from the company pick chemical technologies consultation (Shanghai);
leveling agent: BYK-320, from German diGao;
film forming auxiliary agent: DPM, from Dow chemical (China) Co., ltd;
titanium white powder: r706 is from Dongguan chemical industry Co., ltd;
curing agent: SV-4655 is derived from Sortv.
Example 1: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 1, preparation of aqueous resin:
1.1. mixing linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride with the mass of 56% and maleic anhydride, adding solvent dimethylbenzene, heating to 120 ℃, stirring for 40min, heating to 220 ℃ at the heating rate of 20 ℃/h, and carrying out heat preservation reflux reaction for 150min;
cooling to 180 ℃, adding epoxy resin and phthalic anhydride with the mass of the rest components, and carrying out heat preservation reaction until the acid value of the system is 60mgKOH/g; cooling to 115 ℃, adding ethylene glycol monobutyl ether, reacting for 120min, cooling to 60 ℃, adding triethylamine for reaction neutralization, and distilling under reduced pressure to obtain modified alkyd polyol;
the modified alkyd polyol comprises the following components in parts by mass: 133 parts of linolenic acid, 34 parts of pentaerythritol, 10 parts of 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, 18 parts of phthalic anhydride, 14 parts of maleic anhydride, 20 parts of epoxy resin, 7 parts of ethylene glycol monobutyl ether and 10 parts of triethylamine; the ratio of linolenic acid to dimethylbenzene is 5g/100mL;
1.2. mixing modified alkyd polyol and isophorone diisocyanate, adding a catalyst under the protection of nitrogen atmosphere, and heating to 70 ℃ for reaction for 5 hours; regulating the temperature of the system to 60 ℃, adding 2-bis (hydroxymethyl) propionic acid, hydroxyl-terminated polysiloxane and 1, 4-butanediol, and reacting for 200min; cooling to 50 ℃, adding 2-hydroxyethyl methacrylate phosphate, and reacting for 6 hours; adding triethylamine, and reacting for 20min for neutralization; adding butyl acrylate, styrene, diacetone acrylamide and adipic dihydrazide, mixing, adding an emulsifying agent and deionized water, and stirring and dispersing for 35min at a rotating speed of 180 rpm; adding an initiator, and reacting for 4 hours to obtain aqueous resin;
the aqueous resin comprises the following components in mass percent: 30 parts of modified alkyd polyol, 20 parts of isophorone diisocyanate, 0.1 part of catalyst dibutyltin dilaurate, 3 parts of 2-bis (hydroxymethyl) propionic acid, 2 parts of hydroxyl-terminated polysiloxane, 0.5 part of 1, 4-butanediol, 1.8 parts of 2-hydroxyethyl methacrylate phosphate, 3 parts of triethylamine, 5 parts of butyl acrylate, 4.5 parts of styrene, 0.2 part of diacetone acrylamide, 0.1 part of adipic acid dihydrazide, 0.5 part of emulsifier and 0.3 part of initiator ammonium persulfate; the emulsifier is the mixture of dodecyl sodium sulfate SDS and octyl phenol polyoxyethylene ether OP-10, and the mass ratio is 2:1; the solid content of the aqueous resin is 45%;
step 2, preparation of a component B:
mixing 3- (cyclohexane) -1-propanesulfonic acid, gamma-aminopropyl triethoxysilane and acetone, and reacting for 5min under the protection of nitrogen atmosphere to obtain secondary aminosiloxane; the molar ratio of the 3- (cyclohexane) -1-propanesulfonic acid and the gamma-aminopropyl triethoxysilane is 1.01:1;
mixing 75v% ethanol solution and secondary aminosilicone, regulating the pH of the system to 4 by glacial acetic acid, and stirring at room temperature for hydrolysis for 55min; adding titanium dioxide, heating to 70 ℃, and reacting for 6 hours to obtain sol; centrifuging for 8min, filtering, washing, and vacuum drying at 80deg.C for 12 hr to obtain modified titanium dioxide; the proportion of titanium dioxide, secondary aminosilicone and ethanol solution is 25g:5.3g:100mL;
mixing the HDI trimer and the modified titanium dioxide, stirring and dispersing for 10min, slowly heating to 75 ℃, adding a catalyst, and reacting until the system is transparent; cooling, filtering, washing and drying to obtain the titanium dioxide modified curing agent; the titanium dioxide modified curing agent is prepared from the following components in parts by mass: 42 parts of HDI trimer, 20 parts of modified titanium dioxide and 0.05 part of catalyst dibutyl tin dilaurate;
step 3, preparation of water-based paint:
mixing deionized water, water-based resin and an auxiliary agent at a rotating speed of 600rpm, and dispersing at a rotating speed of 1500rpm for 60min to obtain a component A; titanium dioxide modified curing agent is used as a component B; before use, component B is added to obtain the water-based paint with the solid content of 35 percent.
The water-based paint comprises the following components in mass percent: 40 parts of water-based resin, 62 parts of titanium dioxide modified curing agent and 1.5 parts of auxiliary agent; the auxiliary agent comprises the following components in mass: 0.1 part of wetting agent, 0.3 part of dispersing agent, 0.02 part of defoamer, 0.02 part of rheological additive, 0.03 part of flatting agent, 1 part of film forming additive and 0.05 part of preservative.
Example 2: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 1, preparation of aqueous resin:
1.1. mixing linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride with the weight of 52% and maleic anhydride, adding solvent dimethylbenzene, heating to 125 ℃, stirring for 30min, heating to 230 ℃ at the heating rate of 20 ℃/h, and carrying out heat preservation reflux reaction for 120min;
cooling to 190 ℃, adding epoxy resin and phthalic anhydride with the mass of the rest components, and carrying out heat preservation reaction until the acid value of the system is 50mgKOH/g; cooling to 120 ℃, adding ethylene glycol monobutyl ether, reacting for 100min, cooling to 65 ℃, adding triethylamine for reaction neutralization, and distilling under reduced pressure to obtain modified alkyd polyol;
the modified alkyd polyol comprises the following components in parts by mass: 139 parts of linolenic acid, 37 parts of pentaerythritol, 12 parts of 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, 24 parts of phthalic anhydride, 10.8 parts of maleic anhydride, 30 parts of epoxy resin, 9 parts of ethylene glycol monobutyl ether and 15 parts of triethylamine; the ratio of linolenic acid to dimethylbenzene is 5g/100mL;
1.2. mixing modified alkyd polyol and isophorone diisocyanate, adding a catalyst under the protection of nitrogen atmosphere, and heating to 75 ℃ for reaction for 4.5 hours; regulating the temperature of the system to 62 ℃, adding 2-bis (hydroxymethyl) propionic acid, hydroxyl-terminated polysiloxane and 1, 4-butanediol, and reacting for 180min; cooling to 52 ℃, adding 2-hydroxyethyl methacrylate phosphate, and reacting for 5.5 hours; adding triethylamine, and reacting for 30min for neutralization;
adding butyl acrylate, styrene, diacetone acrylamide and adipic dihydrazide, mixing, adding an emulsifying agent and deionized water, and stirring and dispersing for 30min at a rotating speed of 200 rpm; adding an initiator, and reacting for 4.5 hours to obtain aqueous resin;
the aqueous resin comprises the following components in mass percent: 35 parts of modified alkyd polyol, 22 parts of isophorone diisocyanate, 0.15 part of catalyst dibutyltin dilaurate, 3.5 parts of 2-bis (hydroxymethyl) propionic acid, 3 parts of hydroxyl-terminated polysiloxane, 0.8 part of 1, 4-butanediol, 2.1 parts of 2-hydroxyethyl methacrylate phosphate, 4.5 parts of triethylamine, 6.5 parts of butyl acrylate, 5.5 parts of styrene, 0.25 part of diacetone acrylamide, 0.15 part of adipic dihydrazide, 0.6 part of emulsifier and 0.35 part of initiator ammonium persulfate; the emulsifier is the mixture of dodecyl sodium sulfate SDS and octyl phenol polyoxyethylene ether OP-10, and the mass ratio is 2:1; the solid content of the aqueous resin is 48%;
step 2, preparation of a component B:
mixing 3- (cyclohexane) -1-propanesulfonic acid, gamma-aminopropyl triethoxysilane and acetone, and reacting for 8min under the protection of nitrogen atmosphere to obtain secondary aminosiloxane; the molar ratio of the 3- (cyclohexane) -1-propanesulfonic acid and the gamma-aminopropyl triethoxysilane is 1.03:1;
mixing 75v% ethanol solution and secondary aminosilicone, regulating the pH of the system to 3.5 by glacial acetic acid, and stirring at room temperature for hydrolysis for 65min; adding titanium dioxide, heating to 78 ℃, and reacting for 4.5 hours to obtain sol; centrifuging for 10min, filtering, washing, and vacuum drying at 85deg.C for 10 hr to obtain modified titanium dioxide; the proportion of titanium dioxide, secondary aminosilicone and ethanol solution is 25g:6.6g:100mL;
mixing the HDI trimer and the modified titanium dioxide, stirring and dispersing for 12min, slowly heating to 80 ℃, adding a catalyst, and reacting until the system is transparent; cooling, filtering, washing and drying to obtain the titanium dioxide modified curing agent; the titanium dioxide modified curing agent is prepared from the following components in parts by mass: 53 parts of HDI trimer, 22 parts of modified titanium dioxide and 0.08 part of catalyst dibutyl tin dilaurate;
step 3, preparation of water-based paint:
mixing deionized water, water-based resin and an auxiliary agent at a rotating speed of 650rpm, and dispersing at a rotating speed of 180rpm for 40min to obtain a component A; titanium dioxide modified curing agent is used as a component B; before use, component B is added to obtain the water-based paint with the solid content of 35 percent.
The water-based paint comprises the following components in mass percent: 50 parts of water-based resin, 76 parts of titanium dioxide modified curing agent and 2.8 parts of auxiliary agent; the auxiliary agent comprises the following components in mass: 0.2 part of wetting agent, 0.4 part of dispersing agent, 0.03 part of defoamer, 0.04 part of rheological additive, 0.04 part of flatting agent, 2 parts of film forming additive and 0.08 part of preservative.
Example 3: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 1, preparation of aqueous resin:
1.1. mixing linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride accounting for 48% of the components in mass and maleic anhydride, adding solvent dimethylbenzene, heating to 130 ℃, stirring for 20min, heating to 240 ℃ at a heating rate of 20 ℃/h, and carrying out heat preservation reflux reaction for 100min;
cooling to 200 ℃, adding epoxy resin and phthalic anhydride with the mass of the rest components, and carrying out heat preservation reaction until the acid value of the system is 40mgKOH/g; cooling to 125 ℃, adding ethylene glycol monobutyl ether, reacting for 90min, cooling to 70 ℃, adding triethylamine for reaction neutralization, and distilling under reduced pressure to obtain modified alkyd polyol;
the modified alkyd polyol comprises the following components in parts by mass: 145 parts of linolenic acid, 40 parts of pentaerythritol, 13 parts of 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, 30 parts of phthalic anhydride, 7.7 parts of maleic anhydride, 40 parts of epoxy resin, 12 parts of ethylene glycol monobutyl ether and 20 parts of triethylamine; the ratio of linolenic acid to dimethylbenzene is 5g/100mL;
1.2. mixing modified alkyd polyol and isophorone diisocyanate, adding a catalyst under the protection of nitrogen atmosphere, and heating to 80 ℃ for reaction for 4 hours; regulating the temperature of the system to 70 ℃, adding 2-bis (hydroxymethyl) propionic acid, hydroxyl-terminated polysiloxane and 1, 4-butanediol, and reacting for 160min; cooling to 60 ℃, adding 2-hydroxyethyl methacrylate phosphate, and reacting for 5 hours; adding triethylamine, and reacting for 40min for neutralization;
adding butyl acrylate, styrene, diacetone acrylamide and adipic dihydrazide, mixing, adding an emulsifying agent and deionized water, and stirring and dispersing for 25min at a rotating speed of 220 rpm; adding an initiator, and reacting for 5 hours to obtain aqueous resin;
the aqueous resin comprises the following components in mass percent: 40 parts of modified alkyd polyol, 24 parts of isophorone diisocyanate, 0.2 part of catalyst dibutyltin dilaurate, 4 parts of 2-bis (hydroxymethyl) propionic acid, 4 parts of hydroxyl-terminated polysiloxane, 1.0 part of 1, 4-butanediol, 2.5 parts of 2-hydroxyethyl methacrylate phosphate, 6 parts of triethylamine, 8 parts of butyl acrylate, 6.5 parts of styrene, 0.3 part of diacetone acrylamide, 0.2 part of adipic acid dihydrazide, 0.7 part of emulsifier and 0.4 part of initiator ammonium persulfate; the emulsifier is the mixture of dodecyl sodium sulfate SDS and octyl phenol polyoxyethylene ether OP-10, and the mass ratio is 2:1; the solid content of the aqueous resin is 50%;
step 2, preparation of a component B:
mixing 3- (cyclohexane) -1-propanesulfonic acid, gamma-aminopropyl triethoxysilane and acetone, and reacting for 10min under the protection of nitrogen atmosphere to obtain secondary aminosiloxane; the molar ratio of the 3- (cyclohexane) -1-propanesulfonic acid and the gamma-aminopropyl triethoxysilane is 1.05:1;
mixing 75v% ethanol solution and secondary aminosilicone, regulating the pH of the system to 3 by glacial acetic acid, and stirring at room temperature for hydrolysis for 75min; adding titanium dioxide, heating to 85 ℃, and reacting for 4 hours to obtain sol; centrifuging for 15min, filtering, washing, and vacuum drying at 90 ℃ for 8h to obtain modified titanium dioxide; the proportion of titanium dioxide, secondary aminosilicone and ethanol solution is 25g to 8.0g to 100mL;
mixing the HDI trimer and the modified titanium dioxide, stirring and dispersing for 15min, slowly heating to 85 ℃, adding a catalyst, and reacting until the system is transparent; cooling, filtering, washing and drying to obtain the titanium dioxide modified curing agent; the titanium dioxide modified curing agent is prepared from the following components in parts by mass: 64 parts of HDI trimer, 25 parts of modified titanium dioxide and 0.10 part of catalyst dibutyl tin dilaurate;
step 3, preparation of water-based paint:
mixing deionized water, water-based resin and an auxiliary agent at a rotating speed of 700rpm, and dispersing at a high speed of 2000rpm for 30min to obtain a component A; titanium dioxide modified curing agent is used as a component B; before use, component B is added to obtain the water-based paint with the solid content of 35 percent.
The water-based paint comprises the following components in mass percent: 60 parts of water-based resin, 89 parts of titanium dioxide modified curing agent and 4.0 parts of auxiliary agent; the auxiliary agent comprises the following components in mass: 0.3 part of wetting agent, 0.5 part of dispersing agent, 0.04 part of defoamer, 0.05 part of rheological additive, 0.05 part of leveling agent, 3 parts of film forming additive and 0.10 part of preservative.
Comparative example 1: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 2, preparation of a component B:
mixing methyl methacrylate, gamma-aminopropyl triethoxysilane and acetone, and reacting for 5min under the protection of nitrogen atmosphere to obtain secondary aminosiloxane; the molar ratio of methyl methacrylate to gamma-aminopropyl triethoxysilane is 1.01:1;
mixing 75v% ethanol solution and secondary aminosilicone, regulating the pH of the system to 4 by glacial acetic acid, and stirring at room temperature for hydrolysis for 55min; adding titanium dioxide, heating to 70 ℃, and reacting for 6 hours to obtain sol; centrifuging for 8min, filtering, washing, and vacuum drying at 80deg.C for 12 hr to obtain modified titanium dioxide; the proportion of titanium dioxide, secondary aminosilicone and ethanol solution is 25g:5.3g:100mL;
mixing the HDI trimer and the modified titanium dioxide, stirring and dispersing for 10min, slowly heating to 75 ℃, adding a catalyst, and reacting until the system is transparent; cooling, filtering, washing and drying to obtain the titanium dioxide modified curing agent; the titanium dioxide modified curing agent is prepared from the following components in parts by mass: 42 parts of HDI trimer, 20 parts of modified titanium dioxide and 0.05 part of catalyst dibutyl tin dilaurate;
steps 1 and 3 were the same as in example 1 to obtain an aqueous coating material.
Comparative example 2: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 2, preparation of water-based paint:
mixing deionized water, water-based resin and an auxiliary agent at a rotating speed of 600rpm, and dispersing at a rotating speed of 1500rpm for 60min to obtain a component A; titanium dioxide and a curing agent are taken as a component B; before use, component B is added to obtain the water-based paint with the solid content of 35 percent.
The water-based paint comprises the following components in mass percent: 40 parts of water-based resin, 20 parts of titanium dioxide, 42 parts of curing agent and 1.5 parts of auxiliary agent; the auxiliary agent comprises the following components in mass: 0.1 part of wetting agent, 0.3 part of dispersing agent, 0.02 part of defoamer, 0.02 part of rheological additive, 0.03 part of flatting agent, 1 part of film forming additive and 0.05 part of preservative.
Step 1 was the same as in example 1 to obtain an aqueous coating material.
Comparative example 3: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 1, preparation of aqueous resin:
1.1. mixing linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride and maleic anhydride, adding solvent dimethylbenzene, heating to 120 ℃, stirring for 40min, heating to 220 ℃ at a heating rate of 20 ℃/h, and carrying out heat preservation reflux reaction for 150min to obtain modified alkyd polyol; the modified alkyd polyol comprises the following components in parts by mass: 133 parts of linolenic acid, 37.5 parts of pentaerythritol, 10 parts of 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, 18 parts of phthalic anhydride and 14 parts of maleic anhydride; the ratio of linolenic acid to dimethylbenzene is 5g/100mL;
step 1.2 and step 2 were the same as comparative example 2, to obtain an aqueous coating material.
Comparative example 4: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
step 1, preparation of aqueous resin:
1.1. mixing linolenic acid, pentaerythritol, phthalic anhydride and maleic anhydride, adding solvent dimethylbenzene, heating to 120 ℃, stirring for 40min, heating to 220 ℃ at a heating rate of 20 ℃/h, and carrying out heat preservation reflux reaction for 150min to obtain modified alkyd polyol; the modified alkyd polyol comprises the following components in parts by mass: 134 parts of linolenic acid, 37.5 parts of pentaerythritol, 18 parts of phthalic anhydride and 14 parts of maleic anhydride; the ratio of linolenic acid to dimethylbenzene is 5g/100mL;
step 1.2 and step 2 were the same as comparative example 2, to obtain an aqueous coating material.
Comparative example 5: a preparation process of an automotive corrosion-resistant water-based paint comprises the following steps:
1.2. mixing modified alkyd polyol and isophorone diisocyanate, adding a catalyst under the protection of nitrogen atmosphere, and heating to 70 ℃ for reaction for 5 hours; regulating the temperature of the system to 60 ℃, adding 2-bis (hydroxymethyl) propionic acid, hydroxyl-terminated polysiloxane and 1, 4-butanediol, and reacting for 200min; cooling to 50 ℃, adding triethylamine, reacting for 20min and neutralizing; adding butyl acrylate, styrene, diacetone acrylamide and adipic dihydrazide, mixing, adding an emulsifying agent and deionized water, and stirring and dispersing for 35min at a rotating speed of 180 rpm; adding an initiator, and reacting for 4 hours to obtain aqueous resin;
the aqueous resin comprises the following components in mass percent: 30 parts of modified alkyd polyol, 20 parts of isophorone diisocyanate, 0.1 part of catalyst dibutyltin dilaurate, 3 parts of 2-bis (hydroxymethyl) propionic acid, 3 parts of hydroxyl-terminated polysiloxane, 1 part of 1, 4-butanediol, 3 parts of triethylamine, 5 parts of butyl acrylate, 4.5 parts of styrene, 0.2 part of diacetone acrylamide, 0.1 part of adipic acid dihydrazide, 0.5 part of emulsifier and 0.3 part of initiator ammonium persulfate; the emulsifier is the mixture of dodecyl sodium sulfate SDS and octyl phenol polyoxyethylene ether OP-10, and the mass ratio is 2:1; the solid content of the aqueous resin is 45%;
step 1.1 and step 2 were the same as comparative example 2, to obtain an aqueous coating material.
Experiment: the aqueous coating materials obtained in examples 1 to 3 and comparative examples 1 to 5 were applied to the surface of a tin plate, the thickness of the coating film was 30. Mu.m, and the coating film was dried (GB 1728 was used as a drying reference) to form a film layer, and test pieces were prepared, and the properties thereof were measured and the measurement results were recorded, respectively:
pencil hardness test: using GB/T6739 as a reference standard, and detecting the pencil hardness of the sample by using a pencil hardness tester;
adhesion rating test: using GB/T1720 as a reference standard, testing the adhesive force of a sample by a cross-cut method, and taking the adhesive force grade as a test standard;
mechanical property test: testing a film sample by adopting a tensile machine, wherein the sample is a dumbbell-shaped sample strip, and placing the sample at room temperature for 24 hours to eliminate internal stress, and the stretching rate is 1mm/min;
and (3) water resistance test: using GB/T1733 as a reference standard, placing a sample into deionized water at 25 ℃ for soaking for 10d, and observing the change of the sample;
corrosion resistance test: the electrochemical testing method comprises the steps of carrying out electrochemical testing on a sample by adopting an electrochemical workstation, wherein a reference electrode is a saturated calomel electrode, an auxiliary electrode is a platinum electrode, a working electrode is a film sample, and electrolyte is NaCl solution with the mass fraction of 3.5%.
From the data in the above table, the following conclusions can be clearly drawn:
the aqueous coating materials obtained in examples 1 to 3 were compared with the aqueous coating materials obtained in comparative examples 1 to 5, and it was found that the detection results,
compared with the comparative examples, the water-based paint obtained in examples 1-3 has better data expression of hardness, adhesive force grade, tensile strength, water resistance and corrosion potential after being coated and dried; this fully demonstrates that the invention realizes the improvement of the hardness, adhesive force, mechanical property, water resistance and corrosion resistance of the film layer prepared by the water-based paint.
The preparation process of component B in comparative example 1 is different from that of example 1; component B in comparative example 2 is titanium white powder and a curing agent; on the basis of comparative example 2, the preparation components and processes of the aqueous resins in comparative examples 3 to 5 are different; the water-based paint obtained in comparative examples 1 to 5 was coated and dried to form a film layer, and the data of hardness, adhesive force grade, tensile strength, water resistance and corrosion potential were not excellent, and it was found that the setting of component B, water-based resin component and process thereof according to the present invention can promote improvement of hardness, adhesive force, mechanical properties, water resistance and corrosion resistance of the film layer produced by the water-based paint.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation process of an automotive corrosion-resistant water-based paint is characterized by comprising the following steps of: the method comprises the following steps:
step 1, preparation of aqueous resin:
taking linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, phthalic anhydride, maleic anhydride, epoxy resin and ethylene glycol monobutyl ether as components, and reacting at high temperature to obtain modified alkyd polyol;
reacting modified alkyd polyol with diisocyanate to obtain water-based resin;
step 2, preparation of water-based paint:
mixing deionized water, aqueous resin and an auxiliary agent by stirring, and dispersing at a high speed for 30-60 min to obtain a component A; titanium dioxide and a curing agent are taken as a component B; before use, component B is added to obtain the water-based paint.
2. The process for preparing the corrosion-resistant water-based paint for automobiles according to claim 1, which is characterized in that: in the step 2, the water-based paint comprises the following components in mass percent: 40-60 parts of water-based resin, 20-25 parts of titanium dioxide, 42-64 parts of curing agent and 1.8-4.5 parts of auxiliary agent.
3. The process for preparing the corrosion-resistant water-based paint for automobiles according to claim 2, which is characterized in that: the aqueous resin is prepared by the following process:
step 1, preparing modified alkyd polyol:
mixing linolenic acid, pentaerythritol, 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, 48-56% of phthalic anhydride and maleic anhydride, adding solvent dimethylbenzene, heating to 120-130 ℃, stirring for 20-40 min, heating to 220-240 ℃ at a heating rate of 20 ℃/h, and carrying out heat preservation reflux reaction for 100-150 min;
cooling to 180-200 ℃, adding epoxy resin and phthalic anhydride with the mass of the rest components, and carrying out heat preservation reaction until the acid value of the system is 40-60 mgKOH/g; cooling to 115-125 ℃, adding ethylene glycol monobutyl ether, reacting for 90-120 min, cooling to 60-70 ℃, adding triethylamine for neutralization, and obtaining modified alkyd polyol;
step 2, preparation of aqueous resin:
mixing modified alkyd polyol and isophorone diisocyanate, adding a catalyst under the protection of nitrogen atmosphere, and heating to 70-80 ℃ for reaction for 4-5 h; regulating the temperature of the system to 60-70 ℃, adding 2-bis (hydroxymethyl) propionic acid, hydroxyl-terminated polysiloxane and 1, 4-butanediol, and reacting for 160-200 min; cooling to 50-60 ℃, adding 2-hydroxyethyl methacrylate phosphate, reacting for 5-6 h, and adding triethylamine for neutralization; adding butyl acrylate, styrene, diacetone acrylamide and adipic dihydrazide, mixing, adding an emulsifying agent and deionized water, and stirring and dispersing for 25-35 min at a rotating speed of 180-220 rpm; and adding an initiator, and reacting for 4-5 hours to obtain the water-based resin.
4. A process for preparing a corrosion-resistant aqueous coating for automobiles according to claim 3, which is characterized in that: the modified alkyd polyol comprises the following components in parts by mass: 133 to 145 parts of linolenic acid, 34 to 40 parts of pentaerythritol, 10 to 13 parts of 9- (3, 5-dicarboxyphenyl) -3, 6-carbazole dicarboxylic acid, 18 to 30 parts of phthalic anhydride, 7.7 to 14 parts of maleic anhydride, 20 to 40 parts of epoxy resin, 7 to 12 parts of ethylene glycol monobutyl ether and 10 to 20 parts of triethylamine.
5. The process for preparing the corrosion-resistant water-based paint for automobiles according to claim 4, wherein the process comprises the following steps: the aqueous resin comprises the following components in parts by mass: 30 to 40 parts of modified alkyd polyol, 20 to 24 parts of isophorone diisocyanate, 0.1 to 0.2 part of catalyst dibutyl tin dilaurate, 3 to 4 parts of 2-bis (hydroxymethyl) propionic acid, 2 to 4 parts of hydroxyl-terminated polysiloxane, 0.5 to 1.0 part of 1, 4-butanediol, 1.8 to 2.5 parts of 2-hydroxyethyl methacrylate phosphate, 3 to 6 parts of triethylamine, 5 to 8 parts of butyl acrylate, 4.5 to 6.5 parts of styrene, 0.2 to 0.3 part of diacetone acrylamide, 0.1 to 0.2 part of adipic dihydrazide, 0.5 to 0.7 part of emulsifier and 0.3 to 0.4 part of initiator ammonium persulfate.
6. The process for preparing the corrosion-resistant water-based paint for automobiles according to claim 1, which is characterized in that: the component B is a titanium dioxide modified curing agent and is prepared by the following process:
mixing ethanol solution and secondary aminosilicone, regulating the pH of the system to 3-4 by glacial acetic acid, and stirring and hydrolyzing at room temperature for 55-75 min; adding titanium dioxide, heating to 70-85 ℃, and reacting for 4-6 hours to obtain sol; centrifuging for 8-15 min, filtering, washing, and vacuum drying at 80-90 ℃ for 8-12 h to obtain modified titanium dioxide;
mixing the HDI trimer and the modified titanium dioxide, stirring and dispersing for 10-15 min, slowly heating to 75-85 ℃, adding a catalyst, and reacting until the system is transparent; cooling, suction filtering, washing and drying to obtain the titanium white modified solidifying agent.
7. The process for preparing the corrosion-resistant water-based paint for automobiles according to claim 6, wherein the process comprises the following steps: the ratio of the titanium dioxide, the secondary aminosilicone and the ethanol solution is 25g (5.3-8.0 g) to 100mL.
8. The process for preparing the corrosion-resistant water-based paint for automobiles according to claim 6, wherein the process comprises the following steps: the secondary aminosilicone is prepared by the process of:
mixing 3- (cyclohexane) -1-propanesulfonic acid, gamma-aminopropyl triethoxysilane and acetone, and reacting for 5-10 min under the protection of nitrogen atmosphere.
9. The process for preparing the corrosion-resistant water-based paint for automobiles according to claim 8, wherein the process comprises the following steps: the molar ratio of the 3- (cyclohexane) -1-propanesulfonic acid and the gamma-aminopropyl triethoxysilane is (1.01-1.05): 1.
10. A corrosion-resistant aqueous coating for automobiles prepared by the preparation process according to any one of claims 1 to 9.
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| CN108129667A (en) * | 2017-12-19 | 2018-06-08 | 吉力水性新材料科技（珠海）有限公司 | Phosphate/polyurethane-modified aqueous alkide resin and preparation method thereof |
| CN113278140A (en) * | 2021-05-24 | 2021-08-20 | 江苏华伦化工有限公司 | Epoxy acrylic acid modified waterborne alkyd resin and preparation method thereof |
| CN115831518A (en) * | 2022-11-11 | 2023-03-21 | 宁波振鑫新材料科技有限公司 | Corrosion-resistant neodymium iron boron permanent magnet material and preparation method thereof |
| CN116082597A (en) * | 2022-12-05 | 2023-05-09 | 广州境好新材料有限公司 | Polyurethane-acrylic ester-alkyd aqueous dispersion, preparation method and application thereof |
| CN116178636A (en) * | 2023-02-22 | 2023-05-30 | 湖北双键精细化工有限公司 | Epoxy modified waterborne alkyd resin and preparation method thereof |
| CN116462806A (en) * | 2023-03-30 | 2023-07-21 | 广东恒和永盛集团有限公司 | Composite modified alkyd dispersion and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129667A (en) * | 2017-12-19 | 2018-06-08 | 吉力水性新材料科技（珠海）有限公司 | Phosphate/polyurethane-modified aqueous alkide resin and preparation method thereof |
| CN113278140A (en) * | 2021-05-24 | 2021-08-20 | 江苏华伦化工有限公司 | Epoxy acrylic acid modified waterborne alkyd resin and preparation method thereof |
| CN115831518A (en) * | 2022-11-11 | 2023-03-21 | 宁波振鑫新材料科技有限公司 | Corrosion-resistant neodymium iron boron permanent magnet material and preparation method thereof |
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| CN116178636A (en) * | 2023-02-22 | 2023-05-30 | 湖北双键精细化工有限公司 | Epoxy modified waterborne alkyd resin and preparation method thereof |
| CN116462806A (en) * | 2023-03-30 | 2023-07-21 | 广东恒和永盛集团有限公司 | Composite modified alkyd dispersion and preparation method and application thereof |
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