CN112759999A - Preparation method of organic silicon modified water-based acrylic polyurethane anticorrosive paint - Google Patents
Preparation method of organic silicon modified water-based acrylic polyurethane anticorrosive paint Download PDFInfo
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- CN112759999A CN112759999A CN202110083107.7A CN202110083107A CN112759999A CN 112759999 A CN112759999 A CN 112759999A CN 202110083107 A CN202110083107 A CN 202110083107A CN 112759999 A CN112759999 A CN 112759999A
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- Prior art keywords
- anticorrosive paint
- preparation
- parts
- organic silicon
- emulsion
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000004814 polyurethane Substances 0.000 title claims abstract description 65
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- 239000003973 paint Substances 0.000 title claims abstract description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 34
- 239000010703 silicon Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- -1 ether polyol Chemical class 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 229920006027 ternary co-polymer Polymers 0.000 claims abstract description 10
- 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 abstract description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 4
- 238000013329 compounding Methods 0.000 claims abstract description 3
- GPCIDUIBGGUBJG-UHFFFAOYSA-N hexanedioic acid;hexane-1,1-diol Chemical compound CCCCCC(O)O.OC(=O)CCCCC(O)=O GPCIDUIBGGUBJG-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000576 coating method Methods 0.000 claims description 47
- 239000011248 coating agent Substances 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000001804 emulsifying effect Effects 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000011056 performance test Methods 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 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 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 claims 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 claims 1
- 239000007888 film coating Substances 0.000 claims 1
- 238000009501 film coating Methods 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 229920000151 polyglycol Polymers 0.000 claims 1
- 239000010695 polyglycol Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 230000008719 thickening Effects 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000011258 core-shell material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 abstract 1
- 238000012512 characterization method Methods 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 238000010556 emulsion polymerization method Methods 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 7
- 238000004321 preservation Methods 0.000 description 6
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- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KSFBTBXTZDJOHO-UHFFFAOYSA-N diaminosilicon Chemical compound N[Si]N KSFBTBXTZDJOHO-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 238000007761 roller coating Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- 229920001897 terpolymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation method of an organic silicon modified water-based acrylic polyurethane anticorrosive paint. The preparation method of the anticorrosive paint comprises the following steps: vinyl organic silicon-polyurethane seed emulsion synthesis, organic silicon-acrylic acid-polyurethane copolymer emulsion synthesis, copolymer emulsion compounding, copolymer emulsion application and performance characterization; selecting polyols such as polytetrahydrofuran ether polyol, 1, 4-butanediol adipate, hexanediol adipate and the like, diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate and the like, and introducing an organic silicon intermediate and an acrylic monomer to copolymerize and modify the waterborne polyurethane. The ternary copolymer emulsion is synthesized by adopting a seed emulsion polymerization method, and the core-shell structure emulsion with excellent performance is prepared by two-stage copolymerization. The invention has the beneficial effects that: the preparation method of the high-performance organic silicon modified water-based acrylic polyurethane anticorrosive paint can be used for preparing the water-based metal anticorrosive paint with high gloss, high hardness, high water resistance and corrosion resistance.
Description
Technical Field
The invention relates to the technical field of chemical products, in particular to a preparation method of an organic silicon modified water-based acrylic polyurethane anticorrosive paint.
Background
The chemical, physical or electrochemical effects that occur between metals and the surrounding medium cause the deterioration and deterioration of metals, known as metal corrosion. The corrosion of metal is a very common phenomenon, the damage of metal is rarely caused by simple mechanical or physical factors, most of damaged metal materials have close relationship with the surrounding environment factors, and the environment media contacting with the metal are the origin of the metal corrosion, and comprise naturally occurring atmosphere, rainwater, seawater, soil, raw materials for production, products and the like. The metal corrosion has a very wide range of involvement, exists in various fields of national economy and national defense construction, and has very serious damage to facilities in the national economy and the national defense construction. The global losses due to metal corrosion are quite dramatic for human beings, and statistically, the economic losses due to metal corrosion are about $ 1 trillion each year around the world, while the stress corrosion and corrosion fatigue in metal corrosion often cause unforeseen accidents and harm personal safety. Not only does metal corrosion cause a great deal of energy loss and waste, but also, in the industrial production field, equipment and facility safety problems caused by corrosion often cause serious economic losses and may cause environmental pollution.
At present, the most effective method for metal corrosion is to use a coating to protect the metal, which is the most economical, practical and effective method. The traditional metal anticorrosive paint has good corrosion protection effect on a metal matrix, but almost all anticorrosive paints are solvent-based paints, a large amount of solvent is volatilized in a film forming process, the volatilized solvent can cause damage and pollution to a human body and the surrounding environment, and simultaneously causes resource waste, the solvent-based anticorrosive paint mainly takes red lead, zinc chrome yellow and other toxic pigments containing lead, cadmium and chromium as antirust components, and ions can cause damage to production, construction and users and seriously pollute the environment.
With the continuous improvement of environmental requirements and the gradual enhancement of environmental awareness of people and the strict supervision and control of pollution by laws and regulations, and the fields of various industries, buildings and the like have higher performance requirements on anticorrosive coatings, especially water-based metal anticorrosive coatings, such as high gloss, high hardness, high water resistance and corrosion resistance, so that the development of the water-based metal anticorrosive coating with high performance is realized, and the promotion of clean production in the coating industry is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an organosilicon modified water-based acrylic polyurethane anticorrosive paint aiming at the defects of the prior art, which adopts organosilicon-acrylic acid-polyurethane ternary polymerization and has complementary advantages, overcomes the limitation of single resin anticorrosive paint, endows the paint with excellent weather resistance, water resistance, acid and alkali resistance and other anticorrosive functions, and has good mechanical properties such as high hardness and high wear resistance.
In order to achieve the purpose, the invention provides the following technical scheme:
the advantages are complemented by adopting organosilicon-polyurethane-acrylic acid copolymerization modification. The coating made of the aqueous Polyurethane (PU) has the characteristics of better mechanical property, abrasion resistance, chemical resistance, flexibility and the like, but has poor water resistance and high price. The acrylic resin (PA) prepared coating has good water resistance and solvent resistance, adjustable hardness and low price, but has poor chemical resistance, and the aqueous acrylic polyurethane coating synthesized by the method can overcome respective defects and improve the performances of emulsion and a coating film by copolymerizing and combining PU and PA. Meanwhile, an organic silicon intermediate is further selected for modification, so that the weather resistance, water resistance, acid and alkali resistance and other anticorrosion functions of the coating are further improved, and the organic silicon is enriched on the surface of the coating, so that the coating has good mechanical properties.
The preparation method of the organic silicon modified waterborne acrylic polyurethane anticorrosive paint comprises the following steps:
firstly, synthesizing vinyl organic silicon-polyurethane seed emulsion, adding 5 to 10 parts of polyester polyol, 5 to 10 parts of polyether polyol and 1 to 3 parts of hydrophilic chain extender into a four-neck flask provided with a mechanical stirrer and a thermometer, heating to 110 ℃ and 120 ℃ for vacuum dehydration for 1 to 2 hours, cooling to 40 to 60 ℃, adding 5 to 10 parts of isocyanate and 0.01 to 0.1 part of organic metal catalyst, heating to 90 ℃, keeping the temperature for 2 hours, dropwise adding 1 to 3 parts of organic silicon intermediate, supplementing 5 to 15 parts of N, N-Dimethylformamide (DMF) solvent after dropwise adding to adjust the system viscosity, continuing to keep the temperature for 2 hours, dropwise adding 3 to 8 parts of HEMA, continuing to keep the temperature for 2 hours, measuring the NCO content by adopting a di-N-butylamine method, cooling after the indexes are qualified, adding 5 to 15 parts of acetone to adjust the system viscosity during the cooling process, adding 1 to 3 parts of triethylamine at 60 ℃, carrying out neutralization reaction for 10min, quickly adding 40 to 60 parts of deionized water, carrying out high-speed emulsification and dispersion, adding 0.5 to 2 parts of amine post-chain extender in the emulsification process, and continuously stirring and emulsifying for 1 hour to obtain the vinyl organosilicon-polyurethane seed emulsion;
secondly, synthesizing an organic silicon-acrylic acid-polyurethane copolymer emulsion, adding 20-40 parts of deionized water, 0.3-1.0 part of initiator and 1-3 parts of emulsifier into a reaction container, then sequentially adding various acrylate monomers, starting high-speed stirring and emulsifying, and emulsifying for 1-2 hours for later use; putting the organosilicon-polyurethane emulsion with vinyl prepared in the first step into a reaction vessel, adding 5-15 parts of deionized water, 0.3-1 part of initiator and 10-20 parts of emulsified acrylate monomer, stirring and heating to 75-80 ℃, starting to dropwise add the rest acrylate pre-emulsion and initiator after the system is initiated, reacting for 2 hours at constant temperature after the pre-emulsion is dropwise added, and adding ammonia water to adjust the pH value to obtain organosilicon-acrylic acid-polyurethane ternary copolymer emulsion;
thirdly, compounding copolymerization emulsion, adding 0.5-3 parts of environment-friendly auxiliary agent, 10-25 parts of water-based color paste and 5-15 parts of filler into the prepared terpolymer emulsion, uniformly stirring, detecting viscosity and solid content, and obtaining the organic silicon modified water-based acrylic polyurethane anticorrosive paint after the paint is qualified;
and fourthly, applying the copolymer emulsion and characterizing the performance, applying the anticorrosive paint obtained in the third step to a metal coating, such as an iron casting, an aluminum profile, a galvanized substrate and the like, by adopting a spraying or roller coating mode, and carrying out comprehensive performance test on the anticorrosive paint, and comparing the anticorrosive paint with a commercially available anticorrosive paint product.
Further, the polyester polyol is one or more of polycaprolactone polyol, poly adipic acid-1, 4-butanediol ester, polyethylene glycol adipate and poly adipic acid hexanediol ester.
Further, the polyether polyol is one or more of polytetrahydrofuran polyether polyol, propylene oxide polyether polyol and polytrimethylene ether glycol.
Further, the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
Further, the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid and dihydroxy sulfonate.
Furthermore, the organic metal catalyst is one or more of organic bismuth, organic zinc, organic zirconium and bismuth-zinc alloy catalyst.
Furthermore, the organosilicon intermediate is one or more of a dihydroxy organosilicon intermediate, a diamino silane coupling agent and an amino silane coupling agent.
Further, the amine post-chain extender is one or more of ethylenediamine, diethylenetriamine and isophorone diamine.
Further, the emulsifier is one or more of sodium dodecyl sulfate, alkylphenol polyoxyethylene and allyl ether sulfonate.
Furthermore, the acrylic acid monomer is one or more of methyl methacrylate, butyl acrylate, isooctyl acrylate, acrylic acid, methacrylic acid and glycidyl methacrylate.
Further, the initiator is one or more of potassium persulfate, ammonium persulfate and sodium bisulfite.
Furthermore, the environment-friendly water-based auxiliary agent is one or more of an organic silicon wetting agent, a modified amide dispersing agent, an organic silicon flatting agent, an organic silicon defoaming agent, a water-based flash rust inhibitor, a polyurethane thickener and an acrylic acid thickener.
Furthermore, the filler is one or more of talcum powder, mica powder, precipitated barium sulfate and zinc phosphate.
Furthermore, the performance test is one or more of an adhesion test, a hardness test, a glossiness test, an impact resistance test, a film forming property test and a coating water absorption test.
By adopting the technical scheme, the copolymerization emulsion is synthesized by utilizing a seed emulsion method, and the core-shell structure emulsion with more excellent performance and better stability can be prepared by two-stage copolymerization. The core-shell layer of the core-shell structure latex particle has grafting, interpenetrating network or ionic bonding, thereby showing better film forming property, stability and adhesiveness and being easier to carry out special function design of the emulsion; the product is applied to a water-based metal anticorrosive paint surface layer, and the performances of the product are comprehensively tested to obtain the paint with high-performance anticorrosive functions such as weather resistance, water resistance, acid and alkali resistance and the like.
The invention has the beneficial effects that: by adopting the technical scheme, the organic silicon modified waterborne acrylic polyurethane anticorrosive paint with high performance can be obtained, the dihydroxy or diamino organic silicon intermediate and the acrylic monomer are introduced to compound modify waterborne polyurethane, the three are organically combined, the advantages are complementary, the limitation of a single resin anticorrosive paint is overcome, various performances of the waterborne polyurethane anticorrosive paint are greatly improved, and the waterborne metal anticorrosive paint with high gloss, high hardness, high water resistance and corrosion resistance is prepared.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic diagram of a technical route of the present invention;
FIG. 2 is an enlarged view of the point A in FIG. 1;
FIG. 3 is an enlarged view of the point B in FIG. 1;
FIG. 4 is an enlarged view of FIG. 1 at C;
FIG. 5 is an enlarged view of FIG. 1 at D;
FIG. 6 is an enlarged view of E in FIG. 1;
FIG. 7 is an enlarged view of FIG. 1 at F;
FIG. 8 is an enlarged view of FIG. 1 at G;
FIG. 9 is an enlarged view at H in FIG. 1;
FIG. 10 is an enlarged view at I of FIG. 1;
FIG. 11 is a schematic diagram showing the effect of the amount of dihydroxy organosilicon intermediate on the water absorption of the coating film in the first embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An organosilicon modified waterborne acrylic polyurethane anticorrosive paint comprises isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), polyoxypropylene glycol (PPG 2000), polytetrahydrofuran ether polyol (PTMEG1000), polyethylene glycol adipate (PEA 2000), poly-1, 4-butylene glycol adipate (PBA 2000), poly-hexanediol adipate (PHA 2000), bisaminosilane coupling agent (KH-792), dihydroxyorganosilicon intermediate (Si-15), dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), Triethylamine (TEA), ethylenediamine, acetone, N-Dimethylformamide (DMF), hydroxyethyl methacrylate (HEMA), Methyl Methacrylate (MMA), methacrylic acid (MAA), Glycidyl Methacrylate (GMA), Butyl Acrylate (BA), sodium dodecyl sulfate, alkylphenol polyoxyethylene, allyl ether sulfonate, ammonium persulfate, potassium persulfate, sodium bisulfite, an organic silicon wetting agent, an organic silicon leveling agent, a polyurethane thickener, an organic silicon defoamer, water-based color paste, precipitated barium sulfate, talcum powder, mica powder and deionized water.
Example one
Firstly, 32.1g of PTMEG1000, 55g of PEA2000 and 8.2g of DMBA are added into a four-mouth bottle provided with a thermometer, a reflux condenser tube and a constant speed stirrer, vacuum dehydration is carried out for 2h under the environment with the temperature of 110-120 ℃, then the temperature is reduced to 50 ℃, 62g of IPDI and 0.1g of organic bismuth catalyst are added into a reactor to be gradually heated to 90 ℃ for polymerization reaction for 2h, 6g of organosilicon intermediate Si-15 is dripped, 40g of N, N-Dimethylformamide (DMF) solvent is added after the dripping is finished to adjust the system viscosity, the heat preservation reaction is continued for 2h, 22g of HEMA is dripped, the heat preservation reaction is continued for 2h, the NCO content is measured by adopting a di-N-butylamine method, the temperature is reduced after the index is qualified, 30g of acetone is added in the temperature reduction process to adjust the system viscosity, 5.6g of triethylamine is added at 60 ℃, the neutralization reaction is carried out for 10min, 235g of deionized water is, adding 4g of ethylenediamine during the emulsification process, and continuing stirring and emulsifying for 1 hour to obtain vinyl organosilicon-polyurethane seed emulsion;
secondly, adding 400g of deionized water, 3g of ammonium persulfate initiator, 7g of sodium dodecyl sulfate and 7g of OP-10 emulsifier into a reaction container, then sequentially adding 300g of MMA, 125g of BA and 24g of MAA acrylate monomer, starting high-speed stirring and emulsifying, and emulsifying for 1-2 hours for later use; putting 200g of the organosilicon-polyurethane emulsion with vinyl prepared in the first step into a reaction vessel, adding 3g of ammonium persulfate, 100g of deionized water and 150g of emulsified acrylate monomer, stirring and heating to 75-80 ℃, starting to dropwise add the remaining acrylate pre-emulsion after the system is initiated, reacting for 2 hours at constant temperature after the pre-emulsion is dropwise added, and adding ammonia water to adjust the pH value to 7 to obtain organosilicon-acrylic acid-polyurethane ternary copolymer emulsion;
taking 60g of the prepared ternary copolymer emulsion, adding 25g of aqueous titanium white slurry, 5g of precipitated barium sulfate, 5g of aqueous zinc phosphate, 0.3g of modified amide dispersing agent, 0.2 g of organic silicon wetting agent, 0.2 g of organic silicon leveling agent, 0.3g of aqueous flash rust inhibitor, 0.3g of defoaming agent, 0.3g of polyurethane thickening agent and 3.4g of deionized water, uniformly stirring, and detecting viscosity and solid content to obtain the qualified organic silicon modified aqueous acrylic polyurethane anticorrosive paint;
and fourthly, applying the anticorrosive paint obtained in the third step to a metal coating, such as an iron casting, an aluminum profile, a galvanized base material and the like, by adopting a spraying or roll coating mode, and carrying out comprehensive performance test on the anticorrosive paint, and comparing the anticorrosive paint with a commercially available anticorrosive paint product.
Example two
Firstly, adding 32.1g of PPG2000, 55g of PHA2000 and 8.2g of DMBA into a four-mouth bottle provided with a thermometer, a reflux condenser tube and a constant speed stirrer, carrying out vacuum dehydration for 2h under the environment with the temperature of 110-120 ℃, then cooling to 50 ℃, adding 62g of IPDI and 0.1g of organic bismuth catalyst into a reactor, gradually heating to 90 ℃ for polymerization for 2h, dropwise adding 6g of dihydroxyorganosilicon intermediate, supplementing 40g of N, N-Dimethylformamide (DMF) solvent after dropwise adding to adjust the system viscosity, continuing to carry out heat preservation reaction for 2h, dropwise adding 22g of HEMA, continuing to carry out heat preservation reaction for 2h, measuring the NCO content of the prepolymer by adopting a di-N-butylamine method, cooling after the index is qualified, adding 30g of acetone to adjust the system viscosity during cooling, adding 5.6g of triethylamine at 60 ℃, carrying out neutralization reaction for 10min, rapidly adding 235g of deionized water, emulsifying and dispersing at high speed, adding 4g of ethylenediamine during emulsification, stirring and emulsifying for 1 hour to obtain vinyl organosilicon-polyurethane seed emulsion;
secondly, adding 400g of deionized water, 3g of ammonium persulfate initiator, 7g of sodium dodecyl sulfate and 7g of OP-10 emulsifier into a reaction container, then sequentially adding 300g of MMA, 125g of BA and 24g of MAA acrylate monomer, starting high-speed stirring and emulsifying, and emulsifying for 1-2 hours for later use; putting 200g of the organosilicon-polyurethane emulsion with vinyl prepared in the first step into a reaction vessel, adding 3g of ammonium persulfate, 100g of deionized water and 150g of emulsified acrylate monomer, stirring and heating to 75-80 ℃, starting to dropwise add the remaining acrylate pre-emulsion after the system is initiated, reacting for 2 hours at constant temperature after the pre-emulsion is dropwise added, and adding ammonia water to adjust the pH value to 7 to obtain organosilicon-acrylic acid-polyurethane ternary copolymer emulsion;
taking 60g of the prepared ternary copolymer emulsion, adding 25g of aqueous titanium white slurry, 5g of precipitated barium sulfate, 5g of aqueous zinc phosphate, 0.3g of modified amide dispersing agent, 0.2 g of organic silicon wetting agent, 0.2 g of organic silicon leveling agent, 0.3g of aqueous flash rust inhibitor, 0.3g of defoaming agent, 0.3g of polyurethane thickening agent and 3.4g of deionized water, uniformly stirring, and detecting viscosity and solid content to obtain the qualified organic silicon modified aqueous acrylic polyurethane anticorrosive paint;
and fourthly, applying the anticorrosive paint obtained in the third step to a metal coating, such as an iron casting, an aluminum profile, a galvanized base material and the like, by adopting a spraying or roll coating mode, and carrying out comprehensive performance test on the anticorrosive paint, and comparing the anticorrosive paint with a commercially available anticorrosive paint product.
EXAMPLE III
Firstly, adding 32.1g of PPG2000, 55g of PBA2000 and 8.2g of DMPA into a four-mouth bottle provided with a thermometer, a reflux condenser tube and a constant speed stirrer, dehydrating in vacuum for 2h under the environment with the temperature of 110-120 ℃, then cooling to 50 ℃, adding 62g of IPDI and 0.1g of organic bismuth catalyst into a reactor, gradually heating to 90 ℃ for polymerization for 2h, dropwise adding 6g of dihydroxyorganosilicon intermediate, supplementing 40g of N, N-Dimethylformamide (DMF) solvent after dropwise adding to adjust the system viscosity, continuing to perform heat preservation reaction for 2h, dropwise adding 22g of HEMA, continuing to perform heat preservation reaction for 2h, measuring the NCO content of the prepolymer by a di-N-butylamine method, cooling after the index is qualified, adding 30g of acetone to adjust the system viscosity during cooling, adding 5.6g of triethylamine at 60 ℃, performing neutralization reaction for 10min, rapidly adding 235g of deionized water, emulsifying and dispersing at high speed, adding 4g of isophorone diamine during emulsifying, stirring and emulsifying for 1 hour to obtain vinyl organosilicon-polyurethane seed emulsion;
secondly, adding 400g of deionized water, 3g of ammonium persulfate initiator, 7g of sodium dodecyl sulfate and 7g of OP-10 emulsifier into a reaction container, then sequentially adding 300g of MMA, 125g of BA and 24g of MAA acrylate monomer, starting high-speed stirring and emulsifying, and emulsifying for 1-2 hours for later use; putting 200g of the organosilicon-polyurethane emulsion with vinyl prepared in the first step into a reaction vessel, adding 3g of ammonium persulfate, 100g of deionized water and 150g of emulsified acrylate monomer, stirring and heating to 75-80 ℃, starting to dropwise add the remaining acrylate pre-emulsion after the system is initiated, reacting for 2 hours at constant temperature after the pre-emulsion is dropwise added, and adding ammonia water to adjust the pH value to 7 to obtain organosilicon-acrylic acid-polyurethane ternary copolymer emulsion;
taking 60g of the prepared ternary copolymer emulsion, adding 25g of aqueous titanium white slurry, 5g of precipitated barium sulfate, 5g of aqueous zinc phosphate, 0.3g of modified amide dispersing agent, 0.2 g of organic silicon wetting agent, 0.2 g of organic silicon leveling agent, 0.3g of aqueous flash rust inhibitor, 0.3g of defoaming agent, 0.3g of polyurethane thickening agent and 3.4g of deionized water, uniformly stirring, and detecting viscosity and solid content to obtain the qualified organic silicon modified aqueous acrylic polyurethane anticorrosive paint;
and fourthly, applying the anticorrosive paint obtained in the third step to a metal coating, such as an iron casting, an aluminum profile, a galvanized base material and the like, by adopting a spraying or roll coating mode, and carrying out comprehensive performance test on the anticorrosive paint, and comparing the anticorrosive paint with a commercially available anticorrosive paint product.
Process analysis
1. The molar ratio of-NCO group to-OH group in polyurethane synthesis is called isocyanate value (R value), and the proportion of soft segments and hard segments in polyurethane chain segments is usually controlled by controlling the R value, so that the purpose of controlling the material performance is finally achieved. On the basis of the example I, PTMEG2000, PEA2000, IPDI, Si-15, HEMA, DMBA and the like are used as raw materials, the solid content of the emulsion is designed to be 35 +/-1%, and the influence of different R values on the performance of the coating is researched, and the result is shown in the following table 1.
TABLE 1 influence of the R value on the coating Properties
| R value | Appearance of synthetic emulsion | Centrifugal stability | Film forming property |
| 1.3 | Is transparent | Stabilization | Clear, soft, tacky |
| 1.5 | Transparent blue-emitting light | Stabilization | Clear, soft, slightly tacky |
| 1.7 | Transparent blue-emitting light | Stabilization | Transparent and soft |
| 1.9 | Milky white blue light | Stabilization | Transparent and hard |
| 2.1 | Milk white | Layering | White, hard and crisp |
As shown in table 1, as the R value increased, the emulsion became opaque from transparent, the color changed from bluish light to milky white, the particle size increased, the viscosity decreased, and the emulsion stability became poor. This is because, with the increase of the R value, the amount of free isocyanate groups in the prepolymer increases, the hard segment content increases, the flexibility of the molecular chain becomes poor, the number of urea groups increases, the hydrophilicity decreases, and the particle size becomes large. When the value of R is too large, for example, R =2.1, the-NCO group reacts violently with water upon emulsification with water to form a large amount of urea bonds and biuret, and the particle size of the emulsion rapidly increases, thereby causing the emulsion to be unstable or even gel.
The coating film becomes soft and hard with an increase in the R value because the smaller the R value, the more soft segments increase, and the molecular weight of the molecule increases and the softness of the molecular segment also increases, so that the surface of the film becomes sticky after the film is formed. When the R value is further increased, the more the-NCO is excessive, the more the carbamido group and biuret group are generated by the reaction with water during emulsification, the larger the proportion of rigid chain links in a molecular chain is, the larger the cohesive energy of the molecules is, and the hardness of the adhesive film is improved. In the first example, the R value is 1.9, taking the stability and film-forming effect of the emulsion into consideration.
2. In the first, second and third examples, PPG2000, PEA2000, PBA2000 and PHA2000 with the same molecular weight are respectively selected as the raw materials of the soft segment, the solid content is designed to be 35 +/-1 percent, the R value is 1.9, and the influence of different types of soft segments on the performance of the emulsion and the application performance of the prepared anticorrosive paint is examined. The effect of different polyester polyols on the coating properties is shown in Table 2 below
TABLE 2 Effect of different polyester polyols on coating Properties
| R value | Appearance of synthetic emulsion | Water absorption rate | Centrifugal stability | Film forming property |
| PPG2000 | Light yellow translucent | —— | Stabilization | Transparent and hard to stick to hand |
| PEA2000 | Milky white blue light | 26.2 | Stabilization | Is transparent and hard |
| PBA2000 | Transparent blue light | 13.4 | Stabilization | Is transparent and hard |
| PHA2000 | Transparent blue light | 10.6 | Stabilization | Transparent and very hard |
As can be seen from Table 2, the film forming effect of the emulsion is optimized by PHA2000, and the water absorption of the film is PHA2000< PBA2000< PEA 2000; this is because in the soft segment structural unit with the same molecular weight, the shorter the carbon chain, the more ester groups, the more likely to form hydrogen bonds with water, and the stronger the ability to bind water, so PEA2000 has the highest water absorption; PBA2000 has a regular substructure, high mechanical strength of a formed film and easy crystallization, and the crystallization is beneficial to limiting the formation of pores and preventing water molecules from permeating and swelling, so that the PBA2000 has low water absorption rate and a hard formed film; compared with PBA2000, PHA2000 has a more regular molecular structure and higher mechanical strength and crystallinity of film formation, so that the water absorption rate is lowest and the film formation is hardest. The aqueous polyurethane coating film prepared by PG2000 has low cohesive energy of ether bond in the structure, and is easy to rotate, so that the coating film has good extensibility and is sticky. In combination, the PHA2000 is selected as the raw material for synthesizing the emulsion, so that the water resistance and hardness of the coating can be improved.
3. The effect of the bishydroxy silicone intermediate on the coating can be seen in the figure "11" of the specification. With the increase of the using amount of the dihydroxy organosilicon intermediate, the water absorption of the coating is reduced from 10.6 percent to below 4.5 percent, the introduction of the dihydroxy organosilicon intermediate endows the coating with lower surface tension and surface energy, the coating has excellent hydrophobicity and smoothness, and the water resistance is improved. When the using amount is more than or equal to 6 percent, the water absorption of the coating film changes slowly. As can be seen from Table 3 below, the adhesion, hardness and impact resistance of the resulting coating product are significantly improved with increasing amounts of the bishydroxy organosilicon intermediate. When the adding amount is 6%, the comprehensive performance of the obtained product is optimal. Considering the influence of the cost and the addition amount on the product performance, the final determined dosage is 6 percent.
TABLE 3 Effect of different amounts of dihydroxy organosilicon intermediates on coating application Properties
4、
5. And (3) performing centrifugal stability test on the emulsion to prepare a 0.5% CaCl2 solution, wherein the CaCl2 solution is prepared according to the following components in percentage by weight: CaCl2 solution = 4: 1 into uniform emulsion, centrifuging at 3000 r/min in a centrifuge, sealing and standing in a test tube for 48h, and observing no phenomena such as floating oil, layering, coagulation and the like.
Analysis of results
After the ternary copolymer emulsion prepared in the second embodiment is applied to a high-performance anticorrosive coating, compared with a certain commercially available oily anticorrosive coating, the performance is outstanding, and various performance indexes are detailed in table 4.
TABLE 4 comparison of the product of example two with the product of a commercially available product having high physical properties
As can be seen from table 4, by adopting the components given in the present application and the preparation method, the silicone-acrylic acid-polyurethane ternary polymerization overcomes the limitation of a single resin anticorrosive coating, greatly improves various properties of the water-based anticorrosive coating, can prepare the silicone modified water-based acrylic acid polyurethane anticorrosive coating with high gloss, high hardness, high water resistance and corrosion resistance, has properties completely reaching or even exceeding the effect of an oil-based anticorrosive coating, integrates environmental protection and high physical properties, can completely replace the oil-based anticorrosive coating, and has a wide application prospect.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the scope of the claims.
Claims (14)
1. A preparation method of an organic silicon modified waterborne acrylic polyurethane anticorrosive paint is characterized by comprising the following steps:
(1): vinyl organic silicon-polyurethane seed emulsion is synthesized by adding 5 to 10 parts of polyester polyol, 5 to 10 parts of polyether polyol and 1 to 3 parts of hydrophilic chain extender into a four-neck flask provided with a mechanical stirring and thermometer, heating to 110 ℃ and 120 ℃ for vacuum dehydration for 1 to 2 hours, cooling to 40 to 60 ℃, adding 8 to 12 parts of isocyanate and 0.01 to 0.1 part of organic metal catalyst, heating to 90 ℃ and keeping the temperature for 2 hours, dripping 1 to 3 parts of organic silicon intermediate, replenishing 5 to 15 parts of N, N-Dimethylformamide (DMF) solvent to adjust the system viscosity after dripping is finished, continuing to keep the temperature for reaction for 2 hours, dripping 3 to 8 parts of HEMA, continuing to keep the temperature for reaction for 2 hours, measuring the NCO content of the prepolymer by adopting a di-N-butylamine method, cooling after the index is qualified, adding 5 to 15 parts of acetone to adjust the system viscosity during the cooling process, adding 1 to 3 parts of triethylamine at 60 ℃, carrying out neutralization reaction for 10min, quickly adding 40 to 60 parts of deionized water, carrying out high-speed emulsification and dispersion, adding 0.5 to 2 parts of amine post-chain extender in the emulsification process, and continuously stirring and emulsifying for 1 hour to obtain the vinyl organosilicon-polyurethane seed emulsion;
(2): synthesizing an organic silicon-acrylic acid-polyurethane copolymer emulsion, adding 20-40 parts of deionized water, 0.3-1.0 part of initiator and 1-3 parts of emulsifier into a reaction container, then sequentially adding various acrylate monomers, starting high-speed stirring and emulsifying, and emulsifying for 1-2 hours for later use; putting the organosilicon-polyurethane emulsion with vinyl prepared in the step (1) into a reaction vessel, adding 5-15 parts of deionized water, 0.3-1 part of initiator and 10-20 parts of emulsified acrylate monomer, stirring and heating to 75-80 ℃, starting to dropwise add the rest acrylate pre-emulsion and initiator after the system is initiated, reacting for 2 hours at constant temperature after the pre-emulsion is dropwise added, and adding ammonia water to adjust the pH value to obtain organosilicon-acrylic acid-polyurethane ternary copolymer emulsion;
(3): compounding copolymerization emulsion, adding 0.5-3 parts of environment-friendly auxiliary agent, 10-25 parts of water-based color paste and 5-15 parts of filler into the prepared ternary copolymerization emulsion, uniformly stirring, detecting viscosity and solid content, and obtaining the organic silicon modified water-based acrylic polyurethane anticorrosive paint after the paint is qualified;
(4): and (3) applying the anticorrosive coating obtained in the step (3) to metal coatings such as iron castings, aluminum profiles, galvanized substrates and the like in a spraying or roll coating mode, carrying out comprehensive performance test on the coatings, and comparing the coatings with commercially available anticorrosive coating products.
2. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the polyester polyol in the step (1) is one or more of polycaprolactone polyol, poly adipic acid-1, 4-butanediol ester, poly glycol adipate and poly hexanediol adipate.
3. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the polyether polyol in the step (1) is one or more of polytetrahydrofuran polyether polyol, propylene oxide polyether polyol and polytrimethylene ether glycol.
4. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the isocyanate in the step (1) is one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate.
5. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the hydrophilic chain extender in the step (1) is one or more of dimethylolpropionic acid, dimethylolbutyric acid and dihydroxy sulfonate.
6. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the organic metal catalyst in the step (1) is one or more of organic bismuth, organic zinc, organic zirconium and bismuth-zinc alloy catalyst.
7. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the organosilicon intermediate in the step (1) is one or more of a dihydroxy organosilicon intermediate (Si-15), a bisaminosilane coupling agent (such as KH-792) and an amino-terminated silane coupling agent.
8. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the amine post-chain extender in the step (1) is one or more of ethylenediamine, diethylenetriamine and isophorone diamine.
9. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the emulsifier in the step (2) is one or more of sodium dodecyl sulfate, alkylphenol ethoxylates and allyl ether sulfonate.
10. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the acrylic acid monomer in the step (2) is one or more of methyl methacrylate, butyl acrylate, isooctyl acrylate, acrylic acid, methacrylic acid and glycidyl methacrylate.
11. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the initiator in the step (2) is one or more of potassium persulfate, ammonium persulfate and sodium bisulfite.
12. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the environment-friendly water-based auxiliary agent in the step (3) is one or more of an organic silicon wetting agent, an organic silicon flatting agent, a modified amide dispersing agent, an organic silicon defoaming agent, a water-based flash rust inhibitor, a polyurethane thickening agent and an acrylic acid thickening polymer.
13. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: the filler in the step (3) is one or more of talcum powder, mica powder, precipitated barium sulfate and zinc phosphate.
14. The preparation method of the organosilicon modified waterborne acrylic polyurethane anticorrosive paint as claimed in claim 1 is characterized by comprising the following steps: and (3) testing the performance in the step (3) by one or more of an adhesion test, a hardness test, a glossiness test, an impact resistance test, a film forming property test and a film coating water absorption test.
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Application publication date: 20210507 |