CN110054980B - Single-component moisture-curing polyurethane heavy-duty anticorrosive coating and preparation method thereof - Google Patents
Single-component moisture-curing polyurethane heavy-duty anticorrosive coating and preparation method thereof Download PDFInfo
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- CN110054980B CN110054980B CN201910386931.2A CN201910386931A CN110054980B CN 110054980 B CN110054980 B CN 110054980B CN 201910386931 A CN201910386931 A CN 201910386931A CN 110054980 B CN110054980 B CN 110054980B
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- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 31
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 28
- 238000013008 moisture curing Methods 0.000 title claims description 12
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 42
- -1 good toughness Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002250 absorbent Substances 0.000 claims abstract description 18
- 230000002745 absorbent Effects 0.000 claims abstract description 18
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 238000007667 floating Methods 0.000 claims abstract description 15
- 239000000049 pigment Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000003086 colorant Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 45
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 41
- 229920000570 polyether Polymers 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 33
- 229920005862 polyol Polymers 0.000 claims description 28
- 150000003077 polyols Chemical class 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000005056 polyisocyanate Substances 0.000 claims description 23
- 229920001228 polyisocyanate Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000001723 curing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- 125000005456 glyceride group Chemical group 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000011527 polyurethane coating Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 5
- 239000003973 paint Substances 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 13
- 208000005156 Dehydration Diseases 0.000 description 11
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- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 11
- 229920001451 polypropylene glycol Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000010533 azeotropic distillation Methods 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920003226 polyurethane urea Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- QKOWXXDOHMJOMQ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)biuret Chemical compound O=C=NCCCCCCNC(=O)N(CCCCCCN=C=O)C(=O)NCCCCCCN=C=O QKOWXXDOHMJOMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004588 polyurethane sealant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a moisture-cured polyurethane heavy-duty anticorrosive coating which comprises the following components in parts by mass: 70-99.9 parts of modified polyurethane prepolymer resin, 2-25 parts of pigment and filler, 0.5-3 parts of dispersing agent, 0.1-1 part of anti-settling agent, 0.2-2 parts of anti-floating coloring agent, 0.2-1 part of defoaming agent, 0.1-1 part of flatting agent, 5-15 parts of latent curing agent and 5-20 parts of water absorbent. The polyurethane coating has a series of excellent performances of good storage stability, high surface smoothness, fast curing and film forming, strong adhesion with a substrate, good toughness, chemical resistance, aging resistance, good high temperature resistance and the like.
Description
Technical Field
The invention belongs to the field of polyurethane anticorrosive coatings, and particularly relates to a single-component moisture-cured polyurethane heavy-duty anticorrosive coating and a preparation method thereof.
Background
With the rapid development of national economic construction and national economy, various steel structures, concrete structures, aluminum-plastic structures and the like are increasingly applied to bridges, buildings, ports, traffic and other industrial and civil engineering, but the characteristic of easy corrosion (corrosion) brings huge economic loss to equipment manufacturing industries and damages natural resources and environmental protection. Statistics show that the corrosion loss accounts for 3-5% of GDP, which exceeds the total loss caused by disasters such as fire, flood, drought and typhoon, and in 2010, the corrosion loss of China is at least 1.2 trillion yuan, and if effective corrosion protection measures are taken, 25-40% of the loss can be avoided. Therefore, the anticorrosion is very important, the coating plays a good role in protecting various engineering products and facilities in various anticorrosion technologies, and a series of anticorrosion coatings are developed at home and abroad successively.
Anticorrosive coatings are generally divided into conventional anticorrosive coatings and heavy anticorrosive coatings, and are an essential coating in paint coatings. The conventional anticorrosive paint plays a role in corrosion resistance on metals and the like under general conditions, and protects the service life of nonferrous metals; the heavy anti-corrosion coating is a kind of anti-corrosion coating which can be applied in a relatively harsh corrosion environment, such as steel materials of ships, bridges, wharfs and the like, and has a longer protection period than the conventional anti-corrosion coating.
The current heavy-duty anticorrosive paint mainly comprises three types, namely epoxy resin paint, polyurethane paint and glass flake paint. The polyurethane coating has the characteristics of excellent corrosion resistance, wear resistance, adhesive force, water resistance, low-temperature flexibility and the like because the macromolecular bonds of the polyurethane coating have structures such as urethane bonds, ester bonds, ether bonds, urea bonds, hydrogen bonds and the like, so that the polyurethane coating occupies a main position in the field of heavy corrosion resistance. Among the polyurethane anticorrosive coatings, a one-component moisture-curable polyurethane coating has more excellent chemical resistance, wear resistance, oil resistance, water resistance and the like because of containing a large amount of urea bond structures. The one-component moisture-curable polyurethane coating has high-tolerance construction characteristics at low or high temperature because it is cured into a film by absorbing moisture (water molecules) in the air.
Patent CN201410673312.9 discloses a one-component moisture-curing polyurethane sealant with low viscosity and high thixotropy, which comprises a polyurethane prepolymer, a water absorption stabilizer, a silane coupling agent, a light stabilizer, an antioxidant, a filler for polyurethane, carbon black for polyurethane, a thixotropic agent, a diluent and a catalyst.
In addition, patent CN201510979619.6 discloses a one-component moisture-curable polyurethane plastic track material, patent CN201610016193.9 discloses a one-component moisture-curable polyurethane sealant with low tensile modulus, and patent CN201611108972.8 discloses a one-component moisture-curable elastic adhesive. It follows that the prior art uses single-component moisture-curing polyurethanes mostly for joint sealants or adhesives, while the prior art for single-component moisture-curing polyurethane coatings is less.
Patent CN201510399668.2 discloses a one-component polyurethane coating, which mainly comprises diisocyanate, polyether, chlorinated paraffin, acrylic resin, xylene and butyl acetate, and the polyurethane coating uses xylene as a solvent, and has strong volatility and great environmental hazard.
Patent CN93100973.1 discloses a one-component polyurethane paint, which is mainly prepared from toluene diisocyanate, 6305 polyether, 3010 polyether, xylene, cross-linking agent polyethylene glycol, ester or inorganic acid stabilizer and pigment, wherein the paint is prepared from toluene diisocyanate as a main preparation raw material and has great environmental pollution.
Therefore, the existing single-component polyurethane coating system adopts non-environment-friendly safe Toluene Diisocyanate (TDI) as a main raw material, and simultaneously adopts benzene solvents such as xylene generally, and the two bring serious pollution and harm to the production and application processes. TDI has a high toxicity, LD505800mg/kg, strong volatility, vapor pressure at 25 deg.C of 3Pa, saturated vapor concentration of 142mg/m3(20 ℃ C.). The toxicity of xylene to the human nervous system is well known, its LD501364mg/kg, high volatility, explosion hazard and limited use in view of environmental protection and safety. In contrast, diphenylmethane diisocyanate (MDI) has low toxicity and LD50More than 15000mg/kg, low volatility, vapor pressure at 25 deg.C of 1.3 x 10-3Pa, saturated steam concentration of 0.8mg/m3(20 ℃ C.). In the prior art, a polyurethane coating which is environment-friendly and safe, and has high coating density, high curing and film-forming speed and good corrosion resistance is still needed.
Disclosure of Invention
The invention aims to provide a single-component moisture-curing prepolymer resin and a preparation method thereof, and the invention also aims to provide a single-component moisture-curing heavy-duty anticorrosive coating and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the invention provides an environment-friendly single-component moisture-curable modified polyurethane prepolymer resin, which is prepared by the following steps:
(1) weighing the following main raw materials in parts by weight: 25-40 parts of polyisocyanate compound, 20-35 parts of polyhydroxy and polyamine macromolecular compound mixture, 30-40 parts of sec-butyl acetate solvent and 1-5 parts of stabilizing additive; wherein the polyhydroxy and polyamine-based macromolecular compound mixture consists of polyether polyol, polyhydroxy compound containing fatty glyceride and amine-terminated polyether; the stabilizing auxiliary agent is selected from polyethylene glycol acrylate, such as amino polyethylene glycol acrylate (also called acrylate-polyethylene glycol-amino) or methoxy polyethylene glycol acrylate compound, preferably amino polyethylene glycol acrylate;
(2) putting a polyisocyanate compound and a part of solvent into a reaction kettle, heating to 42-48 ℃, and stirring for 0.5-1h to obtain a mixture, namely a material 1;
(3) putting polyether polyol, a polyhydroxy compound containing fatty glyceride, amine-terminated polyether, a stabilizing additive and a residual solvent into a reaction vessel, and stirring for 0.5-1h at 25-30 ℃ to obtain a mixture, namely a material 2;
(4) adding a proper amount of catalyst into the material 1, slowly adding the material 2 into the material 1 under the stirring condition at 45-47 ℃, heating to 82-88 ℃ after finishing dropping, carrying out heat preservation reaction for 2-3h, cooling to below 50 ℃ after the reaction is finished, discharging under the protection of nitrogen, and preparing the modified polyurethane prepolymer resin, wherein the NCO content is 3-11 wt%.
Preferably, in the step (3) of preparing the modified polyurethane prepolymer resin, a part of the polyether polyol, the polyol containing fatty acid glyceride, the amino-terminated polyether, the acrylate-polyethylene glycol-amino group, a part of the solvent and an optional pigment and filler are dispersed or mixed and ground at a high speed without isolating air, and then the slurry, the rest of the polyether polyol, the polyol containing fatty acid glyceride, the amino-terminated polyether, the acrylate-polyethylene glycol-amino group and the solvent are put into a reaction vessel together for vacuum azeotropic distillation, so that the water absorbed in the system is removed, the temperature is reduced to room temperature, and the mixture is stirred for 0.5 to 1 hour to form the material 2.
Preferably, the preparation raw materials of the modified polyurethane prepolymer resin comprise the following components in parts by mass: 25-40 parts of polyisocyanate compound, 10-15 parts of polyether polyol, 5-10 parts of polyol containing fatty glyceride, 5-10 parts of amine-terminated polyether, 1-5 parts of acrylate-polyethylene glycol-amino, 0.01-0.05 part of catalyst and 30-40 parts of solvent.
Wherein the polyisocyanate compound is selected from aliphatic isocyanates or aromatic isocyanates having an isocyanate group (NCO) content of 28-35%, such as one or a combination of two of Hexamethylene Diisocyanate (HDI) and Hexamethylene Diisocyanate Biuret (HDB), and the aromatic isocyanates are selected from diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PAPI).
Preferably, the polyisocyanate compound is selected from diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl polyisocyanate (PAPI) and has an NCO content of 28 to 32%.
Wherein the polyether polyol is selected from propylene oxide polyether polyols, such as polyoxypropylene glycol (PPG).
Wherein the fatty acid glyceride-containing polyol is selected from natural castor oil, such as natural castor oil having a hydroxyl value of 163 mgKOH/g.
Wherein the amino-terminated polyether is preferably selected from D-2000 (average molecular weight 2000, functionality 2, OH equivalent to 53 mgKOH/g).
The catalyst is one or the combination of more than two of dibutyl tin dilaurate, stannous octoate and dibutyl tin diacetate.
Wherein the molecular weight of the acrylate-polyethylene glycol-amino is preferably 600-1000, and can be selected from the series produced by Shanghai quasi-Biotechnology Limited. The acrylic ester-polyethylene glycol-amino is polymerized in a system to increase the fusibility of the modified polyurethane prepolymer resin and other additives and improve the stability of the prepolymer resin.
Wherein the solvent is an environment-friendly solvent sec-butyl acetate.
In a second aspect, the invention provides a single-component moisture-curing polyurethane heavy-duty anticorrosive coating, which comprises the following components in parts by weight: 70-99.9 parts of the prepared modified polyurethane prepolymer resin, 2-25 parts of pigment and filler, 0.5-3 parts of dispersing agent, 0.2-2 parts of anti-floating coloring agent, 0.2-1 part of defoaming agent, 0.1-1 part of flatting agent, 5-15 parts of latent curing agent, 5-15 parts of water absorbent and a proper amount of other auxiliary agents.
Wherein the other auxiliary agents are selected from anti-settling agents, and the using amount is 0.1-1 part.
Preferably, the moisture-cured polyurethane heavy-duty anticorrosive coating comprises the following components in parts by mass: 72-99 parts of modified polyurethane prepolymer resin, 2-20 parts of pigment and filler, 0.5-1 part of dispersing agent, 0.3-1 part of anti-settling agent, 0.2-0.5 part of anti-floating coloring agent, 0.2-0.4 part of defoaming agent, 0.1-0.3 part of flatting agent, 5-10 parts of latent curing agent and 5-10 parts of water absorbent.
The modified polyurethane prepolymer resin at least comprises polyether polyol, polyol containing fatty glyceride, amine terminated polyether and acrylate-polyethylene glycol-amino, and can be (2-3) to (1-1.5) to (0.1-1) in a mass ratio.
Preferably, the modified polyurethane prepolymer resin comprises the following raw materials in parts by weight: 10-15 parts of polyether polyol, 5-10 parts of fatty glyceride-containing polyol, 5-10 parts of amine-terminated polyether, 1-5 parts of acrylate-polyethylene glycol-amino, 25-40 parts of polyisocyanate compound, 0.01-0.05 part of catalyst and 30-40 parts of solvent.
In a preferred embodiment of the present invention, the pigment and filler is selected from one or a combination of more than two of titanium dioxide, carbon black, mica powder, kaolin and iron blue.
Wherein the dispersant may be one or a combination of two or more selected from Texaphor P63, Texaphor P61, Texaphor P60, Texaphor 963, and Texaphor 3250, which are manufactured by the company keannin auxiliaries, and in a preferred embodiment of the present invention, Texaphor P63 is used as the dispersant.
Wherein the anti-settling agent can be selected from any commercially available species, such as one or more of 201P, BETONE LT, BENTONE SD-2, and 881-S from Haimax corporation.
Wherein the anti-floating colour matching agent may be selected from those commercially available, for example from 921 from TEGO Airex.
Wherein the defoaming agent can be selected from one or more of Perenol E1, Perenol E7, Perenol E8, Perenol E9, Perenol B681F and Dehydram1293 which are produced by German Corning auxiliary company, and in a preferred embodiment of the invention, Perenol E8 is used as the defoaming agent.
Wherein the leveling agent can be one or more selected from O5, Perenol F40, Perenol F60, Perenol S4 and Perenol S-HONZ manufactured by German Corning assistant company, and in a preferred embodiment of the invention, Perenol F40 is used as the leveling agent.
Wherein the latent curing agent is selected from ALT-403, W203 manufactured by Elite.
Wherein the water absorbent is selected from BF-5 polyurethane water absorbent, FO chemical water absorbent, UOP2000 physical water absorbent or their combination.
The polyisocyanate compound is selected from aliphatic isocyanate selected from one or a combination of two of Hexamethylene Diisocyanate (HDI) and Hexamethylene Diisocyanate Biuret (HDB), or aromatic isocyanate selected from diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PAPI).
Preferably, the polyisocyanate compound is selected from diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl polyisocyanate (PAPI) and has an isocyanate group (NCO) content of 28 to 32%.
The solvent is an environment-friendly solvent sec-butyl acetate.
In a third aspect, the invention provides a preparation method of a one-component moisture-curing polyurethane heavy-duty anticorrosive coating, which comprises the following steps:
(1) preparing modified polyurethane prepolymer resin; pre-drying auxiliary components including pigment filler, dispersant, anti-settling agent, anti-floating coloring agent, defoaming agent, leveling agent, latent curing agent and water absorbent;
(2) adding modified polyurethane prepolymer resin, pigment and filler, dispersant and water absorbent in proportion into a closed reaction kettle, heating, controlling the temperature at 50-60 ℃, stirring for 1-2h, cooling to below 50 ℃, introducing dry nitrogen, adding anti-settling agent, anti-floating coloring agent, defoaming agent, leveling agent and latent curing agent in formula amount, mixing uniformly, discharging, and filling for later use.
The preparation process of the polyurethane prepolymer resin in the preparation of the coating can also comprise a step of dehydrating raw materials, and the dehydration process can be completed through the following technical processes: a part of hydroxyl-terminated polyol and polyamine which are distilled and dehydrated in advance and a part of solvent are dispersed or ground and mixed with optional pigment and filler components at a high speed before prepolymer resin is prepared, air isolation is not needed, timed air release is not needed, and NCO groups in the prepolymer resin are not consumed in advance. After high-speed dispersion or mixing and grinding, the slurry, the rest of polyhydric alcohol and solvent are put into a reactor together, azeotropic distillation is carried out at 110 +/-5 ℃ and under the vacuum of-0.1 MPa, and all adsorbed water in the system is effectively removed. After the operation is finished, the temperature is reduced to 70-75 ℃, and the mixture is dripped into other components for reaction, and the reaction temperature is controlled to be 80-85 ℃.
In a fourth aspect, the present invention provides the use of the one-component moisture-curable polyurethane heavy-duty anticorrosive coating in anticorrosive coatings for materials, including wood, metal, plastic, leather, paper, fabric, etc., preferably, for anticorrosive coatings for wood, plastic and metal materials, and particularly preferably, for metal coatings.
In a fifth aspect, the present invention provides the use of the polyurethane prepolymer resin as a one-component moisture-curable polyurethane/polyurea anti-corrosive varnish or primer.
The beneficial effects of the invention are as follows.
1) The environment-friendly single-component moisture-cured polyurethane/polyurea heavy-duty anticorrosive coating (colored paint) prepared by the method has the excellent performances of high surface smoothness, good leveling property, no bubbles, no shrinkage cavity, quick curing and film forming, high coating density, high surface hardness (hardness of 2H), strong scratch resistance, high temperature resistance (200 ℃), strong acid resistance (50% sulfuric acid), strong alkali resistance (50% sodium hydroxide), salt mist resistance (2000H), good storage stability and the like.
2) The modified polyurethane prepolymer prepared by the invention has NCO group content of 3-11% and theoretical solid content of 60-75%. The prepolymer can be used as single-component moisture-cured polyurethane/polyurea anticorrosive varnish or primer, can be used for bottom surface integrated construction, and can be brushed, sprayed or rolled. Because the molecular structure contains a large amount of urethane groups and urea groups and a large amount of urea bonds and hydrogen bonds are formed in the process of curing and film forming, the paint film has unique high chemical corrosion resistance and physical and mechanical properties, and excellent film forming performance and storage stability.
3) The dehydration of the raw materials in the preparation process of the polyurethane heavy-duty anticorrosive paint is quite critical, the problem cannot be solved completely in practice even if the raw materials are dried before the preparation, and the polyurethane paint coating which is not dehydrated completely is easy to generate the phenomena of bubbles, falling off and the like in the use process. The polyurethane heavy-duty anticorrosive coating prepared by the invention thoroughly solves the key problem of raw material dehydration, disperses the pigment and filler and the polyol or the polyamine in advance, removes water by azeotropic distillation on the premise of not consuming NCO groups in prepolymer resin in advance, ensures that the pigment and filler are dispersed more uniformly, and does not leave bubbles or flaw points in the system. In addition, the invention carries out dehydration treatment in the preparation process of the prepolymer, so that the obtained polyurethane coating is environment-friendly and safe, and the coating has high density, high curing and film-forming speed and good corrosion resistance.
4) The formula of the invention only adopts single-component resin, and the moisture in the air is utilized for curing, thereby ensuring the environmental protection and the safety of the coating. Meanwhile, technical innovation is completed on the processes of prepolymerization of resin, dehydration of raw materials and preparation, so that the novel anticorrosive paint with excellent chemical corrosion resistance, high physical and mechanical properties and high and low temperature resistance, reliable storage stability, convenient and safe construction manufacturability is prepared.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all 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.
Example 1
Preparation of modified polyurethane prepolymer resin
S1: putting 2.5kg of polyisocyanate MDI and 2.0kg of sec-butyl acetate solvent into a reaction vessel, heating to 45 ℃, and stirring for 1h to form a material 1;
s2: putting 1.2kg of polyether glycol PPG, 0.55kg of natural castor oil with the hydroxyl value OH being 163mg KOH/g, 0.1kg of amino-terminated polyether D-20000.5 kg, 0.1kg of acrylate-polyethylene glycol-amino and 2kg of sec-butyl acetate into a reaction container, and stirring for 1h at room temperature to form a material 2;
s3: adding 2g of catalyst stannous octoate into the material 1 at 45 ℃ under stirring, slowly dropwise adding the material 2 into the material 1 for 2 hours, heating to 85 ℃ after dropwise adding, and carrying out heat preservation reaction for 2.5 hours to prepare the modified polyurethane prepolymer resin.
Example 2
Preparation of modified polyurethane prepolymer resin
S1: putting 5 parts of polyisocyanate compound MDI, 20 parts of PAPI and 20 parts of sec-butyl acetate solvent into a reaction vessel, heating to 45 ℃, and stirring for 1h to form a material 1;
s2: placing 12 parts of polyether glycol PPG, 5 parts of natural castor oil with OH being 163mg KOH/g, 20005 parts of amine-terminated polyether D and 20 parts of sec-butyl acetate solvent into a reaction container, and stirring for 1h at room temperature to form a material 2;
s3: adding 0.02 part of catalyst stannous octoate into the material 1 at 45 ℃ under stirring, dropwise adding the material 2 into the material 1, heating to 85 ℃ after dropwise adding, and carrying out heat preservation reaction for 2.5 hours to prepare the modified polyurethane prepolymer resin.
Example 3 preparation of modified polyurethane prepolymer resin
S1: placing 25 parts of polyisocyanate compound MDI and 20 parts of sec-butyl acetate solvent into a reaction vessel, heating to 45 ℃, and stirring for 1h to form a material 1;
s2: placing 22 parts of polyether glycol PPG, 2 parts of acrylate-polyethylene glycol-amino and 20 parts of sec-butyl acetate solvent into a reaction container, and stirring at room temperature for 1h to form a material 2;
s3: adding 0.02 part of catalyst stannous octoate into the material 1 at 45 ℃ under stirring, dropwise adding the material 2 into the material 1, heating to 85 ℃ after dropwise adding, and carrying out heat preservation reaction for 2.5 hours to prepare the modified polyurethane prepolymer resin.
Example 4
Preparation of modified polyurethane prepolymer resin
S1: placing 25 parts of polyisocyanate compound MDI and 20 parts of sec-butyl acetate solvent into a reaction vessel, heating to 45 ℃, and stirring for 1h to form a material 1;
s2: placing 22 parts of polyether glycol PPG and 20 parts of sec-butyl acetate solvent into a reaction container, and stirring for 1h at room temperature to form a material 2;
s3: adding 0.02 part of catalyst stannous octoate into the material 1 at 45 ℃ under stirring, dropwise adding the material 2 into the material 1, heating to 85 ℃ after dropwise adding, and carrying out heat preservation reaction for 2.5 hours to prepare the modified polyurethane prepolymer resin.
Effect example 1 comparison of basic Performance indexes of modified polyurethane prepolymer resin
The four polyurethane prepolymer resins prepared in examples 1 to 4 were used as test objects, and the four polyurethane prepolymer resins were applied to a wooden floor as primers to test basic performance indexes of the prepolymer resins, and the results are shown in the following table.
Table 1 basic performance index comparison result of modified polyurethane prepolymer resin
The polyurethane prepolymer resin prepared in example 1 simultaneously contains a certain proportion of polyether polyol PPG, fatty glyceride-containing polyol castor oil, amine-terminated polyether D-2000 and acrylate-polyethylene glycol-amino; in contrast to example 1, no acrylate-polyethylene glycol-amino group was included in example 2; example 3 does not contain castor oil and amino terminated polyether D-2000; example 4 does not contain castor oil, amino terminated polyether D-2000 and acrylate-polyethylene glycol-amino. As can be seen from the comparison results, the difference of polyhydroxy or polyamino compounds has little influence on the NCO content, appearance and viscosity of the prepolymer, but the prepolymer containing polyamino and polyhydroxy compounds has better performances. Comparing the data of example 2 and example 3, it can be found that the acrylate-polyethylene glycol-amino group can increase the adhesion and temperature change resistance of the primer and the substrate material, and is beneficial to improving the stability of the coating.
Example 5
Preparation of modified polyurethane prepolymer resin
S1: placing 25 parts of polyisocyanate compound MDI and 20 parts of sec-butyl acetate solvent into a reaction vessel, heating to 45 ℃, and stirring for 1h to form a material 1;
s2: firstly, 6 parts of PPG, 3 parts of castor oil which is a polyhydroxy compound containing fatty glyceride, D-20003 parts of amine-terminated polyether, 1 part of acrylate-polyethylene glycol-amino and 10 parts of solvent are mixed and ground with 1 part of carbon black and 1.5 parts of mica powder without isolating air, after mixing and grinding, the slurry, 6 parts of PPG, 2 parts of castor oil, D-20002 parts of acrylate-polyethylene glycol-amino and 10 parts of solvent are put into a reaction vessel together, and vacuum azeotropic distillation is carried out at 110 ℃, so that the water absorbed in the system is removed, the temperature is reduced to room temperature, and the mixture is stirred for 1 hour to form a material 2;
s3: adding 0.02 part of catalyst stannous octoate into the material 1 at 45 ℃ under stirring, dropwise adding the material 2 into the material 1, heating to 85 ℃ after dropwise adding, and carrying out heat preservation reaction for 2.5 hours to prepare the modified polyurethane prepolymer resin.
Example 6
Preparation of modified polyurethane prepolymer resin
S1: placing 25 parts of polyisocyanate compound MDI and 20 parts of sec-butyl acetate solvent into a reaction vessel, heating to 45 ℃, and stirring for 1h to form a material 1;
s2: firstly, mixing and grinding 6 parts of polyether glycol PPG, 3 parts of fatty glyceride-containing polyol castor oil, 3 parts of amino-terminated polyether D-20003 parts and 10 parts of solvent, 1 part of carbon black and 1.5 parts of mica powder without isolating air, after mixing and grinding, putting the slurry, 6 parts of PPG, 2 parts of castor oil, D-20002 parts and 10 parts of solvent into a reaction container, carrying out azeotropic distillation at 110 ℃ and-0.1 MPa, removing the adsorbed water in the system, cooling to room temperature, and stirring for 1h to form a material 2;
s3: adding 0.02 part of catalyst stannous octoate into the material 1 at 45 ℃ under stirring, dropwise adding the material 2 into the material 1, heating to 85 ℃ after dropwise adding, and carrying out heat preservation reaction for 2.5 hours to prepare the modified polyurethane prepolymer resin.
Example 6 compared to example 5, the prepolymer resin did not contain the adjuvant acrylate-polyethylene glycol-amino.
Example 7
Preparation of polyurethane heavy-duty coating 1
S1: before preparation, the used dispersing agent, anti-settling agent, anti-floating coloring agent, defoaming agent, flatting agent, latent curing agent and water absorbent are dried in advance;
s2: 9.6kg of the modified polyurethane prepolymer resin prepared in example 5 is added into a closed reaction kettle, a dispersant Texaphor P63 and water absorbents FO 0.1kg and UOP20000.4kg are sequentially added, the temperature is raised and stirred for 2 hours, the temperature is controlled to be about 60 ℃, then the temperature is reduced to be below 50 ℃, dry nitrogen is introduced, and the formula amount of 881-S0.03 kg of anti-settling agent, 9210.02 kg of anti-floating color matching agent, Perenol E80.03kg of defoaming agent, Perenol F400.02kg of flatting agent and W2030.5kg of latent curing agent are added, mixed uniformly and discharged to prepare the coating 1.
Example 8
Preparation of polyurethane heavy-duty coating 2
S1: before preparation, the used dispersing agent, anti-settling agent, anti-floating coloring agent, defoaming agent, flatting agent, latent curing agent and water absorbent are dried in advance;
s2: adding 9.6kg of the modified polyurethane prepolymer resin prepared in example 6 into a closed reaction kettle, sequentially adding 0.1kg of dispersing agent Texaphor P63 and water absorbents FO and UOP20000.4kg, heating and stirring for 2h, controlling the temperature to be about 60 ℃, then cooling to below 50 ℃, introducing dry nitrogen, adding 881-S0.03 kg of anti-settling agent, 9210.02 kg of anti-floating color matching agent, 80.03kg of defoaming agent Perenol E80.03kg, 400.02kg of flatting agent Perenol F and W2030.5kg of curing agent according to the formula, uniformly mixing, discharging, and preparing the latent coating 2.
Example 9
Preparation of polyurethane heavy-duty coating 3
S1: before preparation, the used pigment, the used dispersing agent, the used anti-settling agent, the used anti-floating coloring agent, the used defoaming agent, the used leveling agent, the used latent curing agent and the used water absorbent are dried in advance;
s2: adding 9.6kg of the modified polyurethane prepolymer resin prepared in example 1 into a closed reaction kettle, sequentially adding 0.1kg of carbon black, 0.15kg of mica powder, 0.1kg of dispersing agent Texaphor P63, water absorbents FO and 0.1kg of UOP 20000.4kg, heating and stirring for 2h, controlling the temperature to be about 60 ℃, then cooling to below 50 ℃, introducing dry nitrogen, adding 881-S0.03 kg of anti-settling agent, 9210.02 kg of anti-floating color agent, 80.03kg of defoaming agent, 400.02kg of flatting agent Perenol F and W2030.5kg of latent curing agent according to the formula amount, uniformly mixing, discharging, and preparing the coating 3.
Effect example 2
Comparison of coating 1-3 Properties
The influence of the modified polyurethane prepolymer resin dehydration treatment on the performance of the polyurethane heavy-duty anticorrosive coating is verified.
The test method comprises the following steps: stirring the paint 1-3 until the paint is brushed with viscosity (40S-45S for coating 4 cups), taking a salt spray resistant test steel plate, a high temperature resistant test steel plate with the thickness of 3-5mm and a standard tinplate for oil removal, rust removal and polishing, then carrying out phosphating treatment, scrubbing the surface by using 120# solvent oil, and then filtering and spraying by using a 200-mesh filter screen. The thickness of a paint film of the chemical resistance, weather resistance and salt spray resistance test board is controlled to be 90-100 mu m, and the thickness of a conventional performance test board is controlled to be 20-30 mu m. And (3) after the paint is completely dried for 48 hours, carrying out comprehensive performance test, testing the chemical resistance, salt spray resistance and artificial aging resistance of the paint according to the detection standard, and comparing the results as shown in the following table:
TABLE 2 comparison of paint 1-3 Performance indices
The modified polyurethane prepolymer resins of the coating 1 and the coating 2 are dehydrated, so that the storage period of the coating 1 is longer, the property is more stable, the drying time of the coating 1 is shorter, the dehydration effect is enhanced by the polyethylene glycol acrylate auxiliary agent, and the drying speed of the coating is increased; because the acrylate-polyethylene glycol-amino has good compatibility with other additives, the toughness of the coating and the adhesive force with a substrate are improved, and the impact resistance is improved. The paint 1 has stronger adhesive force with the substrate, so that the acid, alkali, salt and aging resistance and high temperature resistance of the paint are stronger than those of the paint 2.
Compared with the coating 1, the coating 3 does not undergo dehydration treatment in the preparation process of the modified polyurethane prepolymer resin, and comparative test data shows that the coating 1 has longer storage time and more stable property, which indicates that the dehydration treatment is favorable for improving the stability of the coating, and the dehydration treatment enables the drying time of the coating after being coated to be shorter. Because the adhesion between the coating and the substrate is not affected by the dehydration treatment, the acid-base salt resistance of the coating 1 is not obviously different from that of the coating 3, but the aging resistance and the high temperature resistance of the coating 1 are better.
In conclusion, the polyurethane heavy-duty anticorrosive coating provided by the invention has a series of excellent performances of good storage stability, high surface smoothness, fast curing and film forming, strong adhesion with a substrate, good toughness, chemical resistance, aging resistance, good high temperature resistance and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. A moisture-curing polyurethane heavy-duty anticorrosive coating contains a single-component moisture-curing prepolymer resin, and is characterized by comprising the following components in parts by weight: 72-99 parts of prepolymer resin, 2-20 parts of pigment and filler, 0.5-1 part of dispersing agent, 0.3-1 part of anti-settling agent, 0.2-0.5 part of anti-floating coloring agent, 0.2-0.4 part of defoaming agent, 0.1-0.3 part of flatting agent, 5-10 parts of latent curing agent and 5-10 parts of water absorbent; the modified polyurethane prepolymer resin is prepared from the following raw materials in parts by weight: 10-15 parts of polyether polyol, 5-10 parts of fatty glyceride-containing polyol, 5-10 parts of amino-terminated polyether, 1-5 parts of polyethylene glycol acrylate compound, 25-40 parts of polyisocyanate compound, 0.01-0.05 part of catalyst and 30-40 parts of solvent;
the polyethylene glycol acrylate compound is selected from acrylate-polyethylene glycol-amino, the polyether polyol is selected from propylene oxide polyether polyol, the solvent is sec-butyl acetate, the catalyst is one or a combination of more than two of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate, and the polyisocyanate compound is selected from diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate.
2. The preparation method of the moisture-curing polyurethane heavy-duty anticorrosive coating according to claim 1, characterized by comprising the following steps:
(1) weighing the following raw materials in parts by weight: 10-15 parts of polyether polyol, 5-10 parts of fatty glyceride-containing polyol, 5-10 parts of amino-terminated polyether, 1-5 parts of polyethylene glycol acrylate compound, 25-40 parts of polyisocyanate compound, 0.01-0.05 part of catalyst and 30-40 parts of solvent; putting a polyisocyanate compound and a part of solvent into a reaction kettle, heating to 42-48 ℃, and stirring for 0.5-1h to obtain a mixture, namely a material 1; putting polyether polyol, a polyol containing fatty glyceride, amino-terminated polyether, polyethylene glycol acrylate and the rest solvent into a reaction vessel, and stirring for 0.5-1h at 25-30 ℃ to obtain a mixture, namely a material 2; adding a proper amount of catalyst into the material 1, slowly adding the material 2 into the material 1 under the stirring condition at 45-47 ℃, heating to 82-88 ℃ after finishing dripping, carrying out heat preservation reaction for 2-3h, cooling to below 50 ℃ after the reaction is finished, and discharging under the protection of nitrogen to prepare modified polyurethane prepolymer resin; and auxiliary components of pigment and filler, a dispersing agent, an anti-settling agent, an anti-floating coloring agent, a defoaming agent, a leveling agent, a latent curing agent and a water absorbent are dried in advance;
(2) adding modified polyurethane prepolymer resin, pigment and filler, dispersant and water absorbent in proportion into a closed reaction kettle, heating, controlling the temperature at 50-60 ℃, stirring for 1-2h, cooling to below 50 ℃, introducing dry nitrogen, adding anti-settling agent, anti-floating coloring agent, defoaming agent, leveling agent and latent curing agent in formula amount, mixing uniformly, discharging, and filling for later use.
3. Use of the moisture-curable polyurethane heavy duty coating of claim 1 in a metal surface anticorrosive coating.
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