CN117050643B - Water-based long-acting anti-corrosion paint and preparation method thereof - Google Patents
Water-based long-acting anti-corrosion paint and preparation method thereof Download PDFInfo
- Publication number
- CN117050643B CN117050643B CN202311260162.4A CN202311260162A CN117050643B CN 117050643 B CN117050643 B CN 117050643B CN 202311260162 A CN202311260162 A CN 202311260162A CN 117050643 B CN117050643 B CN 117050643B
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- Prior art keywords
- parts
- agent
- repairing
- water
- anticorrosive coating
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- 239000003973 paint Substances 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000005260 corrosion Methods 0.000 title abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 239000013530 defoamer Substances 0.000 claims abstract description 7
- 239000002562 thickening agent Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 9
- CDQBEUOQQTTZQR-UHFFFAOYSA-N 5-amino-3h-1,3-benzothiazole-2-thione Chemical compound NC1=CC=C2SC(S)=NC2=C1 CDQBEUOQQTTZQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- -1 aromatic siloxane Chemical class 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 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 7
- 238000000227 grinding Methods 0.000 claims description 7
- 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 7
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 7
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006880 cross-coupling reaction Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims 3
- 230000007797 corrosion Effects 0.000 abstract description 22
- 230000007246 mechanism Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000008199 coating composition Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 229940074391 gallic acid Drugs 0.000 description 4
- 235000004515 gallic acid Nutrition 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229940093474 manganese carbonate Drugs 0.000 description 4
- 239000011656 manganese carbonate Substances 0.000 description 4
- 235000006748 manganese carbonate Nutrition 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- LYDHLGJJJAWBDY-UHFFFAOYSA-N 1-isocyanato-4-[2-(4-isocyanatocyclohexyl)propan-2-yl]cyclohexane Chemical compound C1CC(N=C=O)CCC1C(C)(C)C1CCC(N=C=O)CC1 LYDHLGJJJAWBDY-UHFFFAOYSA-N 0.000 description 2
- 239000013556 antirust agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004088 microvessel Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008263 repair mechanism Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
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)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of coating compositions, and particularly discloses a water-based long-acting anti-corrosion coating and a preparation method thereof. The anticorrosive paint comprises, by weight, 30-50 parts of modified polyurethane, 5-15 parts of antirust pigment, 8-18 parts of filler, 0.1-2 parts of leveling agent, 0.1-1 part of defoamer, 0.5-1.5 parts of antifreezing agent, 0.1-0.5 part of thickener and 20-35 parts of water. The invention also provides a preparation method of the composite. Compared with the prior art, the anti-corrosion coating prepared by the invention has the advantages of long-acting corrosion resistance, good mechanical property, multiple mechanism self-repairing and the like.
Description
Technical Field
The invention relates to the technical field of coating compositions, in particular to a water-based long-acting anti-corrosion coating and a preparation method thereof.
Background
Corrosion is a phenomenon in which when a metal is in contact with the environment, chemical reactions take place between the metal surface and the active substances in the surrounding environment (e.g. oxygen, water and salts), resulting in chemically more stable compounds and degrading the material properties. Corrosion generally results in a decrease in mechanical properties and chemical stability of the material, thereby causing accidents, such as cracking of petroleum pipelines, collapse of bridges, etc., and causing serious influence on various industries. Also, once the coating surface becomes defective, the metal is exposed to air, water and some corrosive media, causing it to accelerate corrosion.
At present, most damaged anticorrosive coatings are repaired manually, so that the process is complicated, the price is high and the time is wasted. Thus, researchers have turned their eyes towards corrosion-resistant coatings with self-healing capabilities, which are also known as smart corrosion-resistant coatings. The intelligent anti-corrosion coating has long service life, excellent anti-corrosion effect and self-repairing property. The current self-repairing anticorrosive coating materials can be divided into external self-repairing type and intrinsic self-repairing type, wherein external self-repairing type refers to the process of introducing external components such as microcapsules, micro-vessels, glass fibers or nano particles containing repairing agents into a matrix, but the repairing times are limited, the container containing the repairing agent loses the self-repairing effect once being broken to release the repairing agent, and the uniformity of the dispersing of the repairing agent curing agent in the matrix material, the influence of the dispersing of the repairing agent curing agent on the mechanical properties of the matrix and the like are all the problems to be overcome. The intrinsic self-repairing process is realized by the polymer material by means of self-contained reversible covalent bond or non-covalent bond and molecular chain segment motion without introducing an external repairing system into the material, and the method not only can realize repeated repairing of the material, but also can not influence the performance of the matrix material, and meanwhile, the designability of the molecular structure of the material is strong, so that the method has become an important research direction of the self-repairing material.
Chinese patent 201410004130.2 discloses a preparation method of a room temperature rapid self-repairing anticorrosive paint, and relates to a preparation method of an anticorrosive paint, wherein urea resin is adopted as a wall material, the coating rate of the microcapsule repairing agent is high, and the contact probability of the repairing agent and a catalyst is high; the polythiol curing agent is used as an outer core material, so that the effect of rapidly repairing cracks at room temperature can be achieved; the nano titanium dioxide has special photocatalytic performance, super-hydrophilicity and ultraviolet shielding performance, and can be applied to the paint to keep the nano state in the paint, so that the defects of weather resistance, poor Yi Zhanwu and the like of the existing paint can be overcome, and the siphon action of microcracks can be improved due to the porous performance. The self-repairing property of the coating is obviously improved due to the addition of the mesoporous molecular sieve and the self-repairing microcapsule with the double-wall sandwich structure, the self-repairing time is shorter, and the coating has excellent corrosion resistance.
China patent 202110868027.2 discloses a preparation method of a modification-free recyclable photo-thermal driven self-repairing epoxy anti-corrosion coating material, which is prepared by taking bisphenol A type epoxy resin as a film forming substance, taking polybasic acid as a curing agent, introducing a carbon material as photo-thermal filler to construct an epoxy-anhydride curing system without catalyst participation, and finally curing for 4-12 hours at a curing temperature of 110-130 ℃. The preparation process does not involve any organic solvent, does not generate volatile organic matters, and is environment-friendly; the required raw materials are all commercial existing products, no chemical modification is needed in the preparation process, and the coating can be carried out in various modes; the repairing process of the coating is mainly based on solid-liquid phase change of the material caused by temperature rise, and has the advantages of quick and controllable response, capability of being triggered by various modes and the like; the internal crosslinking of the coating is replaced by entanglement of molecular chains, so that the interfacial property and the barrier property of the coating are not greatly influenced.
The self-repairing anticorrosive paint in the prior art is mainly coated in a microcapsule mode or is prepared by mixing a self-repairing resin material and an antirust agent, so that the problems of limited repairing times, poor compatibility of the antirust agent and the resin and the like exist, the coating performance can be influenced, and the corrosion prevention effect is not durable, and therefore, the self-repairing anticorrosive paint with more stability and long-acting property is developed and has quite considerable application prospect.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a water-based long-acting anticorrosive paint and a preparation method thereof.
Compared with the external-aid type self-repairing material, the intrinsic type self-repairing material can repair the wound without adding any repairing agent. The repair mechanism is mainly realized by dynamic exchange of reversible covalent bonds or reversible non-covalent bonds in a polymer chain. The intrinsic self-repairing mechanism is to repair the coating through a series of reactions such as physics, chemistry and the like under the external stimulus of light, temperature, pH value and the like by special functional groups. However, most of the anti-corrosion paint is applied outdoors at present, and the external stimulation approach is insufficient, so that the self-repairing type of a single mechanism cannot fully meet the requirements. In addition, long-term corrosion protection cannot be achieved by merely self-repairing the surface of the coating, and corrosion of the coating can be caused by high humidity or corrosion of chloride ions. Therefore, the polyurethane coating with multiple self-repairing mechanisms is prepared, has a double mechanism of reversible covalent bonds and irreversible covalent bonds, can complete self-repairing under the action of light or heat, and successfully obtains polyurethane with corrosion-resistant components by directly adding benzothiazole-dithiol amine derivatives with corrosion-resistant components into polyurethane molecular chains, so that no additional corrosion inhibitor is required. The prepared polyurethane coating can finish self-repairing under illumination, has little limitation on application scenes, and has wider market prospect.
The invention provides a water-based long-acting anticorrosive paint, which comprises, by weight, 30-50 parts of modified polyurethane, 5-15 parts of antirust pigment, 8-18 parts of filler, 0.1-2 parts of leveling agent, 0.1-1 part of defoamer, 0.5-1.5 parts of antifreezing agent, 0.1-0.5 part of thickener and 20-35 parts of water.
The preparation method of the modified polyurethane comprises the following steps:
x1, adding 5-15 parts by weight of 5-amino-2-mercaptobenzothiazole, 2-8 parts by weight of 4-aminothiophenol, 0.01-0.05 part by weight of gallic acid and 0.01-0.03 part by weight of manganese carbonate into 100-200 parts by weight of water, adding 1mol/L sodium carbonate aqueous solution to adjust the pH value to 8-10, heating to 70-90 ℃ under the oxygen atmosphere after the addition, stirring for 2-6 hours under the airtight condition, cooling to room temperature after the stirring is finished, adding water into the mixed solution for dilution, extracting with ethyl acetate, separating the solution, and performing organic phase drying and concentration to obtain benzothiazole-dithioaniline derivatives;
x2 adding 1.5-4 parts by weight of benzothiazole-dithio aniline derivative in the step X1 into 10-30 parts by weight of N, N-dimethylformamide to obtain solution A, heating 3-8 parts by weight of isophorone diisocyanate to 50-70 ℃, then dropwise adding the solution A, adding 0.0001-0.0005 part by weight of dibutyltin dilaurate, stirring for 12-18 h under an inert atmosphere at 50-70 ℃, adding 20-50 parts by weight of polytetrahydrofuran ether, heating to 95-115 ℃, polymerizing for 2-4 h, adding 3.5-7.5 parts by weight of 2,2-bis (4-cyclohexyl isocyanate) propane, performing chain extension, cooling after finishing 4-6 h, and drying to obtain modified polyurethane.
Further, the rust-proof pigment is one of mica iron oxide, zinc phosphate and aluminum tripolyphosphate.
Further, the filler is one of talcum powder, mica powder, wollastonite and barium sulfate.
Further, the leveling agent is an aromatic siloxane leveling agent.
Further, the defoamer is an organosilicon defoamer.
Further, the antifreezing agent is one of ethylene glycol, propylene glycol and isopropanol.
Further, the thickener is carboxymethyl cellulose.
A preparation method of an aqueous long-acting anticorrosive paint comprises the following steps:
mixing modified polyurethane, antirust pigment, filler and water according to the formula amount, dispersing uniformly at 500-1000 rpm, adding flatting agent, defoamer, antifreezing agent and thickener, dispersing uniformly at 800-1500 rpm, and grinding to fineness less than or equal to 30 mu m to obtain the anticorrosive paint.
The invention has the beneficial effects that:
1. compared with the prior art, the anti-corrosion coating prepared by the invention has better anti-corrosion effect, does not need to be added with a corrosion inhibitor, has good adhesive force and mechanical property, and is suitable for being used in various outdoor scenes.
2. The waterborne polyurethane coating prepared by the invention has multiple self-repairing mechanisms, so that damage repair can be completed without external force, coating performance can be maintained for a long time, and cost can be greatly reduced.
Detailed Description
The model of the aromatic siloxane leveling agent is as follows: BYK-323.
Organosilicon defoamer, model: BYK-024.
5-Amino-2-mercaptobenzothiazole, CAS number: 52386-09-1.
2,2-bis (4-isocyanatocyclohexyl) propane, 2-bis (4-isocyanate-cyclohexyl) propane, CAS number: 26189-89-9.
Polytetrahydrofuran ether, mw=2000.
Comparative example 1
A preparation method of an aqueous long-acting anticorrosive paint comprises the following steps:
mixing 350g of polyurethane, 100g of zinc phosphate, 120g of talcum powder and 300g of water, uniformly dispersing at 800rpm, adding 5g of BYK-323, 4g of BYK-024, 10g of ethylene glycol and 3g of carboxymethyl cellulose, uniformly dispersing at 1200rpm, and grinding until the fineness is less than or equal to 30 mu m, thus obtaining the anti-corrosive paint.
The preparation method of the polyurethane comprises the following steps:
44g of isophorone diisocyanate is heated to 65 ℃, 0.004g of dibutyltin dilaurate is added, stirring is carried out for 18h under inert atmosphere at 65 ℃, 400g of polytetrahydrofuran ether is added, polymerization is carried out for 4h after heating to 110 ℃, 58g of 2,2-bis (4-cyclohexyl isocyanate) propane is added for chain extension, cooling is carried out after 5h is finished, and polyurethane is obtained after drying.
Example 1
A preparation method of an aqueous long-acting anticorrosive paint comprises the following steps:
mixing 350g of modified polyurethane, 100g of zinc phosphate, 120g of talcum powder and 300g of water, uniformly dispersing at 800rpm, adding 5g of BYK-323, 4g of BYK-024, 10g of ethylene glycol and 3g of carboxymethyl cellulose, uniformly dispersing at 1200rpm, and grinding until the fineness is less than or equal to 30 mu m, thus obtaining the anti-corrosive paint.
The preparation method of the modified polyurethane comprises the following steps:
adding 91g of 5-amino-2-mercaptobenzothiazole, 63g of 4-aminothiophenol, 0.3g of gallic acid and 0.2g of manganese carbonate into 1500mL of water, adding 1mol/L sodium carbonate aqueous solution to adjust the pH value to 9, heating to 80 ℃ in an oxygen atmosphere after the addition, stirring for 4 hours under a closed condition, cooling to room temperature after the stirring is finished, adding water into the mixed solution for dilution, extracting with ethyl acetate, separating the solution, and performing organic phase drying concentration to obtain benzothiazole-dithioaniline derivatives;
x2 adding 28g of benzothiazole-dithio aniline derivative in the step X1 into 200mL of N, N-dimethylformamide to obtain solution A, heating 44g of isophorone diisocyanate to 65 ℃, then dropwise adding the solution A, adding 0.004g of dibutyltin dilaurate, stirring for 18h at 65 ℃ under inert atmosphere, adding 400g of polytetrahydrofuran ether, heating to 110 ℃ and polymerizing for 4h, adding 58g of 2,2-bis (4-cyclohexyl isocyanate) propane for chain extension, cooling after 5h, and drying to obtain the modified polyurethane.
Example 2
A preparation method of an aqueous long-acting anticorrosive paint comprises the following steps:
mixing 350g of polyurethane, 100g of zinc phosphate, 120g of talcum powder and 300g of water, uniformly dispersing at 800rpm, adding 3g of benzothiazole, 3g of BYK-323, 4g of BYK-024 g of ethylene glycol, 10g of carboxymethyl cellulose, uniformly dispersing at 1200rpm, and grinding until the fineness is less than or equal to 30 mu m, thus obtaining the anti-corrosive paint.
The preparation method of the polyurethane comprises the following steps:
44g of isophorone diisocyanate is heated to 65 ℃, 0.004g of dibutyltin dilaurate is added, stirring is carried out for 18h under inert atmosphere at 65 ℃, 400g of polytetrahydrofuran ether is added, polymerization is carried out for 4h after heating to 110 ℃, 58g of 2,2-bis (4-cyclohexyl isocyanate) propane is added for chain extension, cooling is carried out after 5h is finished, and polyurethane is obtained after drying.
Example 3
A preparation method of an aqueous long-acting anticorrosive paint comprises the following steps:
mixing 350g of modified polyurethane, 50g of zinc phosphate, 120g of talcum powder and 300g of water, uniformly dispersing at 800rpm, adding 5g of BYK-323, 4g of BYK-024, 10g of ethylene glycol and 3g of carboxymethyl cellulose, uniformly dispersing at 1200rpm, and grinding until the fineness is less than or equal to 30 mu m, thus obtaining the anti-corrosive paint.
The preparation method of the modified polyurethane comprises the following steps:
adding 91g of 5-amino-2-mercaptobenzothiazole, 63g of 4-aminothiophenol, 0.3g of gallic acid and 0.2g of manganese carbonate into 1500mL of water, adding 1mol/L sodium carbonate aqueous solution to adjust the pH value to 9, heating to 80 ℃ in an oxygen atmosphere after the addition, stirring for 4 hours under a closed condition, cooling to room temperature after the stirring is finished, adding water into the mixed solution for dilution, extracting with ethyl acetate, separating the solution, and performing organic phase drying concentration to obtain benzothiazole-dithioaniline derivatives;
x2 adding 28g of benzothiazole-dithio aniline derivative in the step X1 into 200mL of N, N-dimethylformamide to obtain solution A, heating 44g of isophorone diisocyanate to 65 ℃, then dropwise adding the solution A, adding 0.004g of dibutyltin dilaurate, stirring for 18h at 65 ℃ under inert atmosphere, adding 400g of polytetrahydrofuran ether, heating to 110 ℃ and polymerizing for 4h, adding 58g of 2,2-bis (4-cyclohexyl isocyanate) propane for chain extension, cooling after 5h, and drying to obtain the modified polyurethane.
Example 4
A preparation method of an aqueous long-acting anticorrosive paint comprises the following steps:
mixing 350g of modified polyurethane, 100g of zinc phosphate, 180g of talcum powder and 300g of water, uniformly dispersing at 800rpm, adding 5g of BYK-323, 4g of BYK-024, 10g of ethylene glycol and 3g of carboxymethyl cellulose, uniformly dispersing at 1200rpm, and grinding until the fineness is less than or equal to 30 mu m, thus obtaining the anti-corrosive paint.
The preparation method of the modified polyurethane comprises the following steps:
adding 91g of 5-amino-2-mercaptobenzothiazole, 63g of 4-aminothiophenol, 0.3g of gallic acid and 0.2g of manganese carbonate into 1500mL of water, adding 1mol/L sodium carbonate aqueous solution to adjust the pH value to 9, heating to 80 ℃ in an oxygen atmosphere after the addition, stirring for 4 hours under a closed condition, cooling to room temperature after the stirring is finished, adding water into the mixed solution for dilution, extracting with ethyl acetate, separating the solution, and performing organic phase drying concentration to obtain benzothiazole-dithioaniline derivatives;
x2 adding 28g of benzothiazole-dithio aniline derivative in the step X1 into 200mL of N, N-dimethylformamide to obtain solution A, heating 44g of isophorone diisocyanate to 65 ℃, then dropwise adding the solution A, adding 0.004g of dibutyltin dilaurate, stirring for 18h at 65 ℃ under inert atmosphere, adding 400g of polytetrahydrofuran ether, heating to 110 ℃ and polymerizing for 4h, adding 58g of 2,2-bis (4-cyclohexyl isocyanate) propane for chain extension, cooling after 5h, and drying to obtain the modified polyurethane.
Test example 1
The anticorrosive coatings prepared in the comparative examples and examples were subjected to performance tests, and the reference standards are as follows: adhesion, GB/T6739-2022 determination of paint film hardness by the paint and varnish pencil method; water resistance GB/T1733-1993 determination of water resistance of paint film; salt spray resistance, GB/T1771-2007 determination of neutral salt spray resistance of paint and varnish; hardness, GB/T6739-2022 "paint film hardness measured by the paint and varnish pencil method"; aging time, GB/T1865-2009 "Artificial weathering and Artificial radiation Exposure for color paints and varnishes". The specific test results are shown in Table 1.
Table 1 table of test results of anticorrosive paint properties
As can be seen from the comparison of comparative example 1 and example, the anticorrosive effect of the paint is poor without the addition of a corrosion inhibitor such as benzothiazole or the like to the paint, and the effect is limited although the anticorrosive pigment can protect the substrate to some extent. In example 2, benzothiazole was added as a corrosion inhibitor, but the water solubility was poor, and the compatibility was poor in the aqueous paint, so that the corrosion protection effect was not as good as in example 1. In the embodiment 1, the benzothiazole-dithioaniline derivative is obtained by cross coupling of 5-amino-2-mercaptobenzothiazole and 4-aminothiophenol and then polymerized with the polyurethane monomer, so that the problem of poor benzothiazole compatibility is solved, a more stable and durable corrosion-resistant effect is also obtained, and the hard segment alternation effect of the soft segment of polytetrahydrofuran ether and the cyclic isocyanate in the modified polyurethane finally achieves better strength and toughness, so that the coating shows excellent mechanical properties. The amount of rust inhibitive pigment added in example 3 directly affects the corrosion protection of the coating, while the amount of filler added in example 4 directly affects the dispersibility of the coating and thus the coating properties.
Test example 2
The anticorrosive paint prepared in the comparative examples and examples was sprayed on a cold rolled steel sheet (thickness 100 μm), then scratches were left on the surfaces of each group of test pieces, each test piece was left at room temperature to observe scratch repair, and the same test piece was heated at 60 ℃. The corrosion resistance of the treated steel plate is tested in the same way, and the corrosion condition at the scratch is observed by referring to GB/T10125-2012 salt spray test for artificial atmosphere corrosion test. The specific results are shown in Table 2.
Table 2 self-healing and anti-corrosion test results table for anti-corrosion coating
From the difference between comparative example 1, example 2 and example 1, it can be seen that the coating obtained without adding benzothiazole-dithiolane derivative when polyurethane is polymerized does not have self-repairing property, whereas the coating in example 1 can complete self-repairing under the action of light or heat, probably because disulfide bonds can be reversibly rearranged in the presence of light, heat and a reducing agent, and bond energy of aromatic disulfide bonds is lower, so that it can be reversibly rearranged at room temperature. In addition, the aromatic disulfide bond-containing polyurethane prepared by taking isophorone diisocyanate as a hard segment has excellent repairing performance at room temperature, probably because the alicyclic asymmetric structure is beneficial to the dynamic exchange of disulfide bonds to promote repairing. The self-repairing mechanism not only can reduce the damage of the coating, but also can maintain the long-acting property of the outdoor coating for corrosion prevention, and can repair the outdoor coating even if the outdoor coating is damaged without external force. The benzothiazole-dithiol aniline derivative added in the polyurethane polymerization in example 1 has a lone pair electron which can form a complex with the metal surface to achieve an anti-corrosion effect, so that a good anti-corrosion effect can be achieved.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (8)
1. An aqueous long-acting anticorrosive paint is characterized in that: the anti-rust polyurethane paint comprises, by weight, 30-50 parts of modified polyurethane, 5-15 parts of an anti-rust pigment, 8-18 parts of a filler, 0.1-2 parts of a leveling agent, 0.1-1 part of a defoaming agent, 0.5-1.5 parts of an antifreezing agent, 0.1-0.5 part of a thickening agent and 20-35 parts of water; the modified polyurethane is obtained by cross-coupling 5-amino-2-mercaptobenzothiazole and 4-aminothiophenol to obtain benzothiazole-dithio aniline derivatives and then polymerizing the benzothiazole-dithio aniline derivatives with polyurethane monomers.
2. The anticorrosive coating of claim 1, wherein: the rust-proof pigment is one of mica iron oxide, zinc phosphate and aluminum tripolyphosphate.
3. The anticorrosive coating of claim 1, wherein: the filler is one of talcum powder, mica powder, wollastonite and barium sulfate.
4. The anticorrosive coating of claim 1, wherein: the leveling agent is an aromatic siloxane leveling agent.
5. The anticorrosive coating of claim 1, wherein: the defoaming agent is an organosilicon defoaming agent.
6. The anticorrosive coating of claim 1, wherein: the antifreezing agent is one of ethylene glycol, propylene glycol and isopropanol.
7. The anticorrosive coating of claim 1, wherein: the thickener is carboxymethyl cellulose.
8. A method for preparing the anticorrosive paint according to any one of claims 1 to 7, comprising the steps of:
and mixing the modified polyurethane, the antirust pigment, the filler and the water according to the formula amount, uniformly dispersing at 500-1000 rpm, adding the flatting agent, the defoamer, the antifreezing agent and the thickener, uniformly dispersing at 800-1500 rpm, and grinding until the fineness is less than or equal to 30 mu m, thus obtaining the anticorrosive coating.
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