CN116004092A - Dual-curing anticorrosive paint and preparation method and application thereof - Google Patents
Dual-curing anticorrosive paint and preparation method and application thereof Download PDFInfo
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- CN116004092A CN116004092A CN202211582091.5A CN202211582091A CN116004092A CN 116004092 A CN116004092 A CN 116004092A CN 202211582091 A CN202211582091 A CN 202211582091A CN 116004092 A CN116004092 A CN 116004092A
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- 239000003973 paint Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 19
- 239000001205 polyphosphate Substances 0.000 claims abstract description 19
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 6
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 6
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 238000001723 curing Methods 0.000 claims description 31
- 238000005260 corrosion Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 11
- 230000009977 dual effect Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- 150000002513 isocyanates Chemical group 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 claims description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 2
- WNISWKAEAPQCJQ-UHFFFAOYSA-N 2-[(2-nonylphenoxy)methyl]oxirane Chemical compound CCCCCCCCCC1=CC=CC=C1OCC1OC1 WNISWKAEAPQCJQ-UHFFFAOYSA-N 0.000 claims description 2
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 claims description 2
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 claims description 2
- -1 hexafluorophosphate Chemical compound 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims 1
- FWGZLZNGAVBRPW-UHFFFAOYSA-N alumane;strontium Chemical compound [AlH3].[Sr] FWGZLZNGAVBRPW-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 238000000016 photochemical curing Methods 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000013530 defoamer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VGPBPWRBXBKGRE-UHFFFAOYSA-N n-(oxomethylidene)hydroxylamine Chemical compound ON=C=O VGPBPWRBXBKGRE-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013022 formulation composition Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YNDGDLJDSBUSEI-UHFFFAOYSA-N aluminum strontium Chemical compound [Al].[Sr] YNDGDLJDSBUSEI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 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 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 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 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention provides a dual-curing anticorrosive paint, a preparation method and application thereof. The dual-curing anticorrosive paint comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 10 to 30 parts of epoxy resin, 40 to 60 parts of reactive diluent, 10 to 30 parts of filler, 2 to 5 parts of antirust pigment, 2 to 5 parts of aluminum-containing polyphosphate, 0.5 to 1.5 parts of dispersing agent, 0.1 to 0.5 part of defoaming agent, 0.5 to 2.5 parts of cationic photoinitiator and 0.2 to 2 parts of photosensitizer; the component B is isocyanate curing agent. The invention uses Al in the aluminum-containing polyphosphate 3+ The metal coordination effect formed between the ions and the urethane bond ligand in the coating system improves the chemical stability of the urethane bond, inhibits the hydrolysis of the urethane bond, and further improves the acid and alkali resistance of the cured coating and the storage stability of the coating.
Description
Technical Field
The invention relates to the technical field of anti-corrosion materials, in particular to a dual-curing anti-corrosion coating and a preparation method and application thereof.
Background
The photocuring paint is one of the important development directions of green environment-friendly paint due to the characteristics of high production efficiency, low energy consumption and the like. However, there are two problems associated with the use of photocurable coatings in the field of metal corrosion protection: (1) the problem of irradiation intensity attenuation exists in the process of penetrating the coating by ultraviolet light, and the low curing degree of the bottom of a paint film is easy to cause in a thick coating system, so that the performance is influenced; (2) the photo-curing coating system has high crosslinking degree, strong system rigidity and poor adhesive force.
The dual curing system prepared based on photo-curing comprises photo-thermal/photo-room temperature self-crosslinking, photo-oxygen, photo-moisture and other schemes, which are good strategies for solving the defects of the single-use ultraviolet curing scheme.
At present, the dual-curing system mostly adopts free radical type photo-curing, has large volume shrinkage and poor adhesive force, and is not beneficial to preparing thick coatings.
And the acrylate monomer or the acrylated prepolymer used for free radical photo-curing contains a large amount of ester bonds, and the ester bonds are easy to hydrolyze under acidic or alkaline conditions, so that the acid and alkali resistance of the coating is poor, and the application of the free radical photo-curing coating in the heavy-duty field is limited.
Therefore, there is a need to provide an anticorrosive paint excellent in acid and alkali resistance.
Disclosure of Invention
The invention aims to overcome the defect of poor acid and alkali resistance of the existing ester paint and provide the double-curing anticorrosive paint with excellent acid and alkali resistance. The invention uses Al in the aluminum-containing polyphosphate 3+ The metal coordination effect formed between the ions and the urethane bond ligand in the coating system improves the chemical stability of the urethane bond, inhibits the hydrolysis of the urethane bond, and further improves the acid and alkali resistance of the cured coating.
The invention further aims at providing a preparation method of the dual-curing anticorrosive paint.
It is another object of the present invention to provide the use of the dual cure anticorrosive coating in the anticorrosive field.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the dual-curing anticorrosive paint comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
the component B is isocyanate curing agent, and the weight ratio of the component A to the component B is 100: (5-15).
The double-cured coating formed by cationic photo-curing and room-temperature crosslinking curing of hydroxyl (from epoxy resin) -isocyanate can be photo-cured under ultraviolet irradiation and rapidly establish surface hardness and initial corrosion resistance, and the room-temperature crosslinking curing reaction of hydroxyl-isocyanate is utilized to further establish adhesive force and corrosion resistance in the bottom area of the coating with weak ultraviolet irradiation intensity.
However, the urethane linkages formed by hydroxyl-isocyanate crosslinking still hydrolyze to some extent under acidic or basic conditions, reducing the acid and alkali resistance of the coating, and the inventors of the present invention have found through extensive research that, for example, aluminum-containing polyphosphate is added to a coating system: in one aspect, the Al in the aluminum-containing polyphosphate 3+ The metal coordination effect formed between the ions and the urethane bond ligand formed by the hydroxyl-isocyanate crosslinking improves the chemical stability of the urethane bond and the acid and alkali corrosion resistance of the coating; on the other hand, aluminum-containing polyphosphate is a polymer salt, and the polymer segment has good compatibility with an epoxy resin system and improves the storage stability of the coating. The prepared anticorrosive paint has excellent corrosion resistance and can be used in the heavy-duty anticorrosive field.
Conventional epoxy resins may be used in the present invention, preferably epoxy resins containing a benzene ring structure that may have some shielding properties against corrosions, including but not limited to at least one of E-12, E-20.
Preferably, the reactive diluent comprises C 8～10 Glycidyl ether, C 12～14 Glycidyl ether, n-butylAt least one of glycidyl ether, o-cresol glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, benzyl glycidyl ether, nonylphenol glycidyl ether, resorcinol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dipropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, or dimer acid diglycidyl ester.
Preferably, the filler is at least one of wollastonite, silica micropowder, natural barium sulfate or talcum powder.
Preferably, the rust inhibitive pigment is an ion-exchange type rust inhibitive pigment, including but not limited to a calcium ion-exchanged silica type rust inhibitive pigment or a magnesium ion-exchanged silica type rust inhibitive pigment, including the following brands of products: at least one of LM-50, LM-30, SHIELDEX C303, SHIELDEX AC 3 and SHIELDEX AC 5.
Preferably, the aluminum-containing polyphosphate is an aluminum strontium polyphosphate hydrate (e.g
SAPP), calcium aluminum polyphosphate hydrate (e.g.)>
CAPP). />
Preferably, the dispersant includes, but is not limited to, branched polyesters (BYK-2151, BYK-2152).
Preferably, the defoamer includes at least one of a silicon based defoamer, an ether based defoamer, or a silicone based defoamer, such as at least one of BYK-054, BYK-A501, BYK-A530, or BYK-A535 defoamer.
Preferably, the cationic initiator is at least one of 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide-bis hexafluorophosphate, bis [ 4-diphenylthiophenyl ] sulfide di-hexafluoroantimonate, diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate and diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate, and specifically Easepi 1176, easepi 6992 or Easepi 250 can be selected.
Preferably, the photosensitizer is at least one of isopropyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propoxy thioxanthone or 2, 4-diethyl thioxanthone.
Conventional isocyanate curing agents may be used in the present invention, including but not limited to at least one of hexamethylene diisocyanate biuret, hexamethylene diisocyanate trimer, or toluene diisocyanate polycondensate, specifically selected from the following trade mark products: at least one of Desmodur N75, desmodur N3300, desmodur N3390, desmodur N3600, desmodur N3900, or Desmodur L75.
The invention also provides a preparation method of the dual-curing anticorrosive paint, wherein the component B is an independent isocyanate curing agent, and the preparation of the component A comprises the following steps:
uniformly mixing epoxy resin and an active diluent at 40-60 ℃, cooling, adding a dispersing agent, a defoaming agent, a filler, an anti-rust pigment and an aluminum-containing polyphosphate, grinding and mixing until the particle size fineness of a system is less than or equal to 25 mu m, and finally adding a cationic photoinitiator and a photosensitizer, and uniformly mixing to obtain the component A of the dual-curing anti-corrosion coating.
The application of the dual-curing anticorrosive paint in the anticorrosive field is also within the protection scope of the invention.
When the dual-curing anticorrosive paint is used, the component A and the component B of the paint are mixed and stirred according to a certain proportion, and then are coated on a substrate in a brushing, rolling or spraying mode, and are cured by light and then are cured by self-drying.
The conditions of the photo-curing are as follows: under the test of an ultraviolet irradiation energy meter with the wavelength of 250-410 nm, the surface exposure energy value is 5000-10000 mJ/cm 2 。
The self-drying curing is performed at room temperature (20-30 ℃).
Compared with the prior art, the invention has the beneficial effects that:
in the technical proposal provided by the invention, the epoxy resin and the epoxy group on the reactive diluentThe group can be subjected to cationic photo-curing, so that the aim of quickly establishing initial performance is fulfilled, and compared with conventional free radical photo-curing, the group has the characteristic of low shrinkage rate, and is beneficial to establishing better adhesive force and preparing a thick coating; hydroxyl on the epoxy resin can carry out hydroxyl-isocyanate crosslinking reaction with the isocyanate curing agent of the component B, and a carbamate bond generated by the reaction can play a role in internal toughening, so that the adhesive force and the corrosion resistance of the cured epoxy resin after the system is further improved. The coating prepared by the dual-curing system has high density, excellent corrosion resistance and good adhesive force. And, al in the aluminum-containing polyphosphate 3+ The metal coordination effect formed between the ions and the urethane bond ligand in the coating system improves the chemical stability of the urethane bond, inhibits the hydrolysis of the urethane bond, and further improves the acid and alkali resistance of the cured coating and the storage stability of the coating.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
Examples 1 to 9 and comparative examples 1 to 5
The examples and comparative examples of the present invention provide a series of dual cure anticorrosive coatings wherein the a component is prepared according to a process comprising the steps of:
according to the formulas in tables 1 and 2, uniformly mixing epoxy resin and reactive diluent at 50 ℃, cooling to room temperature (20-30 ℃), adding dispersant and defoamer, mixing for 10min at 1000rpm, adding filler, antirust pigment and aluminum-containing polyphosphate, grinding and mixing until the particle size fineness of the system is less than or equal to 25 mu m; and finally, adding a cationic photoinitiator and a photosensitizer, and dissolving and mixing for 20min at a rotation speed of 500rpm to obtain the component A of the dual-curing anticorrosive paint.
And mixing and stirring the coating A and the coating B according to a specified proportion, and then coating the coating A and the coating B on a substrate in a brushing, rolling or spraying mode, and performing photo-curing and self-drying curing to obtain the dry film with the thickness of 100-150 mu m.
The conditions of photo-curing are: under the test of an ultraviolet irradiation energy meter with the wavelength of 250-410 nm, the surface exposure energy value is measured to be 5000-10000 mJ/cm 2 。
The conditions for self-drying curing are as follows: drying at 25deg.C for 14 days.
Table 1 formulation composition (parts by weight) of the double-cured anticorrosive paint of the example
Table 2 formulation composition (parts by weight) of the dual-cure anticorrosive paint of comparative example
Performance testing
The performance of the dual-curing anticorrosive paint obtained in the above examples and comparative examples was characterized, and specific test items, test methods and results are as follows:
table 3 test items and test methods
In the invention, the material and surface treatment of the test base material meet the requirements of GB/T9271-2008. The substrate for pencil hardness test was a tin plate and was polished to St3 grade using 400# sandpaper. The rest of the base materials for the test are sand-blasted steel plates, the rust removal grade of the steel plates reaches the Sa2.5 grade specified in GB/T8923.1-2011, and the surface roughness reaches the fine (G) grade specified in GB/T13288.1-2011.
Table 4 test results of dual cure coatings obtained in examples and comparative examples
From the above results, it can be seen that:
the dual-cured anticorrosive paint prepared by the invention has excellent surface hardness, acid and alkali resistance, salt water resistance, oil resistance, salt fog resistance and adhesive force, and can be used in the heavy-duty anticorrosive coating field.
In comparative example 1, aluminum-containing polyphosphate was not added, in comparative example 2, zinc phosphate was substituted for aluminum-containing polyphosphate, and in comparative example 3, the addition amount of aluminum-containing polyphosphate was excessively large, resulting in a significantly reduced performance of the corrosion-resistant coating.
The cationic photo-curing system was replaced with the radical photo-curing system in comparative example 4, and the properties of the resulting coating were significantly degraded due to the fact that: (1) compared with cationic photo-curing, the free radical photo-curing has weak deep curing capability and affects the adhesive force performance; (2) the volume shrinkage rate of the free radical type photo-curing system is larger than that of the cationic type photo-curing system, and when the thick film anti-corrosion coating is prepared, the internal stress of the coating is large, and microcracks are easy to generate to influence the anti-corrosion performance and the adhesive force of the coating.
The comparative example 5 does not contain isocyanate curing agent, the intensity of illumination radiation received by the bottom of the coating is weak, the crosslinking degree is low, the binding force between the coating and the substrate is affected, the adhesive force is poor, and the corrosion resistance is reduced.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The dual-curing anticorrosive paint comprises a component A and a component B, and is characterized in that the component A comprises the following components in parts by weight:
the component B is isocyanate curing agent, and the weight ratio of the component A to the component B is 100: (5-15).
2. The dual cure anti-corrosive paint of claim 1, wherein said epoxy resin is at least one of E-12, E-20.
3. The dual cure anticorrosive coating of claim 1 wherein the reactive diluent is C 8～10 Glycidyl ether, C 12～14 At least one of glycidyl ether, n-butyl glycidyl ether, o-cresol glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, benzyl glycidyl ether, nonylphenol glycidyl ether, resorcinol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dipropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, or dimer acid diglycidyl ester.
4. The dual cure anticorrosive coating according to claim 1, wherein the filler is at least one of wollastonite, fine silica powder, natural barium sulfate or talc.
5. The dual cure anticorrosive paint of claim 1, wherein the rust inhibiting pigment is an ion exchange type rust inhibiting pigment.
6. The dual cure anticorrosive coating of claim 1 wherein the aluminum-containing polyphosphate is at least one of strontium aluminum polyphosphate hydrate, calcium aluminum polyphosphate hydrate.
7. The dual cure anticorrosive coating of claim 1 wherein the cationic photoinitiator is at least one of 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide-bis hexafluorophosphate, bis [ 4-diphenylsulfanyl ] sulfide di-hexafluoroantimonate, diphenyl- (4-phenylsulfanyl) phenylsulfonium hexafluorophosphate, and diphenyl- (4-phenylsulfanyl) phenylsulfonium hexafluoroantimonate.
8. The dual cure anticorrosive coating according to claim 1, wherein the photosensitizer is at least one of isopropyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propoxy thioxanthone, or 2, 4-diethyl thioxanthone.
9. The method for preparing the dual-curing anticorrosive paint as claimed in any one of claims 1 to 8, wherein the preparation of the component a comprises the following steps:
uniformly mixing epoxy resin and an active diluent at 40-60 ℃, cooling, adding a dispersing agent, a defoaming agent, a filler, an anti-rust pigment and an aluminum-containing polyphosphate, grinding and mixing until the particle size fineness of a system is less than or equal to 25 mu m, and finally adding a cationic photoinitiator and a photosensitizer, and uniformly mixing to obtain the component A of the dual-curing anti-corrosion coating.
10. Use of a dual-cure anticorrosive coating according to any one of claims 1 to 8 in the field of corrosion protection.
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