CN116554772A - Salt-fog-resistant metal antirust paint and preparation method thereof - Google Patents
Salt-fog-resistant metal antirust paint and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/328—Phosphates of heavy metals
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Abstract
The invention discloses a salt spray resistant metal antirust paint and a preparation method thereof, belonging to the technical field of metal corrosion prevention, and comprising the following raw materials in parts by weight: 20-35 parts of modified acrylic ester emulsion, 30-40 parts of waterborne polyurethane, 15-20 parts of composite anti-corrosion filler, 5-10 parts of modified zinc phosphate, 0.8-1.2 parts of dispersing agent, 0.2-0.4 part of defoamer, 0.1-0.2 part of pH regulator, 0.5-1.5 parts of thickener and 10-35 parts of deionized water; mixing the above materials in sequence; the invention adopts the modified acrylic emulsion and the aqueous polyurethane as film forming matrixes, so that the obtained paint film has the performances of acrylic paint and polyurethane paint, and has excellent weather resistance and adhesive force; and the modified zinc phosphate and the composite anti-corrosion filler are introduced, so that the corrosion resistance of the paint is improved, and meanwhile, a good toughening effect is achieved.
Description
Technical Field
The invention belongs to the technical field of metal corrosion prevention, and particularly relates to a salt spray-resistant metal antirust coating and a preparation method thereof.
Background
With the development of economy and the enhancement of environmental awareness of people, the water-based metal anti-corrosion coating is more and more popular, and the water-based coating with more application at present mainly comprises a water-based epoxy resin coating, a water-based acrylic ester resin coating and a water-based polyurethane resin coating.
The aqueous epoxy resin has good adhesive force and high curing speed, but has poor corrosion resistance; the water-based acrylic ester has good film forming property, chemical resistance and weather resistance, but the water absorption is improved and the corrosion resistance is reduced because a paint film of the water-based acrylic ester is easy to form a water penetration channel; the aqueous polyurethane coating has excellent adhesion and good flexibility, but has lower crosslinking density and poorer comprehensive performance compared with solvent polyurethane. It is clear that single-function resins have failed to meet today's demands for superior overall performance.
For example, chinese patent CN112480788A discloses a water-based nano silica salt spray-resistant waterproof coating for steel structures and a preparation method thereof, chinese patent CN111440504B discloses a water-based anticorrosive coating and a preparation method and application thereof, the former uses water-based acrylic emulsion and water-based epoxy emulsion compound emulsion as film forming substances, the latter uses organosilicon modified water-based acrylic emulsion and water-based aliphatic polyurethane as film forming substances, the formed paint film performances are better than single functional resin, and both adopt organosilicon modified water-based acrylic emulsion, although the organosilicon modified water-based acrylic emulsion has weather resistance and stain resistance compared with the water-based acrylic emulsion, when the organosilicon modified water-based acrylic resin is used, the organosilicon is easy to generate hydrolysis and polycondensation reaction in water, so that emulsion stability is low, active group content is reduced, and a stable cross-linked network is difficult to form with epoxy resin emulsion or polyurethane emulsion, so that the obtained anticorrosive coating has poor performances.
In Chinese patent CN111440504B, zinc phosphate is used as antirust pigment, and the zinc phosphate dispersed in the coating dissolves PO through contact with corrosive medium 4 3- The metal surface reacts with corrosive medium to generate Fe 3+ ，PO 4 3- The existence of the catalyst can inhibit the corrosion reaction of metal and form more compact FePO on the surface of the metal 4 ，Fe 2 O 3 And FeO, inhibiting corrosion of metals, but zinc phosphate pigmentsThe self-made water-soluble polymer is a polycrystalline water inorganic substance, has poor compatibility with organic resin, has larger gap defects with a resin interface, and is difficult to play a good anti-corrosion role.
Therefore, there is a need to provide a salt spray resistant metallic rust inhibitive paint with better performance.
Disclosure of Invention
The invention aims to provide a salt spray resistant metal antirust paint and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
(1) The organosilicon modified aqueous acrylic emulsion used in the existing metal antirust coating has low stability and low active group content, and is difficult to form a stable crosslinked network with epoxy resin emulsion or polyurethane emulsion, so that the formed paint film has poor corrosion resistance.
(2) At present, zinc phosphate is adopted as an antirust pigment, and the problems of poor compatibility with organic resin and large gap defect at the interface between the zinc phosphate and the resin exist.
The aim of the invention can be achieved by the following technical scheme:
the salt spray resistant metal antirust paint comprises the following raw materials in parts by weight: 20-35 parts of modified acrylic emulsion, 30-40 parts of waterborne polyurethane, 15-20 parts of composite anti-corrosion filler, 5-10 parts of modified zinc phosphate, 0.8-1.2 parts of dispersing agent, 0.2-0.4 part of defoamer, 0.1-0.2 part of pH regulator, 0.5-1.5 parts of thickener and 10-35 parts of deionized water.
Further, the modified acrylate emulsion is prepared by the following steps:
adding methyl methacrylate, butyl acrylate, acrylic acid, 2- (hydroxymethyl) methyl acrylate, hexafluorobutyl methacrylate and functional monomers into deionized water dissolved with an emulsifier, placing the mixture in a high-speed dispersion homogenizer for dispersion for 15-20min to obtain a pre-emulsion, adding 1/3 of the pre-emulsion, sodium bicarbonate and deionized water into a reaction kettle, stirring and heating to 80 ℃ under nitrogen atmosphere, dropwise adding 1/3 of an initiator solution, preserving heat for 10-15min, dropwise adding the rest of the pre-emulsion and the initiator solution, preserving heat for 1h after the dropwise adding is finished, reacting for 1h at 85 ℃, discharging when the temperature is reduced to 25 ℃, and regulating the pH to 7 by using ammonia water to obtain the modified acrylate emulsion.
Wherein, the mass ratio of the pre-emulsion to the sodium bicarbonate to the deionized water to the initiator solution is 100:0.3-0.6:20-30:10, an initiator solution is prepared from ammonium persulfate and deionized water according to the mass ratio of 0.4-0.6g:10mL of the pre-emulsion comprises methyl methacrylate, butyl acrylate, acrylic acid, 2- (hydroxymethyl) methyl acrylate, hexafluorobutyl methacrylate, a functional monomer, an emulsifier and deionized water in a mass ratio of 15:15-20:1.5:2.5:3-4:4-6:6-8:45-50, wherein the emulsifier is allyloxynonylphenol polyoxyethylene (10) ether ammonium sulfate (DNS-86).
According to the invention, butyl acrylate and methyl methacrylate are used as soft and hard monomers, a functional monomer and hexafluorobutyl methacrylate are compounded, and under the initiation of ammonium persulfate, a modified acrylate emulsion containing an F-C long chain, a Schiff base structure and a benzothiazole structure is obtained; the introduced F-C long chain gradually migrates to the outside of the paint film in the curing process of the paint film, the hydrophobicity of the paint film is improved, compared with the method for improving the weather resistance of emulsion by introducing organosilicon, the formed emulsion is more stable, the N in the Schiff base structure and N, S atoms in the benzothiazole structure have strong interaction with metal, and the existence of the N and the N, S atoms can improve the adhesiveness between the paint film and a metal substrate and improve the corrosion resistance of the paint film.
Further, the functional monomer is prepared by the following steps:
step S1, adding salicylaldehyde into absolute ethyl alcohol, dropwise adding a 2-aminobenzothiazole absolute ethyl alcohol solution after stirring, stirring at 60 ℃ under a nitrogen atmosphere after the dropwise adding is finished for reacting for 4-6 hours, pouring a reaction product into ice water after the reaction is finished, filtering, washing a filter cake with distilled water, and drying at 60 ℃ to obtain an intermediate product;
wherein, the mol ratio of salicylaldehyde to 2-aminobenzothiazole is 1:1-1.2, reacting an aldehyde group of salicylaldehyde with an amino group of 2-aminobenzothiazole to form an intermediate product containing a phenolic hydroxyl group, a Schiff base structure and a benzothiazole structure;
s2, adding an intermediate product, anhydrous potassium carbonate and anhydrous acetone into a flask, adding 4-bromo-1-butene under stirring, heating to reflux for 3-4h under a nitrogen atmosphere, filtering after the reaction is finished, and removing acetone from the filtrate by rotary evaporation to obtain a functional monomer;
wherein the dosage ratio of the intermediate product, anhydrous potassium carbonate, anhydrous acetone and 4-bromo-1-butene is 2.7g:3.36g:100mL:1.8-2.0mL, and the phenolic hydroxyl group of the intermediate product and 4-bromo-1-butene are utilized to carry out elimination reaction to obtain a functional monomer, wherein the structural formula is as follows:
further, the modified zinc phosphate is prepared by the following steps:
adding zinc phosphate into ethanol solution, stirring for 5-10min, adding glacial acetic acid, adding coupling agent KH-560 at 75 ℃, stirring for reaction for 24h, filtering, washing filter cake with distilled water, and vacuum drying at 60 ℃ to constant weight to obtain modified zinc phosphate.
Wherein the dosage ratio of zinc phosphate, ethanol solution, glacial acetic acid and coupling agent KH-560 is 0.3-0.5g:10-15mL:0.6-1.0g:2g, ethanol solution is prepared from absolute ethanol and deionized water according to the volume ratio of 60-70:25-35, the coupling agent KH-560 is taken as a monomer, methoxy groups of the coupling agent KH-560 are hydrolyzed by an acid catalytic hydrolysis method to generate silanol, then the silanol is dehydrated and condensed with hydroxyl groups on the surface of zinc phosphate, the residual hydroxyl groups on the silanol are condensed with each other to form a hyperbranched structure, finally, the zinc phosphate grafted with the epoxy group-terminated hyperbranched polysiloxane is prepared, the zinc phosphate is uniformly dispersed in the coating based on the characteristics of low viscosity and good organic compatibility of the hyperbranched polymer, a connecting bridge is formed between the zinc phosphate and resin by utilizing the characteristics of the hyperbranched polysiloxane, and the defect of low interface bonding strength of the zinc phosphate and the resin base material is overcome by the reaction of active epoxy groups, hydroxyl groups, carboxyl groups and the like.
Further, the composite anti-corrosion filler is prepared by the following steps:
adding glass flakes into DMF, dropwise adding 3-isocyanatopropyl trimethoxy silane while stirring, stirring for 10min, carrying out ultrasonic treatment for 20-30min after the dropwise adding is finished, stirring at 105 ℃ for reacting for 2-3h, centrifuging to remove supernatant, washing with ethanol, drying at 60 ℃ to obtain an intermediate product, adding the intermediate product into absolute ethanol, adding a nano titanium dioxide suspension, stirring at 60 ℃ for reacting for 2-3h, centrifuging, washing precipitate with deionized water and ethanol for three times respectively, and drying at 60 ℃ to constant weight to obtain the composite anti-corrosion filler.
Further, the glass flake, DMF and 3-isocyanatopropyl trimethoxysilane were used in an amount ratio of 1g:50-60mL, 0.3-0.5g, the dosage ratio of the intermediate product, the absolute ethyl alcohol and the nano titanium dioxide is 10g:100-150mL:2.5-3.3g, the suspension of nano titanium dioxide is prepared from nano titanium dioxide and deionized water according to the dosage ratio of 1g:5-8mL ultrasonic mixing; based on the excellent anti-corrosion performance of the glass flakes and the nano titanium dioxide, the composite anti-corrosion filler is obtained by compounding the glass flakes and the nano titanium dioxide through chemical means, and is added into a coating matrix, so that compared with a paint film formed by respectively adding the two fillers, the anti-corrosion performance is stronger, firstly, the existence of the nano titanium dioxide fills the pores among the glass flakes, and the anti-corrosion barrier performance is more excellent; secondly, a more complex maze effect is formed, so that corrosive medium is difficult to permeate into a resin system, and a corrosion path is increased; thirdly, the nano titanium dioxide is stably loaded on the surface of the glass flake through a chemical bonding means to form an anchoring effect, so that the nano titanium dioxide stably plays a weather-proof role and a protective role.
Further, the aqueous polyurethane is one or two of Wanhua chemical Lacper 4211 and European Baodi U7400.
Further, the dispersing agent is one or both of tego755w and tego 3800.
Further, the defoamer is one or more of BKY024, BYK019 and BYK 1770.
Further, the pH regulator is one or two of dimethylethanolamine and 2-amino-2-methyl-1-propanol.
Further, the thickener is a nonionic hydrophobically modified polyurethane rheology agent, preferably PUR42.
A preparation method of a salt spray resistant metal antirust paint comprises the following steps:
mixing deionized water, a dispersing agent, a defoaming agent, a pH regulator and a composite anti-corrosion filler, stirring and mixing at the rotating speed of 500-600r/min for 3-5min, then adding the modified acrylate emulsion, the aqueous polyurethane, the thickening agent and the modified zinc phosphate, and continuing stirring for 3-5min to obtain the salt mist-resistant metal anti-rust paint.
The invention has the beneficial effects that:
1. the metal antirust coating prepared by the invention is green and environment-friendly, does not contain an organic volatile solvent, adopts modified acrylic ester emulsion and aqueous polyurethane as film forming matrixes, active groups in the modified acrylic ester emulsion can be combined with the aqueous polyurethane to form an interpenetrating network, so that a paint film has the performances of acrylic ester coating and polyurethane coating, and F-C long chains, schiff base structures and benzothiazole structures are introduced, so that the paint film has excellent weather resistance and adhesive force;
2. according to the invention, modified zinc phosphate is introduced into the base material, so that the modified zinc phosphate has high compatibility with a resin matrix and strong binding force, and the hyperbranched polysiloxane structure grafted on the surface has a toughening and reinforcing effect on a paint film;
3. compared with the method that the two fillers are respectively added to form a shielding network, the method forms a more complex labyrinth effect and has excellent blocking and shielding effects;
in conclusion, the coating prepared by the invention has the characteristics of high adhesive force, water resistance and salt spray resistance, and has excellent protective effect on metal substrates.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A modified acrylic ester emulsion is prepared by the following steps:
15g of methyl methacrylate, 15g of butyl acrylate, 1.5g of acrylic acid, 2.5g of 2- (hydroxymethyl) methyl acrylate, 3g of hexafluorobutyl methacrylate and 4g of functional monomer are added into 45mL of deionized water dissolved with 6g of emulsifier, and the mixture is placed in a high-speed dispersion homogenizer for dispersion for 15min to obtain a pre-emulsion, 1/3 mass of the pre-emulsion, 0.3g of sodium bicarbonate and 20g of deionized water are added into a reaction kettle, the mixture is stirred and heated to 80 ℃ under nitrogen atmosphere, 1/3 mass of initiator solution is dropwise added, after heat preservation is carried out for 10min, the rest of pre-emulsion and initiator solution are dropwise added, after the dropwise addition is finished, the heat preservation is carried out for 1h, the mixture is heated to 85 ℃ for reaction for 1h, the mixture is discharged after the mixture is cooled to 25 ℃, the pH value is adjusted to 7 by ammonia water, and modified acrylate emulsion is obtained, and the initiator solution is prepared from ammonium persulfate and deionized water according to the mass ratio of 0.4g:10mL, wherein the emulsifier is allyloxy nonylphenol polyoxyethylene (10) ether ammonium sulfate (DNS-86);
the functional monomer is prepared by the following steps:
s1, adding 0.1mol of salicylaldehyde into 150mL of absolute ethyl alcohol, dropwise adding a mixed solution consisting of 0.1mol of 2-aminobenzothiazole and 150mL of absolute ethyl alcohol after stirring, stirring at 60 ℃ under a nitrogen atmosphere for reaction for 4 hours after the dropwise adding is finished, pouring a reaction product into ice water after the reaction is finished, filtering, washing a filter cake with distilled water, and drying at 60 ℃ to obtain an intermediate product;
and S2, adding 2.7g of intermediate product, 3.36g of anhydrous potassium carbonate and 100mL of anhydrous acetone into a flask, adding 1.8mL of 4-bromo-1-butene under stirring, heating to reflux under nitrogen atmosphere, reacting for 3h, filtering after the reaction is finished, and removing acetone from the filtrate by rotary evaporation to obtain the functional monomer.
Example 2
A modified acrylic ester emulsion is prepared by the following steps:
15g of methyl methacrylate, 20g of butyl acrylate, 1.5g of acrylic acid, 2.5g of 2- (hydroxymethyl) methyl acrylate, 4g of hexafluorobutyl methacrylate and 6g of functional monomer are added into 50mL of deionized water dissolved with 8g of emulsifier, the mixture is placed in a high-speed dispersion homogenizer for dispersion for 20min to obtain a pre-emulsion, 1/3 mass of the pre-emulsion, 0.6g of sodium bicarbonate and 30g of deionized water are added into a reaction kettle, stirring and heating to 80 ℃ under nitrogen atmosphere, 1/3 mass of initiator solution is dropwise added, after heat preservation is carried out for 15min, the rest of pre-emulsion and initiator solution are dropwise added, after the dropwise addition is finished, heat preservation is carried out for 1h, heating to 85 ℃ for reaction for 1h, discharging is carried out when the temperature is reduced to 25 ℃, the pH value is regulated to 7 by ammonia water, and modified acrylate emulsion is obtained, and the initiator solution is prepared from ammonium persulfate and deionized water according to the mass ratio of 0.6g:10mL of the composition, and the emulsifier were the same as in example 1;
the functional monomer is prepared by the following steps:
s1, adding 0.1mol of salicylaldehyde into 150mL of absolute ethyl alcohol, dropwise adding a mixed solution consisting of 0.12mol of 2-aminobenzothiazole and 150mL of absolute ethyl alcohol after stirring, stirring at 60 ℃ under a nitrogen atmosphere for reaction for 6 hours after the dropwise adding is finished, pouring a reaction product into ice water after the reaction is finished, filtering, washing a filter cake with distilled water, and drying at 60 ℃ to obtain an intermediate product;
and S2, adding 2.7g of intermediate product, 3.36g of anhydrous potassium carbonate and 100mL of anhydrous acetone into a flask, adding 2.0mL of 4-bromo-1-butene under stirring, heating to reflux under nitrogen atmosphere, reacting for 4h, filtering after the reaction is finished, and removing acetone from the filtrate by rotary evaporation to obtain the functional monomer.
Comparative example 1
The comparative example is an organosilicon modified aqueous acrylic emulsion, which is the Hemsl light XG-908A.
Example 3
A modified zinc phosphate is prepared by the following steps:
adding 0.3g of zinc phosphate into 10mL of ethanol solution, stirring for 5min, adding 0.6g of glacial acetic acid, adding 2g of coupling agent KH-560 at 75 ℃, stirring for reaction for 24h, carrying out suction filtration, washing a filter cake with distilled water, and then carrying out vacuum drying at 60 ℃ until the weight is constant, thereby obtaining modified zinc phosphate, wherein the ethanol solution is prepared from absolute ethanol and deionized water according to a volume ratio of 60: 25.
Example 4
A modified zinc phosphate is prepared by the following steps:
adding 0.5g of zinc phosphate into 15mL of ethanol solution, stirring for 10min, adding 1.0g of glacial acetic acid, adding 2g of coupling agent KH-560 at 75 ℃, stirring for reaction for 24h, carrying out suction filtration, washing a filter cake with distilled water, and then carrying out vacuum drying at 60 ℃ until the weight is constant to obtain modified zinc phosphate, wherein the ethanol solution is prepared from absolute ethanol and deionized water according to a volume ratio of 70: 25.
Comparative example 2
The comparative example is zinc phosphate.
Example 5
The salt spray resistant metal antirust paint comprises the following raw materials in parts by weight: 20 parts of modified acrylic emulsion of example 1, 30 parts of waterborne polyurethane, 15 parts of composite anti-corrosion filler, 5 parts of modified zinc phosphate of example 3, 0.8 part of dispersing agent, 0.2 part of defoaming agent, 0.1 part of dimethylethanolamine, 0.5 part of thickening agent and 10 parts of deionized water;
the preparation method comprises the following steps:
mixing deionized water, a dispersing agent, a defoaming agent, a pH regulator and a composite anti-corrosion filler, stirring and mixing for 3min at the rotating speed of 500r/min, then adding modified acrylate emulsion, aqueous polyurethane, dimethylethanolamine and modified zinc phosphate, and continuing stirring for 3min to obtain the salt spray-resistant metal anti-rust paint, wherein the composite anti-corrosion filler is prepared by the following steps:
adding 1g of glass flake into 50mL of DMF, dropwise adding 0.3g of 3-isocyanatopropyl trimethoxysilane under stirring, stirring for 10min after the dropwise adding is finished, carrying out ultrasonic treatment for 20min under stirring at 105 ℃ for 2h, centrifuging to remove supernatant, washing with ethanol, drying at 60 ℃ to obtain an intermediate product, adding 10g of the intermediate product into 100mL of absolute ethanol, and adding nano titanium dioxide and deionized water according to 2.5g:12.5mL of ultrasonic mixing to obtain suspension, stirring at 60 ℃ for reaction for 2 hours, centrifuging, washing the precipitate with deionized water and ethanol for three times respectively, and drying at 60 ℃ to constant weight to obtain the composite anti-corrosion filler.
Wherein the water-based polyurethane is Wanhua chemical Lacper 4211, the dispersing agent is tego755w, the defoaming agent is BKY024, and the thickening agent is PUR42.
Example 6
The salt spray resistant metal antirust paint comprises the following raw materials in parts by weight: 28 parts of modified acrylic emulsion, 35 parts of waterborne polyurethane, 17 parts of composite anti-corrosion filler, 8 parts of modified zinc phosphate of example 4, 1 part of dispersing agent, 0.3 part of defoaming agent, 0.1 part of dimethylethanolamine, 1.0 part of thickening agent and 25 parts of deionized water; the preparation procedure was as in example 5.
Wherein, the composite anti-corrosion filler is prepared by the following steps:
adding 1g of glass flake into 60mL of DMF, dropwise adding 0.5g of 3-isocyanatopropyl trimethoxysilane under stirring, stirring for 10min after the dropwise adding is finished, carrying out ultrasonic stirring for 30min at 105 ℃ for reaction for 3h, centrifuging to remove supernatant, washing with ethanol, drying at 60 ℃ to obtain an intermediate product, adding 10g of the intermediate product into 150mL of absolute ethanol, and adding nano titanium dioxide and deionized water according to 3.3g:26.4mL of ultrasonic mixing to obtain suspension, stirring at 60 ℃ for reaction for 3 hours, centrifuging, washing the precipitate with deionized water and ethanol for three times respectively, and drying at 60 ℃ to constant weight to obtain the composite anti-corrosion filler.
Wherein the water-based polyurethane is Wanhua chemical Lacper 4211, the dispersing agent is tego3800, the defoaming agent is BKY024, and the thickening agent is nonionic hydrophobic modified polyurethane rheological agent, preferably PUR42.
Example 7
The salt spray resistant metal antirust paint comprises the following raw materials in parts by weight: 35 parts of modified acrylic emulsion of example 2, 40 parts of waterborne polyurethane, 20 parts of composite anti-corrosion filler, 10 parts of modified zinc phosphate of example 4, 1.2 parts of dispersing agent, 0.4 part of defoaming agent, 0.2 part of dimethylethanolamine, 1.5 parts of thickening agent and 35 parts of deionized water; the preparation procedure was as in example 5.
Wherein, the composite anticorrosive filler, the aqueous polyurethane, the dispersing agent, the defoamer and the thickener are the same as in example 6.
Comparative example 3
The modified acrylate emulsion of example 5 was replaced with the one of comparative example 1, the remaining materials and the preparation process were unchanged.
Comparative example 4
The modified zinc phosphate of example 5 was replaced with the material of comparative example 2, and the remaining raw materials and the preparation process were unchanged.
Comparative example 5
The composite anti-corrosion filler in the example 5 is replaced by a mixture composed of glass flakes and nano titanium dioxide in a mass ratio of 3:1, and the rest raw materials and the preparation process are unchanged.
The coatings obtained in examples 5 to 7 and comparative examples 3 to 5 were subjected to performance tests, and the coating matching system was subjected to performance tests with reference to HG/T5176-2017 Water anticorrosive paint for Steel Structure, specifically: freeze thawing stability (3 cycles without deterioration), adhesion (cross-hatch method), impact resistance; each group of the coatings was coated on a standard steel sheet to form a coating film having a film thickness of 50 μm, and the coating film was tested for salt spray resistance at 900 hours with reference to GB-T1771-2007, and the test results are shown in table 1:
TABLE 1
As can be seen from table 1, the coatings prepared in examples 5 to 7 have high adhesion, water resistance, salt spray resistance, and excellent protective effect on metal substrates, compared to comparative examples 3 to 5.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The salt spray resistant metal antirust paint is characterized by comprising the following raw materials in parts by weight: 20-35 parts of modified acrylic ester emulsion, 30-40 parts of waterborne polyurethane, 15-20 parts of composite anti-corrosion filler, 5-10 parts of modified zinc phosphate, 0.8-1.2 parts of dispersing agent, 0.2-0.4 part of defoamer, 0.1-0.2 part of pH regulator, 0.5-1.5 parts of thickener and 10-35 parts of deionized water;
wherein the modified acrylic ester emulsion is prepared by the following steps:
adding methyl methacrylate, butyl acrylate, acrylic acid, 2- (hydroxymethyl) methyl acrylate, hexafluorobutyl methacrylate and functional monomers into deionized water dissolved with an emulsifier, dispersing to obtain a pre-emulsion, adding 1/3 mass of the pre-emulsion, sodium bicarbonate and deionized water into a reaction kettle, stirring and heating to 80 ℃, dropwise adding 1/3 mass of an initiator solution under a nitrogen atmosphere, preserving heat for 10-15min, dropwise adding the rest pre-emulsion and the initiator solution, preserving heat for 1h after the dropwise adding is finished, heating to 85 ℃ for reacting for 1h, discharging when the temperature is reduced to 25 ℃, and adjusting the pH to obtain the modified acrylate emulsion.
2. The salt spray resistant metal antirust coating as claimed in claim 1, wherein the mass ratio of the pre-emulsion to the sodium bicarbonate to the deionized water to the initiator solution is 100:0.3-0.6:20-30:10, an initiator solution is prepared from ammonium persulfate and deionized water according to the mass ratio of 0.4-0.6g:10 mL.
3. The salt spray resistant metal antirust coating as claimed in claim 1, wherein the mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, 2- (hydroxymethyl) methyl acrylate, hexafluorobutyl methacrylate, functional monomer, emulsifier and deionized water in the pre-emulsion is 15:15-20:1.5:2.5:3-4:4-6:6-8:45-50.
4. The salt spray resistant metal rust inhibitive paint of claim 1, wherein the functional monomer is prepared by the steps of:
adding salicylaldehyde into absolute ethyl alcohol, stirring, then dropwise adding 2-aminobenzothiazole absolute ethyl alcohol solution, and stirring at 60 ℃ for reaction for 4-6 hours in a nitrogen atmosphere after the dropwise adding is finished to obtain an intermediate product;
adding the intermediate product, anhydrous potassium carbonate and anhydrous acetone into a flask, adding 4-bromo-1-butene under stirring, and heating to reflux reaction for 3-4h under nitrogen atmosphere to obtain the functional monomer.
5. The salt spray resistant metal rust inhibitive paint of claim 4, wherein the molar ratio of salicylaldehyde to 2-aminobenzothiazole is 1:1-1.2.
6. The salt spray resistant metal rust inhibitive paint of claim 4, wherein the ratio of the intermediate product, anhydrous potassium carbonate, anhydrous acetone and 4-bromo-1-butene is 2.7g:3.36g:100mL:1.8-2.0mL.
7. The salt spray resistant metal rust inhibitive paint of claim 1, wherein the modified zinc phosphate is prepared by the steps of:
adding zinc phosphate into ethanol solution, stirring, adding glacial acetic acid, adding coupling agent KH-560 at 75 ℃, and stirring for reacting for 24h to obtain modified zinc phosphate.
8. The salt spray resistant metal rust inhibitive paint of claim 7, wherein the dosage ratio of zinc phosphate, ethanol solution, glacial acetic acid and coupling agent KH-560 is 0.3-0.5g:10-15mL:0.6-1.0g:2g, ethanol solution is prepared from absolute ethanol and deionized water according to the volume ratio of 60-70: 25-35.
9. The method for preparing the salt spray resistant metal antirust paint as claimed in claim 1, which is characterized by comprising the following steps:
and mixing deionized water, a dispersing agent, a defoaming agent, a pH regulator and a composite anti-corrosion filler, and then adding modified acrylate emulsion, aqueous polyurethane, a thickening agent and modified zinc phosphate, and uniformly mixing to obtain the salt spray resistant metal anti-rust paint.
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