A highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating and its preparation method and application

Abstract

The present invention discloses a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating and a preparation method and application thereof, which belongs to the technical field of metal surface treatment, and comprises the following steps: cleaning and drying the surface of a metal plate substrate, and then evenly spraying the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating on the metal plate, and obtaining the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating after the coating is cured. The coating prepared by the present invention does not contain organic solvents, is safe and environmentally friendly, and by adding modified carbon nanotubes to the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating, the adhesion between the coating and the metal substrate is enhanced, and a certain flexibility is provided to the coating, which plays a role of toughening. By adding coated modified nano zirconium phosphate, the self-repairing effect of the coating can be achieved; the coating can be used in the field of anti-corrosion technology of metal plates.

Description

Technical Field

[0001] The invention relates to the technical field of metal surface coatings, and in particular to a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating and a preparation method and application thereof. Background Art

[0002] Metal sheets are widely used in the construction, automotive, shipbuilding, aerospace and other industries due to their high strength, good processing performance and cost-effectiveness. However, metal sheets are susceptible to factors such as wear, corrosion and ultraviolet rays in the natural environment, resulting in performance degradation and shortened service life. In order to improve the durability of metal sheets, coating technology came into being.

[0003] With the continuous advancement of industrialization, the demand for highly wear-resistant, corrosion-resistant and weather-resistant metal plate coatings is increasing. Such coatings can effectively protect metal surfaces from wear, corrosion and climate effects, extend the service life of metal products, reduce maintenance costs, and improve product quality and reliability. Therefore, researching and developing a high-performance metal plate coating has important practical significance and market prospects.

[0004] Chinese patent document CN117625040A discloses a low-carbon antibacterial and mildew-proof metal plate surface coating, a preparation method and a metal plate, comprising nano silver particles, nano zinc oxide, silicone resin, acrylate monomer, acrylate crosslinking agent, organic solvent and auxiliary agent; wherein the components are as follows in terms of mass percentage: nano silver particles: 1-5%; nano zinc oxide: 2-8%; silicone resin: 10-30%; acrylate monomer: 5-15%; acrylate crosslinking agent: 3-9%; organic solvent: 23-74%; auxiliary agent: 5-10%; the silicone resin is selected from ethylsilane or methylsilane; the acrylate crosslinking agent is specifically a multifunctional acrylate; the organic solvent is toluene or xylene; the auxiliary agent is a leveling agent, a defoaming agent or a stabilizer. Although the invention has good coating properties, durability and stability, the organic solvents toluene or xylene used in the invention are very harmful to the human body and the environment. In addition, during the actual use of the coating, due to the influence of the environment and stress damage, if these damages are not repaired in a timely and effective manner, they will provide a pathway for the corrosive medium to invade, and ultimately cause the coating to fail prematurely and gradually lose its protective ability, thereby greatly shortening the protective period of the coating. Summary of the invention

[0005] The main purpose of the invention is to provide a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating which is environmentally friendly and has excellent anti-corrosion performance.

[0006] To achieve the above-mentioned objectives, the present invention proposes a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating, and its preparation method comprises the following steps: cleaning and drying the surface of the metal plate substrate, and then evenly spraying the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating on the metal plate, and obtaining the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating after the coating is cured.

[0007] Preferably, the metal plate cleaning and drying process is to ultrasonically treat the metal plate substrate in water, anhydrous ethanol and acetone in sequence and then dry it to obtain a cleaned metal plate substrate.

[0008] Preferably, the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating comprises the following components, in parts by weight: 40-60 parts of acrylic emulsion, 10-15 parts of modified carbon nanotubes, 0.1-0.5 parts of dispersant, 0.1-0.3 parts of defoaming agent, 0.2-0.4 parts of antifreeze agent, 0.3-0.5 parts of film-forming aid, 0.1-0.3 parts of thickener, 5-10 parts of coated modified nano zirconium phosphate, and 80-100 parts of water.

[0009] Preferably, the method for preparing the modified carbon nanotubes comprises the following steps:

[0010] M1: Disperse carbon nanotubes in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, perform ultrasonic treatment for 20-40 minutes, then stir at 75-85°C for 3-5 hours, cool to room temperature, filter, wash with water until neutral, and dry to obtain pretreated carbon nanotubes;

[0011] M2: Mix 2-amino-4,6-dimethylpyrimidine and 1,6-hexamethylene diisocyanate and stir at 80-120°C for 5-10 minutes, add N-methylpyrrolidone and react for 10-15 hours; after the reaction is completed, add CH2Cl2 to fully dissolve the product, then add a mixed solution of n-heptane and isopropyl ether to produce precipitation, filter, collect the solid and dry to obtain a methyl amino ester intermediate;

[0012] M3: Dissolve the aminomethyl ester intermediate in chloroform, add polyetheramine and dibutyltin dilaurate, heat to 60-100°C, react for 6-8h under N2 protection, and after the reaction is completed, cool to room temperature and filter, and evaporate the filtrate to remove the solvent to obtain a flexible compound;

[0013] M4: Disperse the pretreated carbon nanotubes in N, N-dimethylformamide, add flexible compounds and dibutyltin laurate, adjust the pH value to 8-10, react at 80-100°C for 8-10h under N2 atmosphere, filter and collect the solids after the reaction is completed, wash and dry the solids to obtain modified carbon nanotubes.

[0014] Preferably, in the M2 step, the molar ratio of 2-amino-4,6-dimethylpyrimidine to hexamethylene diisocyanate is 1:1-1.5; and the volume ratio of n-heptane to isopropyl ether is 4-6:1.

[0015] Preferably, in the M3 step, the mass ratio of the aminomethyl ester intermediate to the polyetheramine is 1:15-20.

[0016] Preferably, in the M4 step, the mass ratio of the pretreated carbon nanotubes to the flexible compound is 6-10:1.

[0017] The invention can improve the mechanical strength and wear resistance of the coating by adding modified carbon nanotubes, and can also improve its dispersion in the matrix resin, thereby reducing the corrosion of the substrate by moisture and corrosive media; by grafting a flexible compound on the carbon nanotube, the flexible compound is obtained by condensing the amino group on 2-amino-4,6-dimethylpyrimidine with the cyanate group on 1,6-hexamethylene diisocyanate to obtain a methyl ester intermediate, and then the cyanate group on the methyl ester intermediate reacts with the amino group on the polyetheramine; the flexible compound can realize multi-site anchoring with the metal plate matrix, and can be cross-linked with the matrix resin, thereby enhancing the adhesion between the coating and the metal matrix, and providing the coating with a certain flexibility, thereby playing a toughening role.

[0018] Preferably, the dispersant is at least one of sodium polyacrylate, trisodium phosphate, alkylphenol polyoxyethylene ether, and sodium alkyl aryl sulfonate; the dispersant can stabilize the dispersion of solid ions such as carbon nanotubes and nano zirconium phosphate, avoid particle agglomeration, and improve the gloss and hiding power of the coating.

[0019] Preferably, the defoaming agent is at least one of a phosphate hydrophobic defoaming agent, polysiloxane, and an organic alcohol compound; the defoaming agent can effectively inhibit and destroy bubbles generated in the coating, thereby avoiding defects such as pores and pinholes on the coating surface, and is beneficial to increasing the surface tension of the coating, and improving the leveling and wettability of the coating.

[0020] Preferably, the antifreeze agent is tristyrylphenol polyoxyethylene ether; the antifreeze agent can lower the freezing point of the coating, prevent the coating from freezing and crystallizing in a low temperature environment, ensure the stability and workability of the coating in cold weather, and thus improve the weather resistance of the coating.

[0021] Preferably, the film-forming aid is at least one of polyvinyl alcohol, propylene glycol butyl ether, and propylene glycol methyl ether acetate; the film-forming aid can synergize with the acrylic emulsion to form a firm coating structure and improve the film-forming performance of the coating.

[0022] Preferably, the thickener is at least one of hydroxyethyl cellulose and methyl cellulose; the thickener can form a highly viscous solution in water, increase the viscosity of the coating, improve the overall suspension stability of the coating, and prevent the precipitation of solid particles.

[0023] Preferably, the preparation method of the coated modified nano zirconium phosphate is as follows:

[0024] Dissolve 3-aminopropyltriethoxysilane in an ethanol aqueous solution, add nano zirconium phosphate, react at 50-70°C for 2-4 hours, filter, and dry to obtain amino-coupled modified nano zirconium phosphate; adjust the pH value of the potato starch aqueous solution to 7.5-9.5 at 20-40°C, add hydroxypropyl guar gum, amino-coupled modified nano zirconium phosphate, and 1,3-malondialdehyde, mix well, react at 40-60°C for 2-4 hours, cool and filter, collect the solid to obtain the coated modified nano zirconium phosphate.

[0025] Preferably, the mass ratio of the 3-aminopropyltriethoxysilane to the nano zirconium phosphate is 1:3-5.

[0026] Preferably, the concentration of the potato starch aqueous solution is 8-15wt%; the dosage ratio of the potato starch aqueous solution, hydroxypropyl guar gum, amino-coupled modified nano zirconium phosphate, and 1,3-malondialdehyde is 50-60g:8-12g:3-5g:2-3mL.

[0027] The invention adds coated modified nano zirconium phosphate and coats the nano zirconium phosphate through complex microcapsules produced by hydroxypropyl guar gum and potato starch. When cracks appear in the coating and water molecules penetrate into it, the complex microcapsules coating the nano zirconium phosphate break, releasing the amino-coupled modified nano zirconium phosphate with anti-corrosion performance and forming a gel state. The released amino-coupled modified nano zirconium phosphate can be adsorbed on the metal surface through amino groups to prevent the corrosion of the metal, while the complex microcapsules fill the pores of the coating to achieve the effect of self-repairing of the coating.

[0028] Preferably, the preparation method of the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating comprises the following steps: weighing each raw material according to the formula, mixing the acrylic emulsion, modified carbon nanotubes, dispersant, defoaming agent, antifreeze agent, film-forming aid, thickener, coated modified nano zirconium phosphate and water, and stirring evenly to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

[0029] The present invention also provides a method for preparing the above-mentioned highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating, comprising the following steps: weighing each raw material according to the formula, mixing acrylic emulsion, modified carbon nanotubes, dispersant, defoaming agent, antifreeze agent, film-forming aid, thickener, coated modified nano zirconium phosphate and water, and stirring evenly to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

[0030] The present invention also discloses the application of the above-mentioned highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating, specifically, the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating is evenly coated on the metal plate for corrosion protection of the metal plate.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating prepared by the present invention does not contain volatile organic compounds such as benzene and toluene that are harmful to the environment, and has excellent adhesion and corrosion resistance. The present invention uses acrylic emulsion as a film-forming agent to give the coating good weather resistance, thereby improving the service life and quality of the coating. By adding modified carbon nanotubes, on the one hand, the mechanical strength and wear resistance of the coating can be improved, and on the other hand, its dispersion in the matrix resin can be improved, and the corrosion of the substrate by moisture and corrosive media can be reduced. It can achieve multi-site anchoring with the metal plate matrix and can be cross-linked with the matrix resin to enhance the adhesion of the coating to the metal matrix, and provide the coating with a certain degree of flexibility. By adding an antifreeze agent, the freezing point of the coating can be lowered, the coating can be prevented from freezing and crystallizing in a low-temperature environment, and the weather resistance of the coating can be improved. By adding coated modified nano zirconium phosphate, the coating can be given good self-repairing properties, so that the coating has a good anti-corrosion effect. DETAILED DESCRIPTION

[0033] To make the purpose, technical scheme and advantages of the embodiment of the present invention clearer, the technical scheme in the embodiment of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiment, it is carried out according to the normal conditions or the conditions recommended by the manufacturer. If the reagents or instruments used do not specify the manufacturer, they are all conventional products that can be purchased commercially. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes, taking "A and / or B" as an example, including scheme A, or scheme B, or schemes that A and B meet at the same time. In addition, the technical schemes between the various embodiments can be combined with each other, but must be based on the ability of ordinary technicians in the field to achieve. When the combination of technical solutions is contradictory or cannot be achieved, it should be considered that the combination of such technical solutions does not exist, and is not within the scope of protection required by the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present invention.

[0034] The sources of some raw materials used in the present invention are as follows:

[0035] Acrylic emulsion, model HBHK-1007, solid content 70%, purchased from Guangzhou Black Panther Waterproof Building Materials Co., Ltd.

[0036] Polyetheramine, model D230, oil absorption value is 43mL / 100g, density is 32kg / m3 , purchased from Jinan Linyan Mandy New Materials Co., Ltd.

[0037] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention, and are not used to limit the present invention.

[0038] Example 1

[0039] A method for preparing a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating comprises the following steps: mixing 500g of acrylic emulsion, 120g of modified carbon nanotubes, 3g of sodium polyacrylate, 2g of tributyl phosphate, 3g of tristyrylphenol polyoxyethylene ether, 4g of propylene glycol methyl ether acetate, 2g of hydroxyethyl cellulose, 80g of coated modified nano zirconium phosphate and 900g of water, and stirring the mixture to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

[0040] The method for preparing the modified carbon nanotubes comprises the following steps:

[0041] M1: 10 g of carbon nanotubes were dispersed in a mixed acid solution of 100 ml of concentrated sulfuric acid and 50 ml of concentrated nitric acid, and then ultrasonically treated for 30 min and stirred at 80 °C for 4 h, cooled to room temperature, filtered, washed with water until neutral, and dried to obtain pretreated carbon nanotubes;

[0042] M2: 2.8 g of 2-amino-4,6-dimethylpyrimidine and 25 g of 1,6-hexamethylene diisocyanate were mixed and stirred at 100°C for 8 min, 5 mL of N-methylpyrrolidone was added, and the reaction was carried out for 12 h. After the reaction was completed, 30 mL of CH2Cl2 was added to fully dissolve the product, and then a mixed solution consisting of 25 mL of n-heptane and 5 mL of isopropyl ether was added to produce a precipitate. The solid was collected by filtration and dried to obtain a methyl amino ester intermediate.

[0043] M3: Dissolve 2.5g of aminomethyl ester intermediate in chloroform, add 40g of polyetheramine and 5mL of dibutyltin dilaurate, heat to 60-100°C, react for 6-8h under N2 protection, and after the reaction is completed, cool to room temperature and filter, and evaporate the filtrate to remove the solvent to obtain a flexible compound;

[0044] M4: Disperse 2 g of pretreated carbon nanotubes in 100 mL of N,N-dimethylformamide, add 2.3 g of flexible compound and 5 mL of dibutyltin laurate, adjust the pH value to 9, react at 90 °C for 8 h under N2 atmosphere, and after the reaction is completed, filter and collect the solids, wash and dry the solids to obtain modified carbon nanotubes.

[0045] The preparation method of the coated modified nano zirconium phosphate is as follows:

[0046] 10 g of 3-aminopropyltriethoxysilane was dissolved in 200 mL of ethanol aqueous solution, 40 g of nano zirconium phosphate was added, the mixture was reacted at 60 ° C for 3 h, filtered, and dried to obtain amino-coupled modified nano zirconium phosphate; at 30 ° C, 53 g of 12 wt% potato starch aqueous solution was adjusted to pH 8, 9.8 g of hydroxypropyl guar gum, 4.5 g of amino-coupled modified nano zirconium phosphate, and 2 mL of 1,3-malondialdehyde were added, and after mixing evenly, the mixture was reacted at 50 ° C for 3 h, cooled and filtered, and the solid was collected to obtain coated modified nano zirconium phosphate.

[0047] Example 2

[0048] A method for preparing a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating comprises the following steps: mixing 400g of acrylic emulsion, 100g of modified carbon nanotubes, 1g of sodium polyacrylate, 1g of tributyl phosphate, 2g of tristyrylphenol polyoxyethylene ether, 3g of propylene glycol methyl ether acetate, 1g of hydroxyethyl cellulose, 50g of coated modified nano zirconium phosphate and 800g of water, and stirring the mixture to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

[0049] The method for preparing the modified carbon nanotubes comprises the following steps:

[0050] M1: 10 g of carbon nanotubes were dispersed in a mixed acid solution of 100 ml of concentrated sulfuric acid and 50 ml of concentrated nitric acid, and then ultrasonically treated for 20 min and stirred at 75 °C for 3 h, cooled to room temperature, filtered, washed with water until neutral, and dried to obtain pretreated carbon nanotubes;

[0051] M2: 2.3 g of 2-amino-4,6-dimethylpyrimidine and 22 g of 1,6-hexamethylene diisocyanate were mixed and stirred at 80°C for 5 min, 3 mL of N-methylpyrrolidone was added, and the reaction was carried out for 10 h. After the reaction was completed, 20 mL of CH2Cl2 was added to fully dissolve the product, and then a mixed solution consisting of 20 mL of n-heptane and 5 mL of isopropyl ether was added to produce a precipitate. The solid was collected by filtration and dried to obtain a methyl amino ester intermediate.

[0052] M3: Dissolve 3g of aminomethyl ester intermediate in chloroform, add 45g of polyetheramine and 5mL of dibutyltin dilaurate, heat to 60°C, react for 6h under N2 protection, and after the reaction is completed, cool to room temperature and filter. After evaporating the filtrate to remove the solvent, obtain a flexible compound;

[0053] M4: Disperse 2 g of pretreated carbon nanotubes in 100 mL of N,N-dimethylformamide, add 2.1 g of flexible compound and 5 mL of dibutyltin laurate, adjust the pH value to 8, react at 60 °C for 6 h under N2 atmosphere, and after the reaction is completed, filter and collect the solids, wash and dry the solids to obtain modified carbon nanotubes.

[0054] The preparation method of the coated modified nano zirconium phosphate is as follows:

[0055] 10 g of 3-aminopropyltriethoxysilane was dissolved in 200 mL of ethanol aqueous solution, 30 g of nano zirconium phosphate was added, the mixture was reacted at 50 °C for 2 h, filtered, and dried to obtain amino-coupled modified nano zirconium phosphate; at 20 °C, 50 g of 8 wt% potato starch aqueous solution was adjusted to pH 7.5, 8 g of hydroxypropyl guar gum, 3 g of amino-coupled modified nano zirconium phosphate, and 2 mL of 1,3-malondialdehyde were added, the mixture was mixed evenly, the mixture was reacted at 40 °C for 2 h, cooled and filtered, and the solid was collected to obtain coated modified nano zirconium phosphate.

[0056] Example 3

[0057] A method for preparing a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating comprises the following steps: mixing 600g of acrylic emulsion, 150g of modified carbon nanotubes, 5g of sodium polyacrylate, 3g of tributyl phosphate, 4g of tristyrylphenol polyoxyethylene ether, 5g of propylene glycol methyl ether acetate, 3g of hydroxyethyl cellulose, 100g of coated modified nano zirconium phosphate and 1000g of water, and stirring the mixture to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

[0058] The method for preparing the modified carbon nanotubes comprises the following steps:

[0059] M1: 10 g of carbon nanotubes were dispersed in a mixed acid solution of 100 ml of concentrated sulfuric acid and 50 ml of concentrated nitric acid, and then ultrasonically treated for 40 min and stirred at 85 °C for 5 h, cooled to room temperature, filtered, washed with water until neutral, and dried to obtain pretreated carbon nanotubes;

[0060] M2: 3.2 g of 2-amino-4,6-dimethylpyrimidine and 28 g of 1,6-hexamethylene diisocyanate were mixed and stirred at 120°C for 10 min, 5 mL of N-methylpyrrolidone was added, and the reaction was carried out for 15 h. After the reaction was completed, 30 mL of CH2Cl2 was added to fully dissolve the product, and then a mixed solution consisting of 30 mL of n-heptane and 5 mL of isopropyl ether was added to produce a precipitate. The solid was collected by filtration and dried to obtain a methyl amino ester intermediate.

[0061] M3: Dissolve 3g of aminomethyl ester intermediate in chloroform, add 50g of polyetheramine and 5mL of dibutyltin dilaurate, heat to 100°C, react for 8h under N2 protection, and after the reaction is completed, cool to room temperature and filter. After evaporating the filtrate to remove the solvent, obtain a flexible compound;

[0062] M4: Disperse 2.5 g of pretreated carbon nanotubes in 100 mL of N, N-dimethylformamide, add 2.8 g of flexible compound and 5 mL of dibutyltin laurate, adjust the pH value to 10, react at 100 °C for 10 h under N2 atmosphere, and after the reaction is completed, filter and collect the solids. The solids are washed and dried to obtain modified carbon nanotubes.

[0063] The preparation method of the coated modified nano zirconium phosphate is as follows:

[0064] 10 g of 3-aminopropyltriethoxysilane was dissolved in 200 mL of ethanol aqueous solution, 40 g of nano zirconium phosphate was added, the mixture was reacted at 60 ° C for 3 h, filtered, and dried to obtain amino-coupled modified nano zirconium phosphate; at 40 ° C, 53 g of 12 wt% potato starch aqueous solution was adjusted to a pH value of 9.5, 9.8 g of hydroxypropyl guar gum, 4.5 g of amino-coupled modified nano zirconium phosphate, and 2 mL of 1,3-malondialdehyde were added, and after mixing evenly, the mixture was reacted at 50 ° C for 34 h, cooled and filtered, and the solid was collected to obtain the coated modified nano zirconium phosphate.

[0065] Comparative Example 1

[0066] A method for preparing a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating is similar to Example 1, except that nano zirconium phosphate is added, and specifically comprises the following steps: 500g acrylic emulsion, 120g modified carbon nanotubes, 3g sodium polyacrylate, 2g tributyl phosphate, 3g tristyrylphenol polyoxyethylene ether, 4g propylene glycol methyl ether acetate, 2g hydroxyethyl cellulose, 80g nano zirconium phosphate and 900g water are mixed and stirred to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

[0067] The method for preparing the modified carbon nanotubes comprises the following steps:

[0068] M1: 10 g of carbon nanotubes were dispersed in a mixed acid solution of 100 ml of concentrated sulfuric acid and 50 ml of concentrated nitric acid, and then ultrasonically treated for 30 min and stirred at 80 °C for 4 h, cooled to room temperature, filtered, washed with water until neutral, and dried to obtain pretreated carbon nanotubes;

[0069] M2: 2.8 g of 2-amino-4,6-dimethylpyrimidine and 25 g of 1,6-hexamethylene diisocyanate were mixed and stirred at 100°C for 8 min, 5 mL of N-methylpyrrolidone was added, and the reaction was carried out for 12 h. After the reaction was completed, 30 mL of CH2Cl2 was added to fully dissolve the product, and then a mixed solution consisting of 25 mL of n-heptane and 5 mL of isopropyl ether was added to produce a precipitate. The solid was collected by filtration and dried to obtain a methyl amino ester intermediate.

[0070] M3: Dissolve 2.5g of aminomethyl ester intermediate in chloroform, add 40g of polyetheramine and 5mL of dibutyltin dilaurate, heat to 60-100°C, react for 6-8h under N2 protection, and after the reaction is completed, cool to room temperature and filter, and evaporate the filtrate to remove the solvent to obtain a flexible compound;

[0071] M4: Disperse 2 g of pretreated carbon nanotubes in 100 mL of N,N-dimethylformamide, add 2.3 g of flexible compound and 5 mL of dibutyltin laurate, adjust the pH value to 9, react at 90 °C for 8 h under N2 atmosphere, and after the reaction is completed, filter and collect the solids, wash and dry the solids to obtain modified carbon nanotubes.

[0072] Comparative Example 2

[0073] A method for preparing a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating is similar to Example 1, except that carbon nanotubes are added. The method specifically comprises the following steps: 500g acrylic emulsion, 120g carbon nanotubes, 3g sodium polyacrylate, 2g tributyl phosphate, 3g tristyrylphenol polyoxyethylene ether, 4g propylene glycol methyl ether acetate, 2g hydroxyethyl cellulose, 80g coated modified nano zirconium phosphate and 900g water are mixed and stirred evenly to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

[0074] The preparation method of the coated modified nano zirconium phosphate is as follows:

[0075] 10 g of 3-aminopropyltriethoxysilane was dissolved in 200 mL of ethanol aqueous solution, 40 g of nano zirconium phosphate was added, the mixture was reacted at 60 ° C for 3 h, filtered, and dried to obtain amino-coupled modified nano zirconium phosphate; at 30 ° C, 53 g of 12 wt% potato starch aqueous solution was adjusted to pH 8, 9.8 g of hydroxypropyl guar gum, 4.5 g of amino-coupled modified nano zirconium phosphate, and 2 mL of 1,3-malondialdehyde were added, and after mixing evenly, the mixture was reacted at 50 ° C for 3 h, cooled and filtered, and the solid was collected to obtain coated modified nano zirconium phosphate.

[0076] Test Case

[0077] The steel plate was ultrasonically treated in water, anhydrous ethanol and acetone for 20 minutes in sequence and then dried to obtain a clean steel plate; then the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating prepared in Examples 1-3 and Comparative Examples 1-2 was evenly sprayed on the surface of the steel plate (three steel plates were sprayed in each example or comparative example, and the test results were averaged), the spraying thickness was uniformly 200 μm, and the coating was cured at 25° C. for 7 days. The obtained coating was tested.

[0078] Wear resistance test: refer to GB / T 1768-2006 "Determination of wear resistance of paints and varnishes - Rotating rubber grinding wheel method"

[0079] Adhesion test: refer to GB / T 5210-2006 "Pull-off adhesion test for paints and varnishes"

[0080] Corrosion resistance test: refer to GB / T 31588.1-2015 "Determination of resistance of paints and varnishes to cyclic corrosion environments Part 1: Wet (salt spray) / dry / humidity"; the test results are shown in Table 1:

[0081] Table 1 Test results of high wear-resistant, corrosion-resistant and weather-resistant metal plate coating performance

[0082]

[0083] It can be seen from the experimental results in Table 1 that the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating prepared by the present invention has good wear resistance, adhesion and anti-corrosion effects.

[0084] The above are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the patent protection scope of the present invention.

Claims

1. A method for preparing a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating, characterized in that: The method comprises the following steps: cleaning and drying the surface of the metal plate substrate, and then uniformly spraying a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating on the metal plate, and obtaining the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating after the coating is cured; The metal plate cleaning and drying process is to sequentially subject the metal plate substrate to ultrasonic treatment in water, anhydrous ethanol and acetone and then dry it to obtain a clean metal plate substrate; The highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating comprises the following components, in parts by weight: 40-60 parts of acrylic emulsion, 10-15 parts of modified carbon nanotubes, 0.1-0.5 parts of dispersant, 0.1-0.3 parts of defoamer, 0.2-0.4 parts of antifreeze agent, 0.3-0.5 parts of film-forming aid, 0.1-0.3 parts of thickener, 5-10 parts of coated modified nano zirconium phosphate, and 80-100 parts of water; The method for preparing the modified carbon nanotubes comprises the following steps: M1: Disperse carbon nanotubes in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, perform ultrasonic treatment for 20-40 minutes, then stir at 75-85°C for 3-5 hours, cool to room temperature, filter, wash with water until neutral, and dry to obtain pretreated carbon nanotubes; M2: Mix 2-amino-4,6-dimethylpyrimidine and 1,6-hexamethylene diisocyanate and stir at 80-120°C for 5-10 minutes, add N-methylpyrrolidone and react for 10-15 hours; after the reaction is completed, add CH2Cl2 to fully dissolve the product, then add a mixed solution of n-heptane and isopropyl ether to produce precipitation, filter, collect the solid and dry to obtain a methyl amino ester intermediate; M3: Dissolve the aminomethyl ester intermediate in chloroform, add polyetheramine and dibutyltin dilaurate, heat to 60-100°C, react for 6-8h under N2 protection, and after the reaction is completed, cool to room temperature and filter, and evaporate the filtrate to remove the solvent to obtain a flexible compound; M4: Dispersing the pretreated carbon nanotubes in N, N-dimethylformamide, adding a flexible compound and dibutyltin laurate, adjusting the pH value to 8-10, reacting at 80-100°C for 8-10h under a N2 atmosphere, filtering after the reaction, collecting the solids, washing the solids and drying them to obtain modified carbon nanotubes; The preparation method of the coated modified nano zirconium phosphate is as follows: Dissolve 3-aminopropyltriethoxysilane in an ethanol aqueous solution, add nano zirconium phosphate, react at 50-70°C for 2-4 hours, filter, and dry to obtain amino-coupled modified nano zirconium phosphate; adjust the pH value of the potato starch aqueous solution to 7.5-9.5 at 20-40°C, add hydroxypropyl guar gum, amino-coupled modified nano zirconium phosphate, and 1,3-malondialdehyde, mix well, react at 40-60°C for 2-4 hours, cool and filter, collect the solid to obtain the coated modified nano zirconium phosphate.

2. The preparation method according to claim 1, characterized in that: In the M2 step, the molar ratio of 2-amino-4,6-dimethylpyrimidine to hexamethylene diisocyanate is 1:1-1.5; and the volume ratio of n-heptane to isopropyl ether is 4-6:

1.

3. The preparation method according to claim 1, characterized in that: The dispersant is at least one of sodium polyacrylate, trisodium phosphate, alkylphenol polyoxyethylene ether, and sodium alkyl aryl sulfonate.

4. The preparation method according to claim 1, characterized in that: The defoaming agent is at least one of a phosphate hydrophobic defoaming agent, polysiloxane, and an organic alcohol compound.

5. The preparation method according to claim 1, characterized in that: The preparation method of the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating comprises the following steps: weighing various raw materials according to a formula, mixing acrylic emulsion, modified carbon nanotubes, dispersant, defoaming agent, antifreeze agent, film-forming aid, thickener, coated modified nano zirconium phosphate and water, and stirring evenly to obtain the highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating.

6. An application of a coating prepared by the method for preparing a highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating according to claim 1, characterized in that: The highly wear-resistant, corrosion-resistant and weather-resistant metal plate coating is uniformly coated on the metal plate for corrosion protection of the metal plate.

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