High-wear-resistance water-based transparent acrylic acid coating for metal surface and preparation method

Abstract

The invention relates to the field of coatings, in particular to a high-wear-resistance water-based transparent acrylic coating for a metal surface and a preparation method of the high-wear-resistance water-based transparent acrylic coating, and aims at solving the problem that an existing water-based acrylic coating for the metal surface is poor in wear resistance. According to the preparation method, modified acrylic resin is used as a main raw material, good film-forming property and adhesive force are provided, meanwhile, the coating has excellent mechanical property, calcium sulfate whiskers and nano silicon dioxide are added to serve as composite modified filler, so that the coating has high hardness and high scraping resistance, the wear resistance of the coating is remarkably improved, and the service life of the coating is prolonged. After the fluorine-containing multi-epoxy-group porous organic framework is added, the wear resistance of the coating is further remarkably improved, the obtained coating is suitable for various metal products with high requirements for appearance and wear resistance and has a wide application prospect, the preparation method adopts a water-based system, the environment-friendly requirement is met, the process is simple and controllable, and the preparation method is suitable for industrial production. The method is suitable for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating, in particular to a high-wear-resistance water-based transparent acrylic coating for metal surface and a preparation method. BACKGROUND

[0002] With the increasingly stringent environmental regulations and the improvement of people's environmental awareness, water-based coatings gradually replace solvent-based coatings as the mainstream choice for metal surface protection due to their low volatile organic compound (VOC) content and small environmental pollution. Among them, water-based acrylic coatings are widely used in metal products with high appearance requirements due to their excellent transparency, weather resistance and decorative properties.

[0003] However, the conventional water-based acrylic coating has the problem of poor wear resistance, which is easily affected by mechanical actions such as friction and scratching in daily use, resulting in surface wear and scratches, and further affecting the appearance and performance of the metal product. Therefore, it is of great practical significance to develop a high-wear-resistance water-based transparent acrylic coating for metal surface and a preparation method. SUMMARY

[0004] In order to overcome the above technical problems, the purpose of the present application is to provide a high-wear-resistance water-based transparent acrylic coating for metal surface and a preparation method, which solves the problem of poor wear resistance of the existing water-based acrylic coating for metal surface.

[0005] The purpose of the present application can be achieved by the following technical solutions: In a first aspect, the present application provides a high-wear-resistance water-based transparent acrylic coating for metal surface, comprising the following components by weight: modified acrylic resin 50-60 parts, calcium sulfate whisker 1-5 parts, nano-silica 11-15 parts, fluorine-containing multi-polyoxy group porous organic framework 3-11 parts, propylene glycol methyl ether acetate 2-6 parts, defoaming agent 0.2-0.6 parts, dispersing agent 0.3-0.5 parts, leveling agent 0.1-0.3 parts, thickening agent 0.2-0.6 parts, antioxidant 1-3 parts, light stabilizer 0.6-0.8 parts, and deionized water 70-80 parts.

[0006] As a preferred embodiment of the present application, the modified acrylic resin is prepared by the following steps: Step a1: 3-amino-1-adamantanol, phenothiazine, triethylamine and dichloromethane were added into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a constant pressure dropping funnel, and then the flask was protected by nitrogen, and stirred at a temperature of 0-5℃ and a stirring speed of 200-300r / min for 15-20min, and then methacryloyl chloride was added drop by drop while stirring, and the dropping speed was controlled at 1-2 drops / s, and after the addition was completed, the reaction was continued at a temperature of 25-30℃ for 20-30h, and after the reaction was completed, the reaction product was vacuum filtered, and the filtrate was washed with hydrochloric acid solution, sodium hydroxide solution and saturated sodium chloride solution for 2-3 times, and then dried with anhydrous magnesium sulfate, and then vacuum filtered, and the filtrate was rotary evaporated to remove the solvent, and thus a hydroxyadamantane monomer was obtained; Step a2: the hydroxyadamantane monomer, vinyl carbazole, KH-570 silane coupling agent, methyl methacrylate, acrylic acid, butyl acrylate, azobisisobutyronitrile and toluene were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, and then the flask was protected by nitrogen, and stirred at a temperature of 20-25℃ and a stirring speed of 200-300r / min for 20-30min, and then the reaction was continued at a temperature of 70-80℃ for 20-30h, and after the reaction was completed, the reaction product was cooled to room temperature, and then poured into methanol, and then vacuum filtered, and the filter cake was washed with tetrahydrofuran for 2-3 times, and then placed in a vacuum drying oven, and dried at a temperature of 70-80℃ for 2-3h, and thus a modified acrylic resin was obtained.

[0007] As a preferred embodiment of the present application, the amount ratio of the 3-amino-1-adamantanol, phenothiazine, triethylamine, dichloromethane and methacryloyl chloride in step a1 is 10mmol:0.01-0.02g:14-16mmol:40-50mL:10mmol.

[0008] As a preferred embodiment of the present application, the mass fraction of the hydrochloric acid solution in step a1 is 8-10%, and the mass fraction of the sodium hydroxide solution is 10-15%.

[0009] As a preferred embodiment of the present application, the amount ratio of the hydroxyadamantane monomer, vinyl carbazole, KH-570 silane coupling agent, methyl methacrylate, acrylic acid, butyl acrylate, azobisisobutyronitrile and toluene in step a2 is 9-23g:15-20g:2-10g:45-55g:6-10g:11-13g:0.8-1.4g:80-90mL.

[0010] As a preferred embodiment of the present application, the fluorine-containing polyepoxy porous organic framework is prepared by the following steps: Step b1: Add trialdehyde phloroglucinol, 2,5-diaminotrifluorotoluene, 1,4-dioxane, mesitylene, and acetic acid solution to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 20-25℃ and 200-300 r / min for 20-30 min. Then raise the temperature to 110-120℃ and continue stirring for 20-30 h. After the reaction is complete, cool the reaction product to room temperature and then filter under vacuum. Wash the filter cake 2-3 times with tetrahydrofuran, dichloromethane, and methanol in sequence. Then place it in a vacuum drying oven and dry it at 80-90℃ for 2-3 h to obtain a fluorinated polyhydroxy porous organic framework. Step b2: Add the fluorinated polyhydroxy porous organic framework, epichlorohydrin, and benzyltriethylammonium chloride to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir the reaction at 20-25℃ and 200-300 r / min for 20-30 min. Then raise the temperature to 110-120℃ and continue stirring for 2-3 h. After that, lower the temperature to 50-60℃ and add sodium hydroxide solution to continue stirring for 5-6 h. After the reaction is complete, cool the reaction product to room temperature, then remove the solvent by rotary evaporation. Wash the product 3-5 times with distilled water and then place it in a vacuum drying oven at 80-90℃ for 3-4 h to obtain the fluorinated polyepoxy porous organic framework.

[0011] In a preferred embodiment of the present invention, the ratio of the amounts of trialdehyde phloroglucinol, 2,5-diaminotrifluorotoluene, 1,4-dioxane, mesitylene, and acetic acid solution in step b1 is 20 mmol: 30 mmol: 50-60 mL: 50-60 mL: 20-30 mL.

[0012] In a preferred embodiment of the present invention, the molar concentration of the acetic acid solution in step b1 is 2-3 mol / L.

[0013] In a preferred embodiment of the present invention, the ratio of the fluorinated polyhydroxy porous organic framework, epichlorohydrin, benzyltriethylammonium chloride and sodium hydroxide solution in step b2 is 5g:20-25g:0.03-0.05g:30-40mL.

[0014] In a preferred embodiment of the present invention, the sodium hydroxide solution in step b2 has a mass fraction of 40-50%.

[0015] Secondly, this application provides a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step 1: Weigh out the following components by weight: 50-60 parts modified acrylic resin, 1-5 parts calcium sulfate whiskers, 11-15 parts nano silica, 3-11 parts fluorinated polyepoxy porous organic framework, 2-6 parts propylene glycol methyl ether acetate, 0.2-0.6 parts defoamer, 0.3-0.5 parts dispersant, 0.1-0.3 parts leveling agent, 0.2-0.6 parts thickener, 1-3 parts antioxidant, 0.6-0.8 parts light stabilizer, and 70-80 parts deionized water. Set aside. Step 2: Add modified acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyepoxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer, and deionized water to a mixer and mix for 30-60 minutes at a temperature of 20-25℃ and a stirring speed of 1500-2500 r / min to obtain abrasion-resistant acrylic coating; Step 3: Apply the wear-resistant acrylic coating evenly to the surface of the metal substrate, control the wet film thickness to be 20-30μm, and then place it in a vacuum drying oven and dry it at a temperature of 80-90℃ for 30-40 minutes. Then raise the temperature to 110-120℃ and dry it for 1-2 hours to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

[0016] In a preferred embodiment of the present invention, the calcium sulfate whiskers have an average diameter of 5 μm and an average length of 60 μm.

[0017] In a preferred embodiment of the present invention, the average particle size of the nano-silica is 80 nm.

[0018] In a preferred embodiment of the present invention, the defoamer is NXZ defoamer.

[0019] In a preferred embodiment of the present invention, the dispersant is BYK-111 dispersant.

[0020] In a preferred embodiment of the present invention, the leveling agent is BYK-330 leveling agent.

[0021] In a preferred embodiment of the present invention, the thickener is sodium carboxymethyl cellulose.

[0022] In a preferred embodiment of the present invention, the antioxidant is antioxidant 1010.

[0023] In a preferred embodiment of the present invention, the light stabilizer is light stabilizer 944.

[0024] Compared with the prior art, the beneficial effects of the present invention are: This invention relates to a highly wear-resistant waterborne transparent acrylic coating for metal surfaces and its preparation method. The method involves mixing modified acrylic resin, calcium sulfate whiskers, nano-silica, a fluorinated polyepoxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer, and deionized water to obtain a wear-resistant acrylic coating. This wear-resistant acrylic coating is then uniformly coated onto the surface of a metal substrate, and after drying, a highly wear-resistant waterborne transparent acrylic coating for metal surfaces is obtained. This preparation method uses modified acrylic resin as the main raw material, providing good film-forming properties and adhesion. The addition of calcium sulfate whiskers and nano-silica as composite modified fillers achieves a good "whisker-particle" combination, resulting in high hardness, high scratch resistance, and significantly improved wear resistance. Furthermore, the addition of a fluorinated polyepoxy porous organic framework further enhances the wear resistance, making the resulting coating suitable for various metal products requiring high appearance and wear resistance, with broad application prospects. Moreover, this preparation method uses an aqueous system, meets environmental protection requirements, and is simple, controllable, and suitable for large-scale production.

[0025] In the preparation of a highly wear-resistant waterborne transparent acrylic coating for metal surfaces, a modified acrylic resin was first prepared. This was achieved through a reaction between 3-amino-1-adamantane alcohol and methacryloyl chloride. The amino group on 3-amino-1-adamantane alcohol reacts with the acyl chloride group on methacryloyl chloride to introduce an alkenyl group, yielding a hydroxyadamantane monomer. This monomer, along with vinylcarbazole, KH-570 silane coupling agent, methyl methacrylate, acrylic acid, and butyl acrylate, was then polymerized to form the modified acrylic resin. This modified acrylic resin contains highly rigid adamantane alcohol and carbazole structures, endowing it with excellent mechanical properties. Simultaneously, the hydroxyl groups in the adamantane alcohol structure can react with carboxyl and epoxy groups, increasing the degree of crosslinking in the acrylic resin and thus improving the wear resistance of the coating. Furthermore, it contains siloxane groups, which can be hydrolyzed and grafted onto the composite modified filler, improving the dispersion performance of the composite modified filler. This allows the composite modified filler to be distributed in the acrylic resin in the form of chemical bonds, fully utilizing the reinforcing effect of the composite modified filler.

[0026] In the process of preparing a highly wear-resistant waterborne transparent acrylic coating for metal surfaces, a fluorinated polyhydroxy porous organic framework was also prepared. This was achieved through the reaction of trialdehyde-based phloroglucinol with 2,5-diaminotrifluorotoluene. The aldehyde group on the trialdehyde-based phloroglucinol reacts with the amino group on the 2,5-diaminotrifluorotoluene to form a Schiff base structure. These reactants then undergo sequential cross-linking reactions to form a covalent organic framework, resulting in a fluorinated polyhydroxy porous organic framework. Further processing was performed using this fluorinated polyhydroxy porous organic framework and epichlorohydrin. The hydroxyl groups on the fluorinated polyhydroxy porous organic framework react with epichlorohydrin through a ring-opening and ring-closing reaction, thereby achieving… A large number of epoxy groups are introduced into the covalent organic framework to obtain a fluorinated polyepoxy porous organic framework. The fluorinated polyepoxy porous organic framework contains a large number of benzene rings, which endow it with excellent mechanical properties. At the same time, the porous nature gives it excellent buffering effect. Adding it to the coating can significantly improve its wear resistance. Moreover, the introduced fluorinated groups can achieve a lubricating effect, further improving its wear resistance. In addition, the large number of epoxy groups can react with the carboxyl and hydroxyl groups in the modified acrylic resin, further improving the crosslinking degree of the coating and significantly improving its ability to resist external impact and scratches. Attached Figure Description

[0027] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to the accompanying drawings.

[0028] Figure 1 This is a schematic diagram showing the wear resistance test results of the high wear-resistant water-based transparent acrylic coatings used on metal surfaces in Examples 1-3 and Comparative Examples 1-5 of the present invention. Detailed Implementation

[0029] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example 1:

[0030] This embodiment describes a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: 10 mmol of 3-amino-1-adamantanol, 0.01 g of phenothiazine, 14 mmol of triethylamine and 40 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and constant pressure dropping funnel. Nitrogen gas was introduced for protection, and the reaction was stirred at 0 °C and 200 r / min for 15 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 1 drop / s. After the addition was completed, the temperature was raised to 25 °C and the reaction was stirred for 20 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed twice with 8% hydrochloric acid solution, 10% sodium hydroxide solution and saturated sodium chloride solution, respectively. Then it was dried with anhydrous magnesium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain hydroxyadamantanane monomer. Step S2: 9g of hydroxyadamantane monomer, 15g of vinylcarbazole, 2g of KH-570 silane coupling agent, 45g of methyl methacrylate, 6g of acrylic acid, 11g of butyl acrylate, 0.8g of azobisisobutyronitrile, and 80mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 20℃ and 200r / min for 20min. Then, the mixture was heated to 70℃ and stirred for 20h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into methanol. The mixture was then vacuum filtered, and the filter cake was washed twice with tetrahydrofuran. The cake was then placed in a vacuum drying oven and dried at 70℃ for 2h to obtain the modified acrylic resin. Step S3: 20 mmol of trialdehyde phloroglucinol, 30 mmol of 2,5-diaminotrifluorotoluene, 50 mL of 1,4-dioxane, 50 mL of mesitylene, and 20 mL of acetic acid solution with a molar concentration of 2 mol / L were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 20 °C and a stirring rate of 200 r / min for 20 min. Then, the temperature was raised to 110 °C and the stirring was continued for 20 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed twice with tetrahydrofuran, dichloromethane, and methanol, respectively. Then, it was placed in a vacuum drying oven and dried at 80 °C for 2 h to obtain a fluorinated polyhydroxy porous organic framework. Step S4: Add 5g of fluorinated polyhydroxy porous organic framework, 20g of epichlorohydrin and 0.03g of benzyltriethylammonium chloride to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 20℃ and 200r / min for 20min. Then raise the temperature to 110℃ and continue stirring for 2h. Then lower the temperature to 50℃ and add 30mL of 40% sodium hydroxide solution and continue stirring for 5h. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, wash three times with distilled water, and then place it in a vacuum drying oven and dry at 80℃ for 3h to obtain fluorinated polyhydroxy porous organic framework. Step S5: Weigh out 50 parts by weight of modified acrylic resin, 1 part by weight of calcium sulfate whiskers, 11 parts by weight of nano-silica, 3 parts by weight of fluorinated polyepoxy porous organic framework, 2 parts by weight of propylene glycol methyl ether acetate, 0.2 parts by weight of defoamer, 0.3 parts by weight of dispersant, 0.1 parts by weight of leveling agent, 0.2 parts by weight of thickener, 1 part by weight of antioxidant, 0.6 parts by weight of light stabilizer, and 70 parts by weight of deionized water, and set aside for later use; the average diameter of the calcium sulfate whiskers is 5 μm and the average length is 60 μm; the average particle size of the nano-silica is 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; and the light stabilizer is light stabilizer 944. Step S6: Add modified acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyepoxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water to a mixer and mix for 30 minutes at a temperature of 20℃ and a stirring speed of 1500 r / min to obtain abrasion-resistant acrylic coating; Step S7: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 80℃ for 30min, then raise the temperature to 110℃ and dry for 1h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces. Example 2:

[0031] This embodiment describes a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: 10 mmol of 3-amino-1-adamantanol, 0.015 g of phenothiazine, 15 mmol of triethylamine and 45 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and constant pressure dropping funnel. Nitrogen gas was introduced for protection, and the reaction was stirred at 3 °C and 250 r / min for 18 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 1 drop / s. After the addition was completed, the temperature was raised to 28 °C and the reaction was stirred for 25 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed twice with 9% hydrochloric acid solution, 12% sodium hydroxide solution and saturated sodium chloride solution, respectively. Then it was dried with anhydrous magnesium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain hydroxyadamantanane monomer. Step S2: 16g of hydroxyadamantane monomer, 18g of vinylcarbazole, 6g of KH-570 silane coupling agent, 50g of methyl methacrylate, 8g of acrylic acid, 12g of butyl acrylate, 1.1g of azobisisobutyronitrile, and 85mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 22℃ and 250r / min for 25min. Then, the mixture was heated to 75℃ and stirred for 25h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into methanol. The mixture was then vacuum filtered, and the filter cake was washed twice with tetrahydrofuran. The filter cake was then placed in a vacuum drying oven and dried at 75℃ for 2.5h to obtain the modified acrylic resin. Step S3: 20 mmol of trialdehyde phloroglucinol, 30 mmol of 2,5-diaminotrifluorotoluene, 55 mL of 1,4-dioxane, 55 mL of mesitylene, and 25 mL of acetic acid solution with a molar concentration of 2.5 mol / L were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 22 °C and a stirring rate of 250 r / min for 25 min. Then, the temperature was raised to 115 °C and the stirring was continued for 25 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed twice with tetrahydrofuran, dichloromethane, and methanol, respectively. Then, it was placed in a vacuum drying oven and dried at 85 °C for 2.5 h to obtain a fluorinated polyhydroxy porous organic framework. Step S4: 5g of fluorinated polyhydroxy porous organic framework, 22g of epichlorohydrin and 0.04g of benzyltriethylammonium chloride were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 22℃ and 250r / min for 25min. Then the temperature was raised to 115℃ and the mixture was stirred for 2.5h. The temperature was then lowered to 55℃ and 35mL of 45% sodium hydroxide solution was added. The mixture was stirred for 5.5h. After the reaction was completed, the reaction product was cooled to room temperature. The solvent was then removed by rotary evaporation. The product was washed four times with distilled water and then placed in a vacuum drying oven and dried at 85℃ for 3.5h to obtain the fluorinated polyhydroxy porous organic framework. Step S5: Weigh out 55 parts by weight of modified acrylic resin, 3 parts by weight of calcium sulfate whiskers, 13 parts by weight of nano-silica, 7 parts by weight of fluorinated polyepoxy porous organic framework, 4 parts by weight of propylene glycol methyl ether acetate, 0.4 parts by weight of defoamer, 0.4 parts by weight of dispersant, 0.2 parts by weight of leveling agent, 0.4 parts by weight of thickener, 2 parts by weight of antioxidant, 0.7 parts by weight of light stabilizer, and 75 parts by weight of deionized water, and set aside for later use; the average diameter of the calcium sulfate whiskers is 5 μm and the average length is 60 μm; the average particle size of the nano-silica is 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; and the light stabilizer is light stabilizer 944. Step S6: Add modified acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyepoxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water to a mixer and mix for 45 minutes at a temperature of 22℃ and a stirring speed of 2000 r / min to obtain abrasion-resistant acrylic coating; Step S7: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 85℃ for 35min, then raise the temperature to 115℃ and dry for 1.5h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces. Example 3:

[0032] This embodiment describes a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: 10 mmol of 3-amino-1-adamantanol, 0.02 g of phenothiazine, 16 mmol of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube, and constant pressure dropping funnel. Nitrogen gas was introduced for protection, and the reaction was stirred at 5 °C and a stirring rate of 300 r / min for 20 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 2 drops / s. After the addition was completed, the temperature was raised to 30 °C and the reaction was stirred for 30 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed three times in succession with 10% hydrochloric acid solution, 15% sodium hydroxide solution, and saturated sodium chloride solution. Then, it was dried with anhydrous magnesium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain hydroxyadamantanane monomer. Step S2: 23g of hydroxyadamantane monomer, 20g of vinylcarbazole, 10g of KH-570 silane coupling agent, 55g of methyl methacrylate, 10g of acrylic acid, 13g of butyl acrylate, 1.4g of azobisisobutyronitrile, and 90mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25℃ and a stirring rate of 300r / min for 30min. Then, the mixture was heated to 80℃ and stirred for 30h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into methanol. The mixture was then vacuum filtered, and the filter cake was washed three times with tetrahydrofuran. The filter cake was then placed in a vacuum drying oven and dried at 80℃ for 3h to obtain the modified acrylic resin. Step S3: 20 mmol of trialdehyde phloroglucinol, 30 mmol of 2,5-diaminotrifluorotoluene, 60 mL of 1,4-dioxane, 60 mL of mesitylene, and 30 mL of acetic acid solution with a molar concentration of 3 mol / L were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and a stirring rate of 300 r / min for 30 min. Then, the temperature was raised to 120 °C and the mixture was stirred for another 30 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times in sequence with tetrahydrofuran, dichloromethane, and methanol. Then, it was placed in a vacuum drying oven and dried at 90 °C for 3 h to obtain a fluorinated polyhydroxy porous organic framework. Step S4: Add 5g of fluorinated polyhydroxy porous organic framework, 25g of epichlorohydrin and 0.05g of benzyltriethylammonium chloride to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 300r / min for 30min. Then raise the temperature to 120℃ and continue stirring for 3h. Then lower the temperature to 60℃ and add 40mL of 50% sodium hydroxide solution and continue stirring for 6h. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, wash with distilled water 5 times, and then place in a vacuum drying oven and dry at 90℃ for 4h to obtain fluorinated polyhydroxy porous organic framework. Step S5: Weigh out 60 parts by weight of modified acrylic resin, 5 parts by weight of calcium sulfate whiskers, 15 parts by weight of nano-silica, 11 parts by weight of fluorinated polyepoxy porous organic framework, 6 parts by weight of propylene glycol methyl ether acetate, 0.6 parts by weight of defoamer, 0.5 parts by weight of dispersant, 0.3 parts by weight of leveling agent, 0.6 parts by weight of thickener, 3 parts by weight of antioxidant, 0.8 parts by weight of light stabilizer, and 80 parts by weight of deionized water, and set aside for later use; the average diameter of the calcium sulfate whiskers is 5 μm and the average length is 60 μm; the average particle size of the nano-silica is 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; and the light stabilizer is light stabilizer 944. Step S6: Add modified acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyepoxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water to a mixer and mix for 60 minutes at a temperature of 25℃ and a stirring speed of 2500 r / min to obtain abrasion-resistant acrylic coating; Step S7: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 90℃ for 40min, then raise the temperature to 120℃ and dry for 2h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

[0033] Comparative Example 1: This comparative example illustrates a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: Add 55g methyl methacrylate, 10g acrylic acid, 13g butyl acrylate, 1.4g azobisisobutyronitrile and 90mL toluene to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 300r / min for 30min. Then raise the temperature to 80℃ and stir for 30h. After the reaction is complete, cool the reaction product to room temperature and pour it into methanol. Then filter under vacuum. Wash the filter cake three times with tetrahydrofuran and then place it in a vacuum drying oven and dry at 80℃ for 3h to obtain acrylic resin. Step S2: Weigh out 60 parts by weight of acrylic resin, 5 parts by weight of calcium sulfate whiskers, 15 parts by weight of nano-silica, 6 parts by weight of propylene glycol methyl ether acetate, 0.6 parts by weight of defoamer, 0.5 parts by weight of dispersant, 0.3 parts by weight of leveling agent, 0.6 parts by weight of thickener, 3 parts by weight of antioxidant, 0.8 parts by weight of light stabilizer, and 80 parts by weight of deionized water. The calcium sulfate whiskers have an average diameter of 5 μm and an average length of 60 μm. The nano-silica has an average particle size of 80 nm. The defoamer is NXZ defoamer. The dispersant is BYK-111 dispersant. The leveling agent is BYK-330 leveling agent. The thickener is sodium carboxymethyl cellulose. The antioxidant is antioxidant 1010. The light stabilizer is light stabilizer 944. Step S3: Add acrylic resin, calcium sulfate whiskers, nano silica, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water to a mixer and mix for 60 minutes at a temperature of 25°C and a stirring speed of 2500 r / min to obtain abrasion-resistant acrylic coating. Step S4: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 90℃ for 40min, then raise the temperature to 120℃ and dry for 2h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

[0034] Comparative Example 2: This comparative example illustrates a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: 10 mmol of 3-amino-1-adamantanol, 0.02 g of phenothiazine, 16 mmol of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube, and constant pressure dropping funnel. Nitrogen gas was introduced for protection, and the reaction was stirred at 5 °C and a stirring rate of 300 r / min for 20 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 2 drops / s. After the addition was completed, the temperature was raised to 30 °C and the reaction was stirred for 30 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed three times in succession with 10% hydrochloric acid solution, 15% sodium hydroxide solution, and saturated sodium chloride solution. Then, it was dried with anhydrous magnesium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain hydroxyadamantanane monomer. Step S2: 23g of hydroxyadamantane monomer, 20g of vinylcarbazole, 10g of KH-570 silane coupling agent, 55g of methyl methacrylate, 10g of acrylic acid, 13g of butyl acrylate, 1.4g of azobisisobutyronitrile, and 90mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25℃ and a stirring rate of 300r / min for 30min. Then, the mixture was heated to 80℃ and stirred for 30h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into methanol. The mixture was then vacuum filtered, and the filter cake was washed three times with tetrahydrofuran. The filter cake was then placed in a vacuum drying oven and dried at 80℃ for 3h to obtain the modified acrylic resin. Step S3: Weigh out 60 parts by weight of modified acrylic resin, 5 parts by weight of calcium sulfate whiskers, 15 parts by weight of nano-silica, 6 parts by weight of propylene glycol methyl ether acetate, 0.6 parts by weight of defoamer, 0.5 parts by weight of dispersant, 0.3 parts by weight of leveling agent, 0.6 parts by weight of thickener, 3 parts by weight of antioxidant, 0.8 parts by weight of light stabilizer, and 80 parts by weight of deionized water for later use; the average diameter of the calcium sulfate whiskers is 5 μm and the average length is 60 μm; the average particle size of the nano-silica is 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; and the light stabilizer is light stabilizer 944. Step S4: Add modified acrylic resin, calcium sulfate whiskers, nano silica, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water to a mixer and stir for 60 minutes at a temperature of 25℃ and a stirring speed of 2500r / min to obtain wear-resistant acrylic coating. Step S5: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 90℃ for 40min, then raise the temperature to 120℃ and dry for 2h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

[0035] Comparative Example 3: This comparative example illustrates a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: Add 55g methyl methacrylate, 10g acrylic acid, 13g butyl acrylate, 1.4g azobisisobutyronitrile and 90mL toluene to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 300r / min for 30min. Then raise the temperature to 80℃ and stir for 30h. After the reaction is complete, cool the reaction product to room temperature and pour it into methanol. Then filter under vacuum. Wash the filter cake three times with tetrahydrofuran and then place it in a vacuum drying oven and dry at 80℃ for 3h to obtain acrylic resin. Step S2: 20 mmol of trialdehyde phloroglucinol, 30 mmol of 2,5-diaminotrifluorotoluene, 60 mL of 1,4-dioxane, 60 mL of mesitylene, and 30 mL of acetic acid solution with a molar concentration of 3 mol / L were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and a stirring rate of 300 r / min for 30 min. Then, the temperature was raised to 120 °C and the mixture was stirred for another 30 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times in sequence with tetrahydrofuran, dichloromethane, and methanol. Then, it was placed in a vacuum drying oven and dried at 90 °C for 3 h to obtain a fluorinated polyhydroxy porous organic framework. Step S3: Weigh out 60 parts by weight of acrylic resin, 5 parts by weight of calcium sulfate whiskers, 15 parts by weight of nano-silica, 11 parts by weight of fluorinated polyhydroxy porous organic framework, 6 parts by weight of propylene glycol methyl ether acetate, 0.6 parts by weight of defoamer, 0.5 parts by weight of dispersant, 0.3 parts by weight of leveling agent, 0.6 parts by weight of thickener, 3 parts by weight of antioxidant, 0.8 parts by weight of light stabilizer, and 80 parts by weight of deionized water. The calcium sulfate whiskers have an average diameter of 5 μm and an average length of 60 μm; the nano-silica has an average particle size of 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; and the light stabilizer is light stabilizer 944. Step S4: Add acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyhydroxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water to a mixer and mix for 60 minutes at a temperature of 25℃ and a stirring speed of 2500 r / min to obtain abrasion-resistant acrylic coating; Step S5: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 90℃ for 40min, then raise the temperature to 120℃ and dry for 2h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

[0036] Comparative Example 4: This comparative example illustrates a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: Add 55g methyl methacrylate, 10g acrylic acid, 13g butyl acrylate, 1.4g azobisisobutyronitrile and 90mL toluene to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 300r / min for 30min. Then raise the temperature to 80℃ and stir for 30h. After the reaction is complete, cool the reaction product to room temperature and pour it into methanol. Then filter under vacuum. Wash the filter cake three times with tetrahydrofuran and then place it in a vacuum drying oven and dry at 80℃ for 3h to obtain acrylic resin. Step S2: 20 mmol of trialdehyde phloroglucinol, 30 mmol of 2,5-diaminotrifluorotoluene, 60 mL of 1,4-dioxane, 60 mL of mesitylene, and 30 mL of acetic acid solution with a molar concentration of 3 mol / L were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and a stirring rate of 300 r / min for 30 min. Then, the temperature was raised to 120 °C and the mixture was stirred for another 30 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times in sequence with tetrahydrofuran, dichloromethane, and methanol. Then, it was placed in a vacuum drying oven and dried at 90 °C for 3 h to obtain a fluorinated polyhydroxy porous organic framework. Step S3: Add 5g of fluorinated polyhydroxy porous organic framework, 25g of epichlorohydrin and 0.05g of benzyltriethylammonium chloride to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and 300r / min for 30min. Then raise the temperature to 120℃ and continue stirring for 3h. Then lower the temperature to 60℃ and add 40mL of 50% sodium hydroxide solution and continue stirring for 6h. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, wash with distilled water 5 times, and then place in a vacuum drying oven and dry at 90℃ for 4h to obtain fluorinated polyhydroxy porous organic framework. Step S4: Weigh out 60 parts by weight of acrylic resin, 5 parts by weight of calcium sulfate whiskers, 15 parts by weight of nano-silica, 11 parts by weight of fluorinated polyepoxy porous organic framework, 6 parts by weight of propylene glycol methyl ether acetate, 0.6 parts by weight of defoamer, 0.5 parts by weight of dispersant, 0.3 parts by weight of leveling agent, 0.6 parts by weight of thickener, 3 parts by weight of antioxidant, 0.8 parts by weight of light stabilizer, and 80 parts by weight of deionized water. The calcium sulfate whiskers have an average diameter of 5 μm and an average length of 60 μm; the nano-silica has an average particle size of 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; and the light stabilizer is light stabilizer 944. Step S5: Add acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyepoxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water into a mixer, and stir and mix for 60 minutes at a temperature of 25℃ and a stirring speed of 2500r / min to obtain abrasion-resistant acrylic coating; Step S6: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 90℃ for 40min, then raise the temperature to 120℃ and dry for 2h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

[0037] Comparative Example 5: This comparative example illustrates a method for preparing a highly wear-resistant water-based transparent acrylic coating for metal surfaces, comprising the following steps: Step S1: 10 mmol of 3-amino-1-adamantanol, 0.02 g of phenothiazine, 16 mmol of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube, and constant pressure dropping funnel. Nitrogen gas was introduced for protection, and the reaction was stirred at 5 °C and a stirring rate of 300 r / min for 20 min. Then, 10 mmol of methacryloyl chloride was added dropwise while stirring, with the dropping rate controlled at 2 drops / s. After the addition was completed, the temperature was raised to 30 °C and the reaction was stirred for 30 h. After the reaction was completed, the reaction product was vacuum filtered. The filtrate was washed three times in succession with 10% hydrochloric acid solution, 15% sodium hydroxide solution, and saturated sodium chloride solution. Then, it was dried with anhydrous magnesium sulfate, vacuum filtered, and the solvent was removed by rotary evaporation to obtain hydroxyadamantanane monomer. Step S2: 23g of hydroxyadamantane monomer, 20g of vinylcarbazole, 10g of KH-570 silane coupling agent, 55g of methyl methacrylate, 10g of acrylic acid, 13g of butyl acrylate, 1.4g of azobisisobutyronitrile, and 90mL of toluene were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25℃ and a stirring rate of 300r / min for 30min. Then, the mixture was heated to 80℃ and stirred for 30h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into methanol. The mixture was then vacuum filtered, and the filter cake was washed three times with tetrahydrofuran. The filter cake was then placed in a vacuum drying oven and dried at 80℃ for 3h to obtain the modified acrylic resin. Step S3: 20 mmol of trialdehyde phloroglucinol, 30 mmol of 2,5-diaminotrifluorotoluene, 60 mL of 1,4-dioxane, 60 mL of mesitylene, and 30 mL of acetic acid solution with a molar concentration of 3 mol / L were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25 °C and a stirring rate of 300 r / min for 30 min. Then, the temperature was raised to 120 °C and the mixture was stirred for another 30 h. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times in sequence with tetrahydrofuran, dichloromethane, and methanol. Then, it was placed in a vacuum drying oven and dried at 90 °C for 3 h to obtain a fluorinated polyhydroxy porous organic framework. Step S4: Weigh out 60 parts by weight of modified acrylic resin, 5 parts by weight of calcium sulfate whiskers, 15 parts by weight of nano-silica, 11 parts by weight of fluorinated polyhydroxy porous organic framework, 6 parts by weight of propylene glycol methyl ether acetate, 0.6 parts by weight of defoamer, 0.5 parts by weight of dispersant, 0.3 parts by weight of leveling agent, 0.6 parts by weight of thickener, 3 parts by weight of antioxidant, 0.8 parts by weight of light stabilizer, and 80 parts by weight of deionized water for later use; the average diameter of the calcium sulfate whiskers is 5 μm and the average length is 60 μm; the average particle size of the nano-silica is 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; and the light stabilizer is light stabilizer 944. Step S5: Add modified acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyhydroxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer and deionized water into a mixer, and stir and mix for 60 min at a temperature of 25℃ and a stirring speed of 2500 r / min to obtain wear-resistant acrylic coating; Step S6: Apply the wear-resistant acrylic coating evenly to the tinplate surface, control the wet film thickness to 25μm, then place it in a vacuum drying oven and dry at 90℃ for 40min, then raise the temperature to 120℃ and dry for 2h to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

[0038] Examples 1-3 and Comparative Examples 1-5, applied to high abrasion-resistant water-based transparent acrylic coatings on metal surfaces, were tested using a Taber abrasion tester with a CS-10 grinding wheel and a 1kg load to measure abrasion loss. The test results are as follows: Figure 1 As shown.

[0039] Please see Figure 1As shown, based on the data from Examples 1-3, it can be seen that the coating of this application has excellent wear resistance. Specifically, a comparison between Example 3 and Comparative Example 1 demonstrates that adding hydroxyadamantane monomer, vinylcarbazole, and KH-570 silane coupling agent as polymerization monomers, and adding a fluorinated polyepoxy porous organic framework, can significantly improve the wear resistance of the coating. A comparison between Example 3 and Comparative Example 2 demonstrates that adding a fluorinated polyepoxy porous organic framework can significantly improve the wear resistance of the coating. The comparison between Example 3 and Comparative Example 3... The comparison between Example 3 and Comparative Example 4 shows that adding hydroxyadamantane monomer, vinylcarbazole, and KH-570 silane coupling agent as polymerization monomers and introducing epoxy groups into the porous organic framework can significantly improve the wear resistance of the coating. The comparison between Example 3 and Comparative Example 5 shows that introducing epoxy groups into the porous organic framework can significantly improve the wear resistance of the coating.

[0040] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0041] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A high-wear-resistant water-based transparent acrylic coating for metal surfaces, characterized in that, Includes the following components by weight: The composition includes 50-60 parts modified acrylic resin, 1-5 parts calcium sulfate whiskers, 11-15 parts nano silica, 3-11 parts fluorinated polyepoxy porous organic framework, 2-6 parts propylene glycol methyl ether acetate, 0.2-0.6 parts defoamer, 0.3-0.5 parts dispersant, 0.1-0.3 parts leveling agent, 0.2-0.6 parts thickener, 1-3 parts antioxidant, 0.6-0.8 parts light stabilizer, and 70-80 parts deionized water. The modified acrylic resin is prepared by the following steps: Step a1: 3-amino-1-adamantanol, phenothiazine, triethylamine and dichloromethane were stirred and reacted. Then, methacryloyl chloride was added dropwise and the reaction was continued with stirring. After the reaction was completed, the reaction product was filtered under vacuum. The filtrate was washed successively with hydrochloric acid solution, sodium hydroxide solution and saturated sodium chloride solution. Then it was dried and rotary evaporated to obtain hydroxyadamantan monomer. Step a2: Hydroxyadamantane monomer, vinylcarbazole, KH-570 silane coupling agent, methyl methacrylate, acrylic acid, butyl acrylate, azobisisobutyronitrile and toluene were stirred and reacted. After the reaction was completed, the reaction product was cooled and then poured into methanol. After vacuum filtration, the filter cake was washed with tetrahydrofuran and then dried to obtain modified acrylic resin.

2. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 1, characterized in that, The ratio of 3-amino-1-adamantanol, phenothiazine, triethylamine, dichloromethane, and methacryloyl chloride used in step a1 is 10 mmol: 0.01-0.02 g: 14-16 mmol: 40-50 mL: 10 mmol.

3. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 1, characterized in that, The hydrochloric acid solution in step a1 has a mass fraction of 8-10%; the sodium hydroxide solution has a mass fraction of 10-15%.

4. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 1, characterized in that, The ratio of the amounts of hydroxyadamantane monomer, vinylcarbazole, KH-570 silane coupling agent, methyl methacrylate, acrylic acid, butyl acrylate, azobisisobutyronitrile, and toluene in step a2 is 9-23g: 15-20g: 2-10g: 45-55g: 6-10g: 11-13g: 0.8-1.4g: 80-90mL.

5. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 1, characterized in that, The fluorinated polyepoxy porous organic framework was prepared by the following steps: Step b1: Trialdehyde resorcinol, 2,5-diaminotrifluorotoluene, 1,4-dioxane, mesitylene and acetic acid solution were stirred and reacted. After the reaction was completed, the reaction product was cooled and then filtered under vacuum. The filter cake was washed with tetrahydrofuran, dichloromethane and methanol in sequence and then dried to obtain a fluorinated polyhydroxy porous organic framework. Step b2: The fluorinated polyhydroxy porous organic framework, epichlorohydrin and benzyltriethylammonium chloride were stirred and reacted. Then sodium hydroxide solution was added and the reaction was continued with stirring. After the reaction was completed, the reaction product was cooled, then evaporated by rotary evaporation, then washed with distilled water and then dried to obtain the fluorinated polyepoxy porous organic framework.

6. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 5, characterized in that, The ratio of the amounts of trialdehyde phloroglucinol, 2,5-diaminotrifluorotoluene, 1,4-dioxane, mesitylene, and acetic acid solution used in step b1 is 20 mmol: 30 mmol: 50-60 mL: 50-60 mL: 20-30 mL.

7. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 5, characterized in that, The molar concentration of the acetic acid solution in step b1 is 2-3 mol / L.

8. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 5, characterized in that, In step b2, the ratio of the fluorinated polyhydroxy porous organic framework, epichlorohydrin, benzyltriethylammonium chloride, and sodium hydroxide solution is 5g: 20-25g: 0.03-0.05g: 30-40mL.

9. The high-wear-resistant water-based transparent acrylic coating for metal surfaces according to claim 5, characterized in that, The sodium hydroxide solution in step b2 has a mass fraction of 40-50%.

10. A method for preparing a high-wear-resistant water-based transparent acrylic coating for metal surfaces as described in any one of claims 1-9, characterized in that, Includes the following steps: Step 1: Weigh out the following components according to weight: 50-60 parts modified acrylic resin, 1-5 parts calcium sulfate whiskers, 11-15 parts nano silica, 3-11 parts fluorinated polyepoxy porous organic framework, 2-6 parts propylene glycol methyl ether acetate, 0.2-0.6 parts defoamer, 0.3-0.5 parts dispersant, 0.1-0.3 parts leveling agent, 0.2-0.6 parts thickener, 1-3 parts antioxidant, 0.6-0.8 parts light stabilizer, and... 70-80 parts deionized water, for later use; the average diameter of the calcium sulfate whiskers is 5 μm and the average length is 60 μm; the average particle size of the nano-silica is 80 nm; the defoamer is NXZ defoamer; the dispersant is BYK-111 dispersant; the leveling agent is BYK-330 leveling agent; the thickener is sodium carboxymethyl cellulose; the antioxidant is antioxidant 1010; the light stabilizer is light stabilizer 944. Step 2: Add modified acrylic resin, calcium sulfate whiskers, nano silica, fluorinated polyepoxy porous organic framework, propylene glycol methyl ether acetate, defoamer, dispersant, leveling agent, thickener, antioxidant, light stabilizer, and deionized water to a mixer and mix for 30-60 minutes at a temperature of 20-25℃ and a stirring speed of 1500-2500 r / min to obtain abrasion-resistant acrylic coating; Step 3: Apply the wear-resistant acrylic coating evenly to the surface of the metal substrate, control the wet film thickness to be 20-30μm, and then place it in a vacuum drying oven and dry it at a temperature of 80-90℃ for 30-40 minutes. Then raise the temperature to 110-120℃ and dry it for 1-2 hours to obtain a high wear-resistant water-based transparent acrylic coating for metal surfaces.

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