Water-based anticorrosive paint and preparation method thereof

Abstract

The invention discloses a water-based anticorrosive paint, which is prepared from the following raw materials in parts by weight: 30 to 50 parts of bisphenol A type epoxy acrylic resin, 50 to 70 parts of water, 0.1 to 0.5 part of trialkyl melamine, 0.1 to 0.5 part of laurinol, 5 to 10 parts of calcium carbonate, 5 to 10 parts of reinforcing filler, 0.2 to 0.8 part of anticorrosive filler and 0.1 to 0.5 part of benzophenone. The anti-corrosion filler enables the coating to be more compact, adsorption of the coating on metal is firmer through electrostatic adsorption and chemical adsorption, the adsorption effect inhibits electrode reaction, corrosion current is reduced, the anti-corrosion performance of the coating is improved, and the lamellar graphene structure forms an isolation layer in the coating to block corrosion factors. The quinoline structure of the reinforcing filler can form a hydrophobic layer on the surface of metal to play a shielding role so as to inhibit migration of a corrosive medium, and N atoms contained in the reinforcing filler can generate adsorption with the surface of the metal through coordination combination, so that the corrosion inhibition performance of the reinforcing filler is improved.

Description

Technical Field

[0001] The present invention relates to the field of coating preparation, and particularly to a preparation method of a waterborne anti-corrosion coating. Background Art

[0002] Anti-corrosion coatings are an important industrial material, widely used for protecting equipment and facilities in various environments. With the development of industry and the improvement of environmental protection requirements, the demand and requirements for anti-corrosion coatings are also getting higher and higher. Traditional anti-corrosion coatings mainly rely on heavy metal components to provide anti-corrosion performance, but these elements pose certain hazards to the environment and human health. Therefore, the development of new and environmentally friendly anti-corrosion coatings has become a current research hotspot. Existing anti-corrosion coatings mainly include silicone anti-corrosion coatings, epoxy resin anti-corrosion coatings, polyurethane anti-corrosion coatings, etc. The anti-corrosion performance of these anti-corrosion coatings is poor. During use, the coating is corroded, resulting in the exposure of the protected substrate and causing economic losses. Therefore, it is very necessary to provide a corrosion-resistant coating.

[0003] In addition, a large amount of organic solvents are required in the preparation process of these anti-corrosion coatings, which not only pollutes the environment but also harms human health. Therefore, the developed coatings need to be water-soluble to reduce the use of organic solvents. Summary of the Invention

[0004] The purpose of the present invention is to provide a waterborne anti-corrosion coating, which solves the problem of poor anti-corrosion effect of current coatings.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A preparation method of a waterborne anti-corrosion coating specifically includes the following steps: Weigh the following raw materials in parts by weight: 30 - 50 parts of bisphenol A epoxy acrylate resin, 50 - 70 parts of water, 0.1 - 0.5 part of trialkyl melamine, 0.1 - 0.5 part of lauryl alcohol, 5 - 10 parts of calcium carbonate, 5 - 10 parts of reinforcing filler, 0.2 - 0.8 part of anti-corrosion filler, and 0.1 - 0.5 part of benzophenone. Mix the raw materials evenly, and under the condition of a rotation speed of 200 - 220 rpm, stir for 10 - 12 h and then stand for 3 - 5 h to obtain the waterborne anti-corrosion coating.

[0006] The viscosity of the bisphenol A epoxy acrylate resin is 4000 - 7000 (cps / 60 °C), the acid value ≤ 3 (mg KOH / g), the functionality is 2 - 3, the refractive index (25 °C) is 1.528 ± 0.005, the density is 1.15 ± 0.02 (g / ml), and the mesh number of calcium carbonate is 200 mesh.

[0007] Furthermore, the anti-corrosion filler is prepared by the following steps: Step A1: Mix sym - tetrachloroethane, 4,4'-bipyridine and acetone evenly. Under the conditions of a rotation speed of 100 - 120 rpm and a temperature of 70 - 80 °C, react for 10 - 12 h to obtain Intermediate 1. Mix Intermediate 1, deionized water and absolute ethanol evenly. Under the conditions of a rotation speed of 100 - 120 rpm, a temperature of 40 - 50 °C and a pH value of 10 - 12, react for 2 - 3 h to obtain Intermediate 2; Step A2: Disperse graphene oxide in deionized water, add KH580 and absolute ethanol. Under the conditions of a rotation speed of 120 - 150 rpm and a temperature of 50 - 60 °C, react for 3 - 5 h to obtain modified graphene. Mix modified graphene, Intermediate 2, toluene and p - toluenesulfonic acid evenly. Under the conditions of a rotation speed of 90 - 110 rpm and a temperature of 70 - 80 °C, react for 6 - 8 h to obtain the anticorrosive filler.

[0008] Furthermore, the dosage ratio of the sym - tetrachloroethane, 4,4'-bipyridine and acetone described in Step A1 is 1 g: 0.9 g: 20 mL, and the dosage ratio of Intermediate 1, deionized water and absolute ethanol is 1 g: 20 mL: 10 mL.

[0009] Furthermore, the dosage ratio of the graphene oxide, deionized water, KH580 and absolute ethanol described in Step A2 is 1 g: 30 mL: 5 mL: 20 mL, the dosage ratio of the modified graphene, Intermediate 2 and toluene is 1 g: 1.2 g: 20 mL, and the dosage of p - toluenesulfonic acid is 2% of the mass of Intermediate 2.

[0010] Furthermore, the reinforcing filler is prepared by the following steps: Step B1: Mix 6 - iodoquinoline, magnesium chips and diethyl ether evenly. Under the conditions of a rotation speed of 100 - 120 rpm, a temperature of 37 - 47 °C and nitrogen protection, react for 1 - 2 h to obtain Intermediate 3. Mix Intermediate 3, titanium tetrachloride and diethyl ether evenly. Under the conditions of a rotation speed of 80 - 100 rpm, a temperature of 2 - 10 °C and nitrogen protection, react for 3 - 5 h, then raise the temperature to 25 - 35 °C and continue to react for 9 - 12 h to obtain Intermediate 4; Step B2: Mix Intermediate 4, deionized water and absolute ethanol evenly. Under the conditions of a rotation speed of 100 - 120 rpm and a temperature of 40 - 50 °C, react for 0.5 - 1 h. Transfer the solution to a reaction kettle and react at a temperature of 120 - 140 °C for 24 - 28 h to obtain mesoporous titanium dioxide; Step B3: Disperse zinc oxide into deionized water, add γ-chloropropyltriethoxysilane and absolute ethanol, and react for 2 - 3 h under the conditions of a rotation speed of 70 - 90 rpm and a temperature of 50 - 60 °C to obtain modified zinc oxide. Mix the modified zinc oxide, mesoporous titanium dioxide, and dimethylformamide evenly, and react for 3 - 5 h under the conditions of a rotation speed of 200 - 220 rpm and a temperature of 70 - 80 °C to obtain the reinforcing filler.

[0011] Furthermore, the dosage ratio of 6-iodoquinoline, magnesium chips, and diethyl ether in Step B1 is 1 g : 1.2 g : 20 mL, and the dosage ratio of intermediate 3, titanium tetrachloride, and diethyl ether is 1 g : 5 mL : 15 mL.

[0012] Furthermore, the dosage ratio of intermediate 4, deionized water, and absolute ethanol in Step B2 is 1 g : 20 mL : 10 mL.

[0013] Furthermore, the dosage ratio of zinc oxide, deionized water, γ-chloropropyltriethoxysilane, and absolute ethanol in Step B3 is 1 g : 30 mL : 5 mL : 20 mL, and the dosage ratio of modified zinc oxide, mesoporous titanium dioxide, and dimethylformamide is 1 g : 0.8 g : 18 mL.

[0014] The beneficial effects of the present invention: The present invention discloses a waterborne anti-corrosion coating, which specifically includes the following component raw materials: 30 - 50 parts of bisphenol A epoxy acrylate resin, 50 - 70 parts of water, 0.1 - 0.5 part of trialkyl melamine, 0.1 - 0.5 part of lauryl alcohol, 5 - 10 parts of calcium carbonate, 5 - 10 parts of reinforcing filler, 0.2 - 0.8 part of anti-corrosion filler, and 0.1 - 0.5 part of benzophenone.

[0015] The anti-corrosion filler uses 1,1,2,2-tetrachloroethane and 4,4'-bipyridine as raw materials. The chlorine atom of the excessive tetrachloroethane undergoes a Menshutkin reaction with the nitrogen atom of 4,4'-bipyridine to obtain a hyperbranched intermediate 1 with a chlorine atom end. Under the action of water and ethanol, the chlorine atom of intermediate 1 undergoes hydrolysis to generate a hydroxyl group, obtaining intermediate 2. Graphene oxide is surface thiolated under the action of KH550 to obtain modified graphene. The carboxyl group of the modified graphene and the hydroxyl group of intermediate 2 undergo an esterification reaction under the action of p-toluenesulfonic acid to obtain the anti-corrosion filler.

[0016] The reinforcing filler uses 6-iodoquinoline and magnesium chips as raw materials. 6-iodoquinoline and magnesium chips react to generate quinoline-MgI to obtain intermediate 3. One chlorine atom of the -MgI of intermediate 3 undergoes a nucleophilic substitution reaction with titanium tetrachloride to obtain intermediate 4. Intermediate 4 undergoes a hydrolysis reaction to obtain mesoporous titanium dioxide. Zinc oxide is treated with γ-chloropropyltriethoxysilane to make the surface of zinc oxide carry halogen atoms to obtain modified zinc oxide. The modified zinc oxide and mesoporous titanium dioxide then undergo a Menshutkin reaction to obtain the reinforcing filler.

[0017] The waterborne anticorrosive coating disclosed by the present invention has an anticorrosive filler which is a hyperbranched pyridinium quaternary salt polymer based on 4,4'-bipyridine. By changing the activation energy of the electrode reaction through the adsorption effect, the corrosion rate is slowed down. In an acidic corrosive medium, quaternary ammonium cations and inorganic chloride ions are dissociated. The quaternary ammonium cations contain hydrophobic groups and hydrophilic groups, making the cations have a strong surface activity effect and being prone to physical adsorption on the steel surface. The quaternary ammonium cations are also adsorbed on the steel surface through electrostatic attraction. In addition, the quaternary ammonium ions contain a benzene ring structure and can form a coordination bond with iron atoms on the steel to form chemical adsorption. These adsorption effects greatly inhibit the anodic reaction and reduce the corrosion current; the hydrophobic groups of the quaternary ammonium cations can form a hydrophobic film covering the surface, preventing the movement of related substances and charges, and at the same time inhibiting the anodic and cathodic reactions. The quaternary ammonium cations are adsorbed on the steel surface to form a shielding positive electric field, hindering the corrosion factors from reaching the metal surface and hindering the discharge of hydrogen ions on the metal surface, inhibiting the cathodic process. The hyperbranched compound itself has good fluidity and is easy to form a film. The two-dimensional sheet structure of graphene can form an isolation layer in the coating to isolate the corrosion factors. Under the condition of light, the thiol group in the anticorrosive filler and the double bonds at both ends of the bisphenol A type epoxy acrylate resin undergo a click reaction. After the coating is photocured and crosslinked, the density and strength of the coating increase. The high density makes it difficult for corrosion factors to invade, further increasing the anticorrosive performance of the coating.

[0018] The reinforcing filler has a quinoline-functionalized mesoporous titanium dioxide as the core, and zinc oxide, a corrosion-resistant component, is incorporated with the N atom of quinoline as the reaction point. The mesoporous structure of titanium dioxide can absorb corrosion factors and prevent the progress of the corrosion reaction. Zinc oxide and titanium dioxide can cooperate with each other to generate a dense zinc-titanium compound, further reducing the invasion of corrosion factors. The quinoline structure can form a hydrophobic layer on the surface of the metal, thereby playing a certain shielding role and inhibiting the migration of the corrosive medium. The N atom contained therein has a lone pair of electrons in the outermost layer of the nucleus, which will adsorb with the metal surface through coordination bonding, thereby improving its corrosion inhibition performance. The mutual cooperation of the reinforcing filler and the anticorrosive filler greatly improves the corrosion resistance of the coating. Specific embodiments

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts belong to the scope of protection of the present invention. Example 1

[0020] A preparation method of a waterborne anticorrosive coating specifically includes the following steps: Weigh the following raw materials in parts by weight: 30 parts of bisphenol A epoxy acrylate resin, 50 parts of water, 0.1 part of trialkyl melamine, 0.1 part of lauryl alcohol, 5 parts of calcium carbonate, 5 parts of reinforcing filler, 0.2 part of anti-corrosion filler and 0.1 part of benzophenone. Mix the raw materials evenly, stir at a speed of 200 rpm for 10 h, and let stand for 3 h to obtain the waterborne anti-corrosion coating.

[0021] The viscosity of the bisphenol A epoxy acrylate resin is 5500 (cps / 60 °C), the acid value = 3 (mg KOH / g), the functionality is 2, the refractive index (25 °C) is 1.530, the density is 1.15 (g / ml), and the mesh number of calcium carbonate is 200 mesh. The anti-corrosion filler is prepared by the following steps: Step A1: Mix 1,1,2,2-tetrachloroethane, 4,4'-bipyridine and acetone evenly, and react at a speed of 100 rpm and a temperature of 70 °C for 10 h to obtain Intermediate 1. Mix Intermediate 1, deionized water and absolute ethanol evenly, and react at a speed of 100 rpm, a temperature of 40 °C and a pH value of 10 for 2 h to obtain Intermediate 2; Step A2: Disperse graphene oxide in deionized water, add KH580 and absolute ethanol, and react at a speed of 120 rpm and a temperature of 50 °C for 3 h to obtain modified graphene. Mix the modified graphene, Intermediate 2, toluene and p-toluenesulfonic acid evenly, and react at a speed of 90 rpm and a temperature of 70 °C for 6 h to obtain the anti-corrosion filler.

[0022] The dosage ratio of 1,1,2,2-tetrachloroethane, 4,4'-bipyridine and acetone in Step A1 is 1 g: 0.9 g: 20 mL, and the dosage ratio of Intermediate 1, deionized water and absolute ethanol is 1 g: 20 mL: 10 mL. The dosage of 1,1,2,2-tetrachloroethane is 350 g, and the dosage of Intermediate 1 is 500 g.

[0023] The dosage ratio of graphene oxide, deionized water, KH580 and absolute ethanol in Step A2 is 1 g: 30 mL: 5 mL: 20 mL, and the dosage ratio of modified graphene, Intermediate 2 and toluene is 1 g: 1.2 g: 20 mL. The dosage of p-toluenesulfonic acid is 2% of the mass of Intermediate 2. The dosage of graphene oxide is 200 g, and the dosage of modified graphene is 200 g.

[0024] The reinforcing filler is prepared by the following steps: Step B1: Mix 6-iodoquinoline, magnesium chips and diethyl ether evenly. Under the conditions of a rotation speed of 100 rpm, a temperature of 37 °C, and nitrogen protection, react for 1 h to obtain Intermediate 3. Mix Intermediate 3, titanium tetrachloride and diethyl ether evenly. Under the conditions of a rotation speed of 80 rpm, a temperature of 2 °C, and nitrogen protection, react for 3 h, then raise the temperature to 25 °C and continue to react for 9 h to obtain Intermediate 4; Step B2: Mix Intermediate 4, deionized water and absolute ethanol evenly. Under the conditions of a rotation speed of 100 rpm and a temperature of 40 °C, react for 0.5 h. Transfer the solution to a reaction kettle and react at a temperature of 120 °C for 24 h to obtain mesoporous titanium dioxide; Step B3: Disperse zinc oxide in deionized water, add γ-chloropropyltriethoxysilane and absolute ethanol, and react under the conditions of a rotation speed of 70 rpm and a temperature of 50 °C for 2 h to obtain modified zinc oxide. Mix the modified zinc oxide, mesoporous titanium dioxide and dimethylformamide evenly and react under the conditions of a rotation speed of 200 rpm and a temperature of 70 °C for 3 h to obtain the reinforcing filler.

[0025] The dosage ratio of 6-iodoquinoline, magnesium chips and diethyl ether described in Step B1 is 1 g: 1.2 g: 20 mL. The dosage ratio of Intermediate 3, titanium tetrachloride and diethyl ether is 1 g: 5 mL: 15 mL. The dosage of 6-iodoquinoline is 400 g, and the dosage of Intermediate 3 is 500 g.

[0026] The dosage ratio of Intermediate 4, deionized water and absolute ethanol described in Step B2 is 1 g: 20 mL: 10 mL. The dosage of Intermediate 4 is 500 g.

[0027] The dosage ratio of zinc oxide, deionized water, γ-chloropropyltriethoxysilane and absolute ethanol described in Step B3 is 1 g: 30 mL: 5 mL: 20 mL. The dosage ratio of modified zinc oxide, mesoporous titanium dioxide and dimethylformamide is 1 g: 0.8 g: 18 mL. The dosage of zinc oxide is 600 g, and the dosage of modified zinc oxide is 600 g. Example 2

[0028] A preparation method of a waterborne anticorrosive coating specifically includes the following steps: Weigh the following raw materials in parts by weight: 50 parts of bisphenol A epoxy acrylate resin, 70 parts of water, 0.5 part of trialkyl melamine, 0.5 part of lauryl alcohol, 10 parts of calcium carbonate, 10 parts of reinforcing filler, 0.8 part of anticorrosive filler and 0.5 part of benzophenone. Mix the raw materials evenly and stir at a rotation speed of 220 rpm for 12 h, then let it stand for 5 h to obtain the waterborne anticorrosive coating.

[0029] The viscosity of the bisphenol A epoxy acrylate resin is 5500 (cps / 60 °C), the acid value is 3 (mg KOH / g), the functionality is 2, the refractive index (25 °C) is 1.530, the density is 1.15 (g / ml), and the calcium carbonate mesh number is 200 mesh.

[0030] The anti-corrosion filler is prepared by the following steps: Step A1: Mix 1,1,2,2-tetrachloroethane, 4,4'-bipyridine, and acetone evenly. Under the conditions of a rotation speed of 120 rpm and a temperature of 80 °C, react for 12 h to obtain Intermediate 1. Mix Intermediate 1, deionized water, and absolute ethanol evenly. Under the conditions of a rotation speed of 120 rpm, a temperature of 50 °C, and a pH value of 12, react for 3 h to obtain Intermediate 2; Step A2: Disperse graphene oxide in deionized water, add KH580 and absolute ethanol, and react for 5 h under the conditions of a rotation speed of 150 rpm and a temperature of 60 °C to obtain modified graphene. Mix the modified graphene, Intermediate 2, toluene, and p-toluenesulfonic acid evenly. Under the conditions of a rotation speed of 110 rpm and a temperature of 80 °C, react for 8 h to obtain the anti-corrosion filler.

[0031] The dosage ratio of 1,1,2,2-tetrachloroethane, 4,4'-bipyridine, and acetone in Step A1 is 1 g:0.9 g:20 mL, and the dosage ratio of Intermediate 1, deionized water, and absolute ethanol is 1 g:20 mL:10 mL. The dosage of 1,1,2,2-tetrachloroethane is 350 g, and the dosage of Intermediate 1 is 500 g.

[0032] The dosage ratio of graphene oxide, deionized water, KH580, and absolute ethanol in Step A2 is 1 g:30 mL:5 mL:20 mL, and the dosage ratio of modified graphene, Intermediate 2, and toluene is 1 g:1.2 g:20 mL. The dosage of p-toluenesulfonic acid is 2% of the mass of Intermediate 2. The dosage of graphene oxide is 200 g, and the dosage of modified graphene is 200 g.

[0033] The reinforcing filler is prepared by the following steps: Step B1: Mix 6-iodoquinoline, magnesium chips, and diethyl ether evenly. Under the conditions of a rotation speed of 120 rpm, a temperature of 47 °C, and nitrogen protection, react for 2 h to obtain Intermediate 3. Mix Intermediate 3, titanium tetrachloride, and diethyl ether evenly. Under the conditions of a rotation speed of 100 rpm, a temperature of 10 °C, and nitrogen protection, react for 5 h, then raise the temperature to 35 °C and continue to react for 12 h to obtain Intermediate 4; Step B2: Mix Intermediate 4, deionized water, and absolute ethanol evenly. Under the conditions of a rotation speed of 120 rpm and a temperature of 50 °C, react for 1 h. Transfer the solution to a reaction kettle and react for 28 h under the condition of a temperature of 140 °C to obtain mesoporous titanium dioxide; Step B3: Disperse zinc oxide into deionized water, add γ-chloropropyltriethoxysilane and absolute ethanol, and react for 3 h under the conditions of a rotation speed of 90 rpm and a temperature of 60 °C to obtain modified zinc oxide. Mix the modified zinc oxide, mesoporous titanium dioxide and dimethylformamide evenly, and react for 5 h under the conditions of a rotation speed of 220 rpm and a temperature of 80 °C to obtain the reinforcing filler.

[0034] The dosage ratio of 6-iodoquinoline, magnesium chips and diethyl ether described in Step B1 is 1 g: 1.2 g: 20 mL, the dosage ratio of intermediate 3, titanium tetrachloride and diethyl ether is 1 g: 5 mL: 15 mL, the dosage of 6-iodoquinoline is 400 g, and the dosage of intermediate 3 is 500 g.

[0035] The dosage ratio of intermediate 4, deionized water and absolute ethanol described in Step B2 is 1 g: 20 mL: 10 mL, and the dosage of intermediate 4 is 500 g.

[0036] The dosage ratio of zinc oxide, deionized water, γ-chloropropyltriethoxysilane and absolute ethanol described in Step B3 is 1 g: 30 mL: 5 mL: 20 mL, the dosage ratio of modified zinc oxide, mesoporous titanium dioxide and dimethylformamide is 1 g: 0.8 g: 18 mL, the dosage of zinc oxide is 600 g, and the dosage of modified zinc oxide is 600 g. Example 3

[0037] A preparation method of a waterborne anticorrosive coating specifically includes the following steps: Weigh the following raw materials in parts by weight: 40 parts of bisphenol A epoxy acrylate resin, 60 parts of water, 0.3 part of trialkyl melamine, 0.3 part of lauryl alcohol, 8 parts of calcium carbonate, 8 parts of reinforcing filler, 0.5 part of anticorrosive filler and 0.3 part of benzophenone. Mix the raw materials evenly, stir for 11 h under the condition of a rotation speed of 210 rpm, and let stand for 4 h to obtain the waterborne anticorrosive coating.

[0038] The viscosity of the bisphenol A epoxy acrylate resin is 5500 (cps / 60 °C), the acid value = 3 (mg KOH / g), the functionality is 2, the refractive index (25 °C) is 1.530, the density is 1.15 (g / ml), and the mesh number of calcium carbonate is 200 mesh. The anticorrosive filler is prepared by the following steps: Step A1: Mix 1,1,2,2-tetrachloroethane, 4,4'-bipyridine and acetone evenly, and react for 11 h under the conditions of a rotation speed of 110 rpm and a temperature of 75 °C to obtain intermediate 1. Mix intermediate 1, deionized water and absolute ethanol evenly, and react for 2.5 h under the conditions of a rotation speed of 110 rpm, a temperature of 45 °C and a pH value of 11 to obtain intermediate 2; Step A2: Disperse graphene oxide in deionized water, add KH580 and absolute ethanol, and react for 4 h under the conditions of a rotation speed of 135 rpm and a temperature of 55 °C to obtain modified graphene. Mix the modified graphene, intermediate 2, toluene, and p-toluenesulfonic acid evenly, and react for 7 h under the conditions of a rotation speed of 100 rpm and a temperature of 75 °C to obtain the anticorrosive filler.

[0039] The dosage ratio of the 1,1,2,2-tetrachloroethane, 4,4'-bipyridine, and acetone described in Step A1 is 1 g: 0.9 g: 20 mL, the dosage ratio of intermediate 1, deionized water, and absolute ethanol is 1 g: 20 mL: 10 mL, the dosage of 1,1,2,2-tetrachloroethane is 350 g, and the dosage of intermediate 1 is 500 g.

[0040] The dosage ratio of the graphene oxide, deionized water, KH580, and absolute ethanol described in Step A2 is 1 g: 30 mL: 5 mL: 20 mL, the dosage ratio of the modified graphene, intermediate 2, and toluene is 1 g: 1.2 g: 20 mL, the dosage of p-toluenesulfonic acid is 2% of the mass of intermediate 2, the dosage of graphene oxide is 200 g, and the dosage of modified graphene is 200 g.

[0041] The reinforcing filler is prepared by the following steps: Step B1: Mix 6-iodoquinoline, magnesium chips, and diethyl ether evenly, and react for 1.5 h under the conditions of a rotation speed of 110 rpm, a temperature of 42 °C, and nitrogen protection to obtain intermediate 3. Mix intermediate 3, titanium tetrachloride, and diethyl ether evenly, and react for 4 h under the conditions of a rotation speed of 90 rpm, a temperature of 6 °C, and nitrogen protection, then raise the temperature to 30 °C and continue to react for 10.5 h to obtain intermediate 4; Step B2: Mix intermediate 4, deionized water, and absolute ethanol evenly, and react for 0.8 h under the conditions of a rotation speed of 110 rpm and a temperature of 45 °C. Transfer the solution to a reaction kettle and react for 26 h under the condition of a temperature of 130 °C to obtain mesoporous titanium dioxide; Step B3: Disperse zinc oxide in deionized water, add γ-chloropropyltriethoxysilane and absolute ethanol, and react for 2.5 h under the conditions of a rotation speed of 80 rpm and a temperature of 55 °C to obtain modified zinc oxide. Mix the modified zinc oxide, mesoporous titanium dioxide, and dimethylformamide evenly, and react for 4 h under the conditions of a rotation speed of 210 rpm and a temperature of 75 °C to obtain the reinforcing filler.

[0042] The dosage ratio of the 6-iodoquinoline, magnesium chips, and diethyl ether described in Step B1 is 1 g: 1.2 g: 20 mL, the dosage ratio of intermediate 3, titanium tetrachloride, and diethyl ether is 1 g: 5 mL: 15 mL, the dosage of 6-iodoquinoline is 400 g, and the dosage of intermediate 3 is 500 g.

[0043] In step B2, the usage ratio of intermediate 4, deionized water and anhydrous ethanol is 1 g: 20 mL: 10 mL, and the usage of intermediate 4 is 500 g.

[0044] In step B3, the dosage ratio of zinc oxide, deionized water, γ-chloropropyltriethoxysilane and anhydrous ethanol is 1g:30mL:5mL:20mL, the dosage ratio of modified zinc oxide, mesoporous titanium dioxide and dimethylformamide is 1g:0.8g:18mL, the dosage of zinc oxide is 600g, and the dosage of modified zinc oxide is 600g.

[0045] Comparative Example 1 Compared with Example 1, this comparative example uses ethylene glycol instead of 4,4'-bipyridine, and the specific steps are as follows: Tetrachloroethane, ethylene glycol, acetonitrile and sodium hydroxide solution were mixed evenly, and reacted for 11 hours at a rotation speed of 110 rpm and a temperature of 75° C. to obtain intermediate 1′, which was used to carry out subsequent reactions.

[0046] The usage ratio of tetrachloroethane, ethylene glycol, acetonitrile and sodium hydroxide solution is 1g:0.2mL:10mL:2mL, and the concentration of sodium hydroxide solution is 20%.

[0047] Comparative Example 2 Compared with Example 1, this comparative example uses graphene oxide instead of modified graphene, and the other steps are the same.

[0048] Comparative Example 3 Compared with Example 1, this comparative example uses mesoporous titanium dioxide instead of the reinforcing filler, and the other steps are the same.

[0049] The coatings prepared in Examples 1-3 and Comparative Examples 1-3 were coated on 50mm*100mm*0.3mm tinplates and photocured under ultraviolet light for 10 minutes. A neutral salt spray test was performed according to the standard of GB / T 10125-2021 to test the weight loss rate of the tinplate at 24h, 48h, 96h, 168h, and 480h. The test results are as follows:

[0050] As can be seen from the above table, the coatings prepared in Examples 1-3 have better anti-corrosion effects compared to Comparative Examples 1-3. In Comparative Example 1, ethylene glycol was used instead of 4,4'-bipyridine, lacking the adsorption of quaternary ammonium ions and the coordination bond effect of the benzene ring structure, resulting in a significant reduction in anti-corrosion performance. In Comparative Example 2, graphene oxide was used instead of modified graphene, and the anti-corrosion filler failed to form a cross-linked structure with bisphenol A epoxy acrylate resin, reducing the density of the coating and resulting in a decrease in anti-corrosion performance. In Comparative Example 3, mesoporous titanium dioxide was used instead of the reinforcing filler, lacking zinc oxide, and the single titanium oxide component could not form a dense zinc-titanium compound on the metal surface, resulting in a decrease in anti-corrosion performance. In summary, the waterborne anti-corrosion coating provided by the present invention has good anti-corrosion effects.

[0051] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the specific embodiments described or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by the claims of the present invention, they should fall within the protection scope of the present invention.

Claims

1. A method for preparing a water-based anticorrosive coating, characterized in that: The specific steps include: Weigh the following raw materials in parts by weight: 30-50 parts of bisphenol A epoxy acrylic resin, 50-70 parts of water, 0.1-0.5 parts of trialkyl melamine, 0.1-0.5 parts of lauryl alcohol, 5-10 parts of calcium carbonate, 5-10 parts of reinforcing filler, 0.2-0.8 parts of anticorrosive filler and 0.1-0.5 parts of benzophenone, mix the raw materials evenly, stir for 10-12 hours at a rotation speed of 200-220rpm, and let stand for 3-5 hours to prepare a water-based anticorrosive coating.

2. The method for preparing a water-based anticorrosive coating according to claim 1, characterized in that: The anticorrosive filler is made by the following steps: Step A1: uniformly mix tetrachloroethane, 4,4'-bipyridine and acetone, and react to obtain intermediate 1; uniformly mix intermediate 1, deionized water and anhydrous ethanol, and react to obtain intermediate 2; Step A2: dispersing graphene oxide in deionized water, adding KH580 and anhydrous ethanol, reacting to obtain modified graphene, and uniformly mixing the modified graphene, intermediate 2, toluene and p-toluenesulfonic acid, and reacting to obtain an anti-corrosion filler.

3. The method for preparing a water-based anticorrosive coating according to claim 2, characterized in that: In step A1, the usage ratio of tetrachloroethane, 4,4'-bipyridine and acetone is 1 g:0.9 g:20 mL, and the usage ratio of intermediate 1, deionized water and anhydrous ethanol is 1 g:20 mL:10 mL.

4. The method for preparing a water-based anticorrosive coating according to claim 2, characterized in that: In step A2, the amount ratio of graphene oxide, deionized water, KH580 and anhydrous ethanol is 1 g: 30 mL: 5 mL: 20 mL, the amount ratio of modified graphene, intermediate 2 and toluene is 1 g: 1.2 g: 20 mL, and the amount of p-toluenesulfonic acid is 2% of the mass of intermediate 2.

5. The method for preparing a water-based anticorrosive coating according to claim 1, characterized in that: The reinforcing filler is prepared by the following steps: Step B1: 6-iodoquinoline, magnesium chips and diethyl ether are mixed evenly, and reacted to obtain intermediate 3; intermediate 3, titanium tetrachloride and diethyl ether are mixed evenly, and reacted, and the temperature is raised to continue the reaction to obtain intermediate 4; Step B2: The intermediate 4, deionized water and anhydrous ethanol are mixed evenly, reacted, and the solution is transferred to a reaction kettle to react to obtain mesoporous titanium dioxide; Step B3: Disperse zinc oxide in deionized water, add γ-chloropropyltriethoxysilane and anhydrous ethanol, react to obtain modified zinc oxide, mix the modified zinc oxide, mesoporous titanium dioxide and dimethylformamide evenly, and react to obtain a reinforcing filler.

6. The method for preparing a water-based anticorrosive coating according to claim 5, characterized in that: In step B1, the usage ratio of 6-iodoquinoline, magnesium chips and diethyl ether is 1 g:1.2 g:20 mL, and the usage ratio of intermediate 3, titanium tetrachloride and diethyl ether is 1 g:5 mL:15 mL.

7. The method for preparing a water-based anticorrosive coating according to claim 5, characterized in that: The usage ratio of the intermediate 4, deionized water and anhydrous ethanol in step B2 is 1 g: 20 mL: 10 mL.

8. The method for preparing a water-based anticorrosive coating according to claim 5, characterized in that: In step B3, the dosage ratio of zinc oxide, deionized water, γ-chloropropyltriethoxysilane and anhydrous ethanol is 1 g: 30 mL: 5 mL: 20 mL, and the dosage ratio of modified zinc oxide, mesoporous titanium dioxide and dimethylformamide is 1 g: 0.8 g: 18 mL.

9. A water-based anticorrosive coating, characterized in that: Prepared according to any one of the preparation methods described in claims 1-8.

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