A wear-resistant and highly elastic colored polyurethane coating

Abstract

The invention discloses a wear-resistant and highly elastic colored polyurethane coating, and relates to the technical field of coatings. The invention discloses a wear-resistant and highly elastic colored polyurethane coating as a polyurethane floor finish; the polyurethane floor finish comprises a main agent and a curing agent; the main agent comprises the following raw materials in weight percentage: 20-25% water, 5-8% wax powder, 1.5-2.6% auxiliary agent, 10-20% pigment, the remainder is a modified hydroxyl acrylic resin, and the sum of the raw material weight percentages is 100%; the curing agent is a hydrophilic modified polyisocyanate curing agent; the present application adds modified graphene oxide grafted and modified by epoxidized octavinyl silsesquioxane during the preparation process of the hydroxyl acrylic resin to prepare a modified hydroxyl acrylic resin; the modified hydroxyl acrylic resin prepared by the present application is added to the coating as a hydroxyl component, effectively improving the wear resistance and antistatic properties of the polyurethane coating.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to a wear-resistant and highly elastic colored polyurethane coating. Background Art

[0002] In modern production and living spaces, the concrete floors and building surfaces of buildings may crack due to environmental changes and vehicle loads. They may also be eroded or even structurally damaged by concrete carbonization, acid rain corrosion, and other corrosive liquids. Floor coating is considered an indispensable measure for building protection and decoration. As a direct contact layer for vehicle traffic and personnel activities, the primary function of floor coating is to absorb and disperse static and dynamic loads. If epoxy floor coatings with high rigidity are used, they will break due to cracking of the ground, and the coating will lose its protection of the ground. In recent years, the popular ultra-wear-resistant floor topcoat reflects the market's high requirements for multiple technical indicators of floor paint, such as hardness, wear resistance, and scratch resistance. Excellent floor topcoat needs to achieve the lowest possible wear under the condition of external wear, and weaken the scratches, gloss changes, or other defects on the surface of the paint film.

[0003] Polyurethane floor coatings have certain elasticity and flexibility. The matching system of solvent-free polyurethane primer, solvent-free polyurethane topcoat, and solvent-free polyurethane floor topcoat has the characteristics of crack resistance, anti-slip, wear resistance, weather resistance and environmental protection, which can well protect the building floor. Waterborne polyurethane resin is the main base material for today's high-quality waterborne coatings. The waterborne two-component polyurethane system is composed of acrylic polyols with -OH groups and hydrophilic modified polyisocyanate curing agents containing -NCO groups. Among them, hydroxy acrylic polyols have an important influence on the performance of waterborne two-component polyurethane coatings. According to different preparation methods, hydroxyl polyols can be divided into hydroxyl acrylic emulsions and hydroxyl acrylic aqueous dispersions, but the hydroxyl acrylic resins currently prepared by emulsion polymerization have the problems of low stability and poor compatibility with isocyanate curing agents. Summary of the invention

[0004] The purpose of the present invention is to provide a wear-resistant and highly elastic colored polyurethane coating to solve the following technical problems:

[0005] Existing hydroxy polyols, as raw materials for two-component polyurethanes, have problems of low stability and poor compatibility with isocyanate curing agents.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A wear-resistant and highly elastic colored polyurethane coating, which is a polyurethane floor topcoat;

[0008] Polyurethane floor topcoat includes a main agent and a curing agent;

[0009] The main agent includes the following raw materials in weight percentage: 20-25% water, 5-8% wax powder, 1.5-2.6% auxiliary agent, 10-20% pigment, and the balance is modified hydroxyl acrylic resin, and the sum of the raw materials weight percentage is 100%;

[0010] The preparation method of the modified hydroxy acrylic resin comprises the following steps:

[0011] S1: 3-m-chloroperbenzoic acid and dichloromethane 1 are added to the reaction kettle A and dispersed evenly, octavinylsilsesquioxane and dichloromethane 2 are mixed and added to the reaction kettle A and dispersed evenly, the temperature is controlled at 35-45°C, the reaction is kept warm for 12-24 hours, and then filtered, washed and dried to obtain epoxidized octavinylsilsesquioxane;

[0012] S2: Add epoxidized octavinyl silsesquioxane, modified graphene oxide and anhydrous ethanol into reactor B and disperse them evenly, control the temperature to 80-90°C, keep the reaction temperature for 12-24h, wash and dry, component one;

[0013] S3: In a nitrogen atmosphere, add the composite emulsifier, deionized water and benzoyl peroxide 1 into the reaction kettle and disperse them evenly, control the temperature at 75-85°C, add component 1 and seed monomer component 1, and keep warm for 0.2-0.4h; add seed monomer component 2 and benzoyl peroxide 2, keep warm for 0.5-1h, add shell monomer, keep warm for 6-9h, adjust the pH to 7-8, filter the material, and obtain modified hydroxy acrylic resin.

[0014] As a further embodiment of the present invention, the addition ratio of 3-m-chloroperbenzoic acid, dichloromethane 1, octavinylsilsesquioxane and dichloromethane 2 in S1 is 0.75-1.5 g: 10-20 mL: 10 g: 100-150 mL.

[0015] As a further solution of the present invention: the addition ratio of epoxidized octavinylsilsesquioxane, modified graphene oxide and anhydrous ethanol in S2 is 1-1.5 g: 10 g: 100-200 mL.

[0016] As a further embodiment of the present invention: the composite emulsifier in S3 is obtained by mixing sodium dodecyl benzene diphenyl ether disulfonate and sodium 2-acrylamido-2-methylpropane sulfonate in a mass ratio of 1:1-2;

[0017] The seed monomer component 1 and the seed monomer component 2 are both obtained by mixing methyl methacrylate and butyl acrylate in a mass ratio of 3:1-2; the mass ratio of the seed monomer component 1 to the seed monomer component 2 is 10:90;

[0018] The shell monomer is obtained by mixing methacrylic acid, hydroxyethyl acrylate and hydroxypropyl acrylate in a mass ratio of 16-24:68-100:65-100;

[0019] The addition ratio of composite emulsifier, deionized water, benzoyl peroxide 1, component 1, seed monomer component 1, benzoyl peroxide 2, and shell monomer is 0.75-1.5g: 50-75mL: 0.04-0.06g: 2-5g: 1-2g: 0.05-0.1g: 22-32g.

[0020] As a further scheme of the present invention: a method for preparing octavinyl silsesquioxane comprises the following steps: adding anhydrous ethanol, distilled water and vinyl triethoxysilane into a reaction kettle and dispersing them uniformly, adding hydrochloric acid to adjust the pH to 2-4, controlling the temperature to 55-65°C, keeping the temperature for reaction for 9-15h, cooling, filtering, washing and drying to obtain octavinyl silsesquioxane.

[0021] As a further solution of the present invention: a method for preparing modified graphene oxide comprises the following steps:

[0022] A1: Add graphene oxide and concentrated ammonia water into a reaction bottle and disperse them evenly. Control the temperature at 45-55°C, keep the temperature for 4-10 hours, cool to room temperature, filter, wash with water until neutral, and vacuum dry to obtain aminated graphene oxide.

[0023] A2: Add aminated graphene oxide and deionized water into a reactor and disperse them evenly. Mix aniline and hydrochloric acid solution 1 and add them into the reactor and disperse them evenly. Mix ammonium persulfate and hydrochloric acid solution 2 and add them into the reactor and disperse them evenly. Control the temperature at 0-5°C, keep the reaction warm for 9-12h, filter, wash until neutral, and dry to obtain modified graphene oxide.

[0024] As a further solution of the present invention: the concentrated ammonia water in A1 is 22-28wt% ammonia water; the addition ratio of graphene oxide and concentrated ammonia water is 10g:20-40mL.

[0025] As a further solution of the present invention: in A2, hydrochloric acid solution 1 and hydrochloric acid solution 2 are both 1.5-2.5 mol / L hydrochloric acid aqueous solutions; the addition ratio of aminated graphene oxide, deionized water, aniline, hydrochloric acid solution 1, ammonium persulfate, and hydrochloric acid solution 2 is 10g: 150-250mL: 8-12g: 120-180mL: 15-20g: 20-30mL.

[0026] As a further solution of the present invention: the mass ratio of the main agent to the curing agent in the polyurethane floor topcoat is 100:60-100.

[0027] As a further solution of the present invention: the auxiliary agent is obtained by mixing a defoamer, a wetting and leveling agent, a thickener and a dispersant in a mass ratio of 0.3-0.4:0.2-0.4:0.5-0.8:0.5-1.

[0028] As a further embodiment of the present invention: the curing agent is a hydrophilic modified polyisocyanate curing agent; the preparation method of the hydrophilic modified polyisocyanate curing agent comprises the following steps: in a nitrogen atmosphere, adding HDI trimer into a reaction kettle, controlling the temperature at 70-80°C, adding polyethylene glycol monomethyl ether, keeping the temperature for reaction for 3-4 hours, adding benzoyl chloride to terminate the reaction, and obtaining a hydrophilic modified polyisocyanate curing agent.

[0029] As a further solution of the present invention: during the preparation of the hydrophilic modified polyisocyanate curing agent, the molar ratio of the addition of HDI trimer and polyethylene glycol monomethyl ether is n(-NCO):n(-OH)=6-8:1.

[0030] Beneficial effects of the present invention:

[0031] (1) The present application uses the Hummers method to chemically oxidize natural graphite and ultrasonically exfoliate to prepare graphene oxide, and uses ammonia water to hydrothermally treat the graphene oxide, introduces amine groups on the surface of the graphene oxide, and then grafts polyaniline, so that the polyaniline and graphene are conjugated to obtain modified graphene oxide; the modified graphene oxide prepared in the present application not only plays the structural skeleton role of graphene, but also improves the conductive properties of the material; the present application uses vinyl trimethoxysilane as a raw material and hydrochloric acid as a catalyst to synthesize octaethylene oxide through a hydrolysis condensation reaction. The invention discloses a method for preparing a hydroxyl core-shell acrylic ester emulsion with good stability and high solid content by using the epoxy group on the molecular structure of epoxidized octavinyl silsesquioxane and the amino group on the modified graphene oxide; and epoxidizing octavinyl cage silsesquioxane with 3-chloroperoxybenzoic acid to obtain octavinyl cage silsesquioxane with epoxy groups, i.e., epoxidized octavinyl silsesquioxane; the present invention utilizes the epoxy group on the molecular structure of epoxidized octavinyl silsesquioxane to react with the amino group of modified graphene oxide to prepare component one; in the copolymerization process of acrylate monomers, component one is added to synthesize a hydroxyl core-shell acrylic ester emulsion with good stability and high solid content, i.e., modified hydroxyl acrylic resin. In the preparation process of the hydroxyl acrylic resin, a film-forming substance of the coating, the present invention copolymerizes and grafts graphene oxide having a Si iOS i molecular chain and an aniline copolymer on the acrylic resin molecular chain, so that a double cross-linked structure of carbamate bonds and Si iOS i bonds is formed in the polyurethane two-component coating film, giving the coating film the characteristics of high hardness, high wear resistance, and antistatic properties.

[0032] (2) The defoaming agent added in this application effectively avoids and eliminates bubbles generated during the production process and construction of the coating, and also helps to remove the carbon dioxide generated by the reaction between the hydrophilic modified isocyanate and water during the curing process of the floor coating. The wetting and leveling agent added in this application improves the wettability of the coating to the base layer, effectively reduces the surface tension of the system, improves the wettability and permeability of the coating to the substrate, and improves adhesion. The thickener added in this application effectively increases the dry film thickness of one-time construction and improves the fullness of the coating. The wax powder added in this application improves the smoothness of the paint film surface, thereby reducing the friction coefficient of the paint film, thereby improving the scratch resistance of the coating; the wetting and dispersing agent added in this application facilitates the dispersion of the wax powder in the water-based coating to obtain good dispersion uniformity and stability.

[0033] (3) This application uses polyethylene glycol polyether to modify isocyanate trimer to obtain hydrophilic modified polyisocyanate curing agent; this application uses modified hydroxy acrylic resin as film-forming material, and is compounded with pigments, solvents, wax powder, and additives to form wear-resistant and highly elastic colored polyurethane coatings; this application uses non-ionic modification method to introduce polyethylene glycol polyether into HDI isocyanate curing material. Polyethylene glycol polyether not only serves as a hydrophilic functional group, but also reduces the crystallinity of the product molecule, thereby reducing the viscosity of the product and improving the dispersibility of the product in coatings and water. This application introduces a hydrophilic modifier to make the polyisocyanate curing agent have good water dispersibility, improve its compatibility with modified hydroxy acrylic resin, and improve the water resistance, chemical resistance, hardness and other properties of the two-component coating. DETAILED DESCRIPTION

[0034] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] Embodiment 1 The preparation method of modified graphene oxide comprises the following steps:

[0036] A1: Add 10g natural graphite powder, 200mL concentrated sulfuric acid and 5g sodium nitrate into a reaction bottle, control the temperature at 0°C, add 20g potassium permanganate under stirring, control the temperature at 30°C, and keep the reaction for 1h; add 200mL distilled water, control the temperature at 80°C, add 20mL hydrogen peroxide under stirring, cool to room temperature, let stand, remove the supernatant, filter and wash with 5wt% dilute hydrochloric acid and distilled water until neutral, ultrasonically vibrate for 6h, and dry to obtain graphene oxide;

[0037] A2: 10 g of graphene oxide and 20 mL of 22 wt% concentrated ammonia water were added to a reaction bottle and dispersed evenly. The temperature was controlled at 50°C and the reaction was kept warm for 5 h. The mixture was cooled to room temperature, filtered, washed with water until neutral, and dried in vacuum to obtain aminated graphene oxide.

[0038] A3: Add 10 g of aminated graphene oxide and 200 mL of deionized water into a reactor and disperse them evenly. Mix 10 g of aniline and 150 mL of 2 mol / L hydrochloric acid aqueous solution and add them into the reactor and disperse them evenly. Mix 17 g of ammonium persulfate and 25 mL of 2 mol / L hydrochloric acid aqueous solution and add them into the reactor and disperse them evenly. Control the temperature at 0°C, keep the reaction warm for 9 hours, filter, wash until neutral, and dry to obtain modified graphene oxide.

[0039] The preparation method of the hydrophilic modified polyisocyanate curing agent comprises the following steps:

[0040] In a nitrogen atmosphere, HDI trimer (TPA-100, purchased from Asahi Chemical Co., Ltd., Japan) with a molar ratio of n(-NCO):n(-OH)=6:1 and polyethylene glycol monomethyl ether (MPEG550) were added to the reactor, the temperature was controlled at 70-80°C, the reaction was kept warm for 3 hours, and 3 drops of benzoyl chloride were added to terminate the reaction to obtain a hydrophilic modified polyisocyanate curing agent.

[0041] Embodiment 2 The preparation method of modified hydroxy acrylic resin comprises the following steps:

[0042] S1: 240 mL of anhydrous ethanol, 30 mL of distilled water, and 95 g of vinyl triethoxysilane were added to a reaction kettle and dispersed evenly, hydrochloric acid was added to adjust the pH to 2, the temperature was controlled at 55°C, the reaction was kept warm for 9 hours, cooled, filtered, washed, and dried to obtain octavinyl silsesquioxane;

[0043] S2: 0.75 g of 3-m-chloroperbenzoic acid and 10 mL of dichloromethane were added to reactor A and dispersed evenly, 10 g of octavinyl silsesquioxane and 100 mL of dichloromethane were mixed and added to reactor A and dispersed evenly, the temperature was controlled at 35° C., the reaction was kept warm for 12 h, and the mixture was filtered, washed, and dried to obtain epoxidized octavinyl silsesquioxane;

[0044] S3: 1 g of epoxidized octavinyl silsesquioxane, 10 g of modified graphene oxide prepared in Example 1, and 100 mL of anhydrous ethanol were added to reactor B and dispersed evenly, the temperature was controlled at 80° C., the reaction was kept warm for 12 h, and then washed and dried to obtain component one;

[0045] S4: In a nitrogen atmosphere, 0.5 g of sodium dodecylbenzene diphenyl oxide disulfonate, 0.5 g of sodium 2-acrylamido-2-methylpropane sulfonate, 50 mL of deionized water, and 0.04 g of benzoyl peroxide were added to a reactor and dispersed evenly. The temperature was controlled at 75°C, and 5 g of component 1, 0.6 g of methyl methacrylate, and 0.4 g of butyl acrylate were added, and the mixture was kept warm for 0.2 h; 5.4 g of methyl methacrylate, 3.6 g of butyl acrylate, and 0.05 g of benzoyl peroxide were added, and the mixture was kept warm for 0.5 h. 2.5 g of methacrylic acid, 10 g of hydroxyethyl acrylate, and 12.5 g of hydroxypropyl acrylate were added, and the mixture was kept warm for 6 h. Ammonia water was added to adjust the pH to 7, and the material was filtered to obtain a modified hydroxy acrylic resin.

[0046] Embodiment 3 The preparation method of modified hydroxy acrylic resin comprises the following steps:

[0047] S1: 240 mL of anhydrous ethanol, 30 mL of distilled water, and 95 g of vinyl triethoxysilane were added to a reaction kettle and dispersed evenly, hydrochloric acid was added to adjust the pH to 3, the temperature was controlled at 60°C, the reaction was kept warm for 12 hours, cooled, filtered, washed, and dried to obtain octavinyl silsesquioxane;

[0048] S2: 1 g of 3-m-chloroperbenzoic acid and 15 mL of dichloromethane were added to the reaction kettle A and dispersed evenly. 10 g of octavinyl silsesquioxane and 120 mL of dichloromethane were mixed and added to the reaction kettle A and dispersed evenly. The temperature was controlled at 40°C, and the reaction was kept warm for 16 hours. The reaction was filtered, washed, and dried to obtain epoxidized octavinyl silsesquioxane.

[0049] S3: 1.2 g of epoxidized octavinyl silsesquioxane, 10 g of modified graphene oxide prepared in Example 1, and 150 mL of anhydrous ethanol were added to reactor B and dispersed evenly, the temperature was controlled at 85° C., the reaction was kept warm for 16 h, washed, dried, and component one;

[0050] S4: In a nitrogen atmosphere, 0.5 g of sodium dodecylbenzene diphenyl oxide disulfonate, 0.5 g of sodium 2-acrylamido-2-methylpropane sulfonate, 60 mL of deionized water, and 0.05 g of benzoyl peroxide were added to a reactor and dispersed evenly. The temperature was controlled at 80°C, and 5 g of component 1, 0.6 g of methyl methacrylate, and 0.4 g of butyl acrylate were added, and the mixture was kept warm for 0.3 h; 5.4 g of methyl methacrylate, 3.6 g of butyl acrylate, and 0.07 g of benzoyl peroxide were added, and the mixture was kept warm for 0.7 h. 2.5 g of methacrylic acid, 10 g of hydroxyethyl acrylate, and 12.5 g of hydroxypropyl acrylate were added, and the mixture was kept warm for 7.5 h. Ammonia water was added to adjust the pH to 7.5, and the material was filtered to obtain a modified hydroxy acrylic resin.

[0051] Embodiment 4 The preparation method of modified hydroxy acrylic resin comprises the following steps:

[0052] S1: 240 mL of anhydrous ethanol, 30 mL of distilled water, and 95 g of vinyl triethoxysilane were added to a reaction kettle and dispersed evenly, hydrochloric acid was added to adjust the pH to 4, the temperature was controlled at 65°C, the reaction was kept warm for 15 hours, cooled, filtered, washed, and dried to obtain octavinyl silsesquioxane;

[0053] S2: 1.5 g 3-m-chloroperbenzoic acid and 20 mL dichloromethane were added to reactor A and dispersed evenly, 10 g octavinyl silsesquioxane and 150 mL dichloromethane were mixed and added to reactor A and dispersed evenly, the temperature was controlled at 45°C, the reaction was kept warm for 24 hours, and then filtered, washed and dried to obtain epoxidized octavinyl silsesquioxane;

[0054] S3: 1.5 g of epoxidized octavinylsilsesquioxane, 10 g of modified graphene oxide prepared in Example 1, and 200 mL of anhydrous ethanol were added to reactor B and dispersed evenly, the temperature was controlled at 90° C., the reaction was kept warm for 24 h, washed, dried, and component one;

[0055] S4: In a nitrogen atmosphere, 0.5 g of sodium dodecylbenzene diphenyl oxide disulfonate, 0.5 g of sodium 2-acrylamido-2-methylpropane sulfonate, 75 mL of deionized water, and 0.06 g of benzoyl peroxide were added to a reactor and dispersed evenly. The temperature was controlled at 85°C, and 5 g of component 1, 0.6 g of methyl methacrylate, and 0.4 g of butyl acrylate were added, and the mixture was kept warm for 0.4 h; 5.4 g of methyl methacrylate, 3.6 g of butyl acrylate, and 0.1 g of benzoyl peroxide were added, and the mixture was kept warm for 1 h. 2.5 g of methacrylic acid, 10 g of hydroxyethyl acrylate, and 12.5 g of hydroxypropyl acrylate were added, and the mixture was kept warm for 9 h. Ammonia water was added to adjust the pH to 8, and the material was filtered to obtain a modified hydroxy acrylic resin.

[0056] Embodiment 5 A method for preparing a wear-resistant and highly elastic colored polyurethane coating comprises the following steps:

[0057] 25g water, 5g wax powder, 0.3g BYK-025 defoamer, 0.3g BYK-346 wetting and leveling agent, 0.2g R-420 thickener, 0.4g RM8W thickener, 1g BYK-161 dispersant, 15g pigment (iron red powder), 52.8g modified hydroxy acrylic resin prepared in Example 2, and 90g hydrophilic modified polyisocyanate curing agent prepared in Example 1 were blended to obtain a wear-resistant and highly elastic colored polyurethane coating.

[0058] Embodiment 6 A method for preparing a wear-resistant and highly elastic colored polyurethane coating comprises the following steps:

[0059] 25g water, 5g wax powder, 0.3g BYK-025 defoamer, 0.3g BYK-346 wetting and leveling agent, 0.2g R-420 thickener, 0.4g RM8W thickener, 1g BYK-161 dispersant, 15g pigment (iron red powder), 52.8g modified hydroxy acrylic resin prepared in Example 3, and 90g hydrophilic modified polyisocyanate curing agent prepared in Example 1 were blended to obtain a wear-resistant and highly elastic colored polyurethane coating.

[0060] Embodiment 7 A method for preparing a wear-resistant and highly elastic colored polyurethane coating comprises the following steps:

[0061] 25g water, 5g wax powder, 0.3g BYK-025 defoamer, 0.3g BYK-346 wetting and leveling agent, 0.2g R-420 thickener, 0.4g RM8W thickener, 1g BYK-161 dispersant, 15g pigment (iron red powder), 52.8g modified hydroxy acrylic resin prepared in Example 4, and 90g hydrophilic modified polyisocyanate curing agent prepared in Example 1 were blended to obtain a wear-resistant and highly elastic colored polyurethane coating.

[0062] Comparative Example 1 A method for preparing modified graphene oxide comprises the following steps:

[0063] A1: Add 10g natural graphite powder, 200mL concentrated sulfuric acid and 5g sodium nitrate into a reaction bottle, control the temperature at 0°C, add 20g potassium permanganate under stirring, control the temperature at 30°C, and keep the reaction for 1h; add 200mL distilled water, control the temperature at 80°C, add 20mL hydrogen peroxide under stirring, cool to room temperature, let stand, remove the supernatant, filter and wash with 5wt% dilute hydrochloric acid and distilled water until neutral, ultrasonically vibrate for 6h, and dry to obtain graphene oxide;

[0064] A2: 10 g of graphene oxide and 20 mL of 22 wt% concentrated ammonia water were added to a reaction bottle and dispersed evenly. The temperature was controlled at 50°C and the reaction was kept warm for 5 hours. The mixture was cooled to room temperature, filtered, washed with water until neutral, and dried in vacuum to obtain modified graphene oxide.

[0065] Comparative Example 2 The preparation method of the modified hydroxy acrylic resin comprises the following steps:

[0066] S1: 240 mL of anhydrous ethanol, 30 mL of distilled water, and 95 g of vinyl triethoxysilane were added to a reaction kettle and dispersed evenly, hydrochloric acid was added to adjust the pH to 3, the temperature was controlled at 60°C, the reaction was kept warm for 12 hours, cooled, filtered, washed, and dried to obtain octavinyl silsesquioxane;

[0067] S2: 1 g of 3-m-chloroperbenzoic acid and 15 mL of dichloromethane were added to the reaction kettle A and dispersed evenly. 10 g of octavinyl silsesquioxane and 120 mL of dichloromethane were mixed and added to the reaction kettle A and dispersed evenly. The temperature was controlled at 40°C, and the reaction was kept warm for 16 hours. The reaction was filtered, washed, and dried to obtain epoxidized octavinyl silsesquioxane.

[0068] S3: 1.2 g of epoxidized octavinyl silsesquioxane, 10 g of modified graphene oxide prepared in Comparative Example 1, and 150 mL of anhydrous ethanol were added to reactor B and dispersed evenly, the temperature was controlled at 85° C., the reaction was kept warm for 16 h, washed, dried, and component one;

[0069] S4: In a nitrogen atmosphere, 0.5 g of sodium dodecylbenzene diphenyl oxide disulfonate, 0.5 g of sodium 2-acrylamido-2-methylpropane sulfonate, 60 mL of deionized water, and 0.05 g of benzoyl peroxide were added to a reactor and dispersed evenly. The temperature was controlled at 80°C, and 5 g of component 1, 0.6 g of methyl methacrylate, and 0.4 g of butyl acrylate were added, and the mixture was kept warm for 0.3 h; 5.4 g of methyl methacrylate, 3.6 g of butyl acrylate, and 0.07 g of benzoyl peroxide were added, and the mixture was kept warm for 0.7 h. 2.5 g of methacrylic acid, 10 g of hydroxyethyl acrylate, and 12.5 g of hydroxypropyl acrylate were added, and the mixture was kept warm for 7.5 h. Ammonia water was added to adjust the pH to 7.5, and the material was filtered to obtain a modified hydroxy acrylic resin.

[0070] Comparative Example 3 The preparation method of the modified hydroxy acrylic resin comprises the following steps:

[0071] S1: 240 mL of anhydrous ethanol, 30 mL of distilled water, and 95 g of vinyl triethoxysilane were added to a reaction kettle and dispersed evenly, hydrochloric acid was added to adjust the pH to 4, the temperature was controlled at 65°C, the reaction was kept warm for 15 hours, cooled, filtered, washed, and dried to obtain octavinyl silsesquioxane;

[0072] S2: 1.5 g 3-m-chloroperbenzoic acid and 20 mL dichloromethane were added to reactor A and dispersed evenly, 10 g octavinyl silsesquioxane and 150 mL dichloromethane were mixed and added to reactor A and dispersed evenly, the temperature was controlled at 45°C, the reaction was kept warm for 24 hours, and then filtered, washed and dried to obtain epoxidized octavinyl silsesquioxane;

[0073] S3: 1.5 g of epoxidized octavinylsilsesquioxane, 10 g of modified graphene oxide prepared in Example 1, and 200 mL of anhydrous ethanol were added to reactor B and dispersed evenly, the temperature was controlled at 90° C., the reaction was kept warm for 24 h, washed, dried, and component one;

[0074] S4: In a nitrogen atmosphere, 0.5 g of sodium dodecyl benzene diphenyl ether disulfonate, 0.5 g of sodium 2-acrylamido-2-methylpropane sulfonate, 75 mL of deionized water, and 0.06 g of benzoyl peroxide were added to a reactor and dispersed evenly. The temperature was controlled at 85°C, 0.6 g of methyl methacrylate and 0.4 g of butyl acrylate were added, and the mixture was kept warm for 0.4 h; 5.4 g of methyl methacrylate, 3.6 g of butyl acrylate, and 0.1 g of benzoyl peroxide were added, and the mixture was kept warm for 1 h. 2.5 g of methacrylic acid, 10 g of hydroxyethyl acrylate, and 12.5 g of hydroxypropyl acrylate were added, and the mixture was kept warm for 9 h. Ammonia water was added to adjust the pH to 8, the material was filtered out, and the mixture was blended with 5 g of component 1 to obtain a modified hydroxy acrylic resin.

[0075] Comparative Example 4 A method for preparing a wear-resistant and highly elastic colored polyurethane coating comprises the following steps:

[0076] 25g water, 5g wax powder, 0.3g BYK-025 defoamer, 0.3g BYK-346 wetting and leveling agent, 0.2g R-420 thickener, 0.4g RM8W thickener, 1g BYK-161 dispersant, 15g pigment (iron red powder), 52.8g modified hydroxy acrylic resin prepared in Example 3, and 90g hexamethylene diisocyanate were blended to obtain a wear-resistant and highly elastic colored polyurethane coating.

[0077] Comparative Example 5 A method for preparing a wear-resistant and highly elastic colored polyurethane coating comprises the following steps:

[0078] 25g water, 5g wax powder, 0.3g BYK-025 defoamer, 0.3g BYK-346 wetting and leveling agent, 0.2g R-420 thickener, 0.4g RM8W thickener, 1g BYK-161 dispersant, 15g pigment (iron red powder), 52.8g modified hydroxy acrylic resin prepared in Example 3, and 90g hydrophilic modified polyisocyanate curing agent prepared in Comparative Example 2 were blended to obtain a wear-resistant and highly elastic colored polyurethane coating.

[0079] Comparative Example 6 A method for preparing a wear-resistant and highly elastic colored polyurethane coating comprises the following steps:

[0080] 25g water, 5g wax powder, 0.3g BYK-025 defoamer, 0.3g BYK-346 wetting and leveling agent, 0.2g R-420 thickener, 0.4g RM8W thickener, 1g BYK-161 dispersant, 15g pigment (iron red powder), 52.8g modified hydroxy acrylic resin prepared in Example 3, and 90g hydrophilic modified polyisocyanate curing agent prepared in Comparative Example 3 were blended to obtain a wear-resistant and highly elastic colored polyurethane coating.

[0081] Performance Testing

[0082] (1) Pencil hardness: Tested according to GB / T 6739-2006 “Determination of film hardness of paints and varnishes by pencil method”. The test results are shown in Table 1.

[0083] (2) Gloss: The gloss of the coating film was tested according to HG / T3828-2006 "Water-based Wood Coatings for Indoor Use" using a WGG60-E4 gloss meter at a 60° angle. The test results are shown in Table 1.

[0084] (3) Abrasion resistance: The test was conducted according to GB / T 22374-2018 Floor Coating Materials. A 1000g test hammer was loaded, a CS-17 rubber grinding wheel was used as the friction medium, and the grinding was performed for 500r. The mass difference before and after grinding was measured, m1. The test results are shown in Table 1.

[0085] (4) Conductivity: Tested according to SJ / T 11294-2003 "General Specification for Antistatic Floor Coatings", the test results are shown in Table 1;

[0086] (5) Storage stability: According to GB / T 6753.3-1986 "Test method for storage stability of coatings", the coatings prepared in Examples 5-7 and Comparative Examples 4-6 were stored in a constant temperature drying oven at 50±2°C for 30 days to observe whether there were changes in flocculation, sedimentation, skinning and agglomeration. The test results are shown in Table 1.

[0087] Table 1: Statistical table of physical and chemical performance test data of Examples 5-7 and Comparative Examples 4-6

[0088]

[0089] It can be seen from Table 1 that the coating prepared in the present application has high hardness, high wear resistance, high gloss and antistatic properties, and has high storage stability after production.

[0090] Table 2: Statistical table of weather resistance test data of Examples 5-7 and Comparative Examples 4-6

[0091]

[0092] It can be seen from Table 2 that the coating prepared in the present application has good acid and alkali resistance and aging resistance.

[0093] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A wear-resistant and highly elastic colored polyurethane coating, characterized in that: The wear-resistant and highly elastic colored polyurethane coating is a polyurethane floor finish paint; The polyurethane floor finish paint comprises a main agent and a curing agent; The main agent comprises the following raw materials in weight percentage: 20-25% water, 5-8% wax powder, 1.5-2.6% auxiliary agent, 10-20% pigment, and the remainder is modified hydroxyl acrylic resin, and the sum of the raw materials weight percentage is 100%; The preparation method of the modified hydroxy acrylic resin comprises the following steps: S1: 3-m-chloroperbenzoic acid and dichloromethane 1 are added to the reaction kettle A and dispersed evenly, octavinylsilsesquioxane and dichloromethane 2 are mixed and added to the reaction kettle A and dispersed evenly, the temperature is controlled at 35-45°C, the reaction is kept warm for 12-24 hours, and then filtered, washed and dried to obtain epoxidized octavinylsilsesquioxane; S2: Add epoxidized octavinyl silsesquioxane, modified graphene oxide and anhydrous ethanol into reactor B and disperse them evenly, control the temperature to 80-90°C, keep the reaction temperature for 12-24h, wash and dry, component one; S3: In a nitrogen atmosphere, add the composite emulsifier, deionized water and benzoyl peroxide 1 into the reaction kettle and disperse them evenly, control the temperature at 75-85°C, add component 1 and seed monomer component 1, and keep warm for 0.2-0.4h; add seed monomer component 2 and benzoyl peroxide 2, keep warm for 0.5-1h, add shell monomer, keep warm for 6-9h, adjust the pH to 7-8, filter the material, and obtain modified hydroxy acrylic resin.

2. The wear-resistant and highly elastic colored polyurethane coating according to claim 1, characterized in that: The addition ratio of 3-m-chloroperbenzoic acid, dichloromethane 1, octavinylsilsesquioxane, and dichloromethane 2 in S1 is 0.75-1.5 g: 10-20 mL: 10 g: 100-150 mL.

3. The wear-resistant and highly elastic colored polyurethane coating according to claim 1, characterized in that: The addition ratio of epoxidized octavinyl silsesquioxane, modified graphene oxide, and anhydrous ethanol in S2 is 1-1.5 g: 10 g: 100-200 mL.

4. The wear-resistant and highly elastic colored polyurethane coating according to claim 1, characterized in that: The composite emulsifier in S3 is a mixture of sodium dodecyl benzene diphenyl ether disulfonate and sodium 2-acrylamido-2-methylpropane sulfonate in a mass ratio of 1:1-2; The seed monomer component 1 and the seed monomer component 2 are both obtained by mixing methyl methacrylate and butyl acrylate in a mass ratio of 3:1-2; the mass ratio of the seed monomer component 1 to the seed monomer component 2 is 10:90; The shell monomer is obtained by mixing methacrylic acid, hydroxyethyl acrylate and hydroxypropyl acrylate in a mass ratio of 16-24:68-100:65-100; The addition ratio of composite emulsifier, deionized water, benzoyl peroxide 1, component 1, seed monomer component 1, benzoyl peroxide 2, and shell monomer is 0.75-1.5g: 50-75mL: 0.04-0.06g: 2-5g: 1-2g: 0.05-0.1g: 22-32g.

5. The wear-resistant and highly elastic colored polyurethane coating according to claim 1, characterized in that: The preparation method of the modified graphene oxide comprises the following steps: A1: Add graphene oxide and concentrated ammonia water into a reaction bottle and disperse them evenly. Control the temperature at 45-55°C, keep the temperature for 4-10 hours, cool to room temperature, filter, wash with water until neutral, and vacuum dry to obtain aminated graphene oxide. A2: Add aminated graphene oxide and deionized water into a reactor and disperse them evenly. Mix aniline and hydrochloric acid solution 1 and add them into the reactor and disperse them evenly. Mix ammonium persulfate and hydrochloric acid solution 2 and add them into the reactor and disperse them evenly. Control the temperature at 0-5°C, keep the reaction warm for 9-12h, filter, wash until neutral, and dry to obtain modified graphene oxide.

6. The wear-resistant and highly elastic colored polyurethane coating according to claim 5, characterized in that: In A2, hydrochloric acid solution 1 and hydrochloric acid solution 2 are both 1.5-2.5 mol / L hydrochloric acid aqueous solutions; the addition ratio of aminated graphene oxide, deionized water, aniline, hydrochloric acid solution 1, ammonium persulfate, and hydrochloric acid solution 2 is 10g: 150-250mL: 8-12g: 120-180mL: 15-20g: 20-30mL.

7. The wear-resistant and highly elastic colored polyurethane coating according to claim 1, characterized in that: The mass ratio of the main agent to the curing agent in the polyurethane floor finishing paint is 100:60-100.

8. The wear-resistant and highly elastic colored polyurethane coating according to claim 1, characterized in that: The auxiliary agent is obtained by mixing a defoamer, a wetting and leveling agent, a thickener and a dispersant in a mass ratio of 0.3-0.4:0.2-0.4:0.5-0.8:0.5-1.

9. The wear-resistant and highly elastic colored polyurethane coating according to claim 1, characterized in that: The curing agent is a hydrophilic modified polyisocyanate curing agent; the preparation method of the hydrophilic modified polyisocyanate curing agent comprises the following steps: in a nitrogen atmosphere, adding HDI trimer into a reaction kettle, controlling the temperature at 70-80°C, adding polyethylene glycol monomethyl ether, keeping the temperature for reaction for 3-4 hours, adding benzoyl chloride to stop the reaction, and obtaining the hydrophilic modified polyisocyanate curing agent.

10. The wear-resistant and highly elastic colored polyurethane coating according to claim 9, characterized in that: In the preparation process of the hydrophilic modified polyisocyanate curing agent, the added molar ratio of HD I trimer and polyethylene glycol monomethyl ether is n(-NCO):n(-OH)=6-8:1.

Images