A high entropy coating for architectural glass coating and preparation method thereof

Abstract

The present invention belongs to the field of coatings and discloses a high-entropy coating for architectural glass coatings and a preparation method thereof. The high-entropy coating is composed of the following raw materials in parts by weight: 25-30 parts of high-entropy material powder; 10-15 parts of coated titanium dioxide powder; 20-30 parts of alcohol-soluble acrylate resin; 10-15 parts of anhydrous ethanol; 3-7 parts of polymethacrylate ammonium salt dispersant; 6-8 parts of polyether-modified organosilicon leveling agent; 4-6 parts of polyether-modified silicone defoamer; 3-5 parts of associative polyurethane thickener; 8-10 parts of benzotriazole ultraviolet absorber; 1-4 parts of sodium tetraborate; 4-5 parts of mixed phosphate; and 1-4 parts of potassium hydrogen phthalate. The high-entropy coating for architectural glass coatings of the present invention can comprehensively address the shortcomings of existing coatings and has important practical significance and broad application prospects.

Description

Technical Field

[0001] The invention belongs to the field of coatings, and in particular relates to a high-entropy coating for architectural glass coating and a preparation method thereof. Background Art

[0002] Architectural glass is widely used in residential buildings, office buildings, stadiums, and other venues. It not only impacts a building's aesthetics but is also closely linked to its functionality. With increasing demands for environmental comfort and energy efficiency in buildings, architectural glass coating technology has become a research hotspot. Architectural glass coating technology aims to impart various superior properties to glass, such as thermal insulation, wear resistance, and anti-condensation and icing properties, thereby enhancing the overall performance and user experience of a building.

[0003] Traditionally, architectural glass protection and maintenance has relied on methods such as thermal insulation film, conventional thermal insulation coatings, and manual cleaning. Thermal insulation film reduces heat transfer by applying a thin, insulating film to the glass surface. Conventional thermal insulation coatings utilize the insulating ingredients in the coating to form an insulating layer on the glass surface, achieving a certain degree of insulation. Manual cleaning involves regularly wiping the glass to keep it clean and reduce the impact of dirt on its performance.

[0004] High-entropy coatings, an emerging branch of coating technology, leverage their unique multi-principal-element synergistic effect to form a highly disordered and uniform solid solution structure at the atomic scale, endowing them with excellent physical and chemical properties, including high stability, UV resistance, thermal insulation, corrosion resistance, and self-cleaning properties. This high mixing entropy effect enhances the coating's environmental adaptability, enabling it to maintain stable performance under frequently changing temperature and humidity conditions. At the same time, lattice distortion improves its ability to block ultraviolet and infrared wavelengths, thereby reducing indoor temperature rise. Furthermore, the coating's superhydrophobicity effectively prevents condensation, frost, and ice, ensuring the safety and normal use of glass buildings. However, relatively few existing documents have reported the use of high-entropy materials in architectural glass coatings, and there is an urgent need to develop a high-entropy material for architectural glass coatings. Summary of the Invention

[0005] The present invention aims to provide a high entropy coating for architectural glass coating and a method for preparing the high entropy coating.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: high entropy material powder: 25-30 parts;

[0008] Coated titanium dioxide powder: 10-15 parts;

[0009] Alcohol-soluble acrylic resin: 20-30 parts;

[0010] Anhydrous ethanol: 10-15 parts;

[0011] Polymethacrylate ammonium salt dispersant: 3-7 parts;

[0012] Polyether modified silicone leveling agent: 6-8 parts;

[0013] Polyether modified silicone defoamer: 4-6 parts;

[0014] Associative polyurethane thickener: 3-5 parts;

[0015] Benzotriazole ultraviolet absorber: 8-10 parts;

[0016] Sodium tetraborate: 1-4 parts;

[0017] Mixed phosphate: 4-5 parts;

[0018] 1-4 parts of potassium hydrogen phthalate;

[0019] The metal elements in the high entropy material powder include at least three of iron, nickel, cobalt, copper, palladium, manganese, zinc, and chromium, and the atomic ratios of the metal elements are equal;

[0020] The mixed phosphate is composed of the following raw materials in weight percentage: 30-50% zinc phosphate; 20-40% calcium phosphate; 10-30% sodium tripolyphosphate;

[0021] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, dispersing the titanium dioxide powder under ultrasonication at 60-80 kHz for 30-60 minutes, stirring the mixture at 60-80° C. for reaction for 2-3 hours, and drying the mixture; wherein the mass of the silane coupling agent is 3%-5% of the mass of the ethanol solution of the silane coupling agent; and the mass of the titanium dioxide powder is 10-12% of the mass of the ethanol solution of the silane coupling agent.

[0022] Preferably, a high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: high entropy material powder: 27-30 parts;

[0023] Coated titanium dioxide powder: 10-12 parts;

[0024] Alcohol-soluble acrylate resin: 22-25 parts;

[0025] Anhydrous ethanol: 13-15 parts;

[0026] Polymethacrylate ammonium salt dispersant: 4-6 parts;

[0027] Polyether modified silicone leveling agent: 6-8 parts;

[0028] Polyether modified silicone defoamer: 4-6 parts;

[0029] Associative polyurethane thickener: 3-5 parts;

[0030] Benzotriazole ultraviolet absorber: 8-10 parts;

[0031] Sodium tetraborate: 2-3 parts;

[0032] Mixed phosphate: 4-5 parts;

[0033] 2-3 parts of potassium hydrogen phthalate;

[0034] The metal elements in the high entropy material powder include at least three of iron, nickel, cobalt, copper, palladium, manganese, zinc, and chromium, and the atomic ratios of the metal elements are equal;

[0035] The mixed phosphate is composed of the following raw materials in weight percentage: zinc phosphate 40-50%; calcium phosphate 30-40%; sodium tripolyphosphate 10-20%;

[0036] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, dispersing the titanium dioxide powder under ultrasonication at 70-80 kHz for 30-40 minutes, stirring the mixture at 60-80° C. for reaction for 2-3 hours, and drying the mixture; wherein the mass of the silane coupling agent is 3%-4% of the mass of the ethanol solution of the silane coupling agent; and the mass of the titanium dioxide powder is 10-11% of the mass of the ethanol solution of the silane coupling agent.

[0037] Preferably, a high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: high entropy material powder: 30 parts;

[0038] Coated titanium dioxide powder: 10 parts;

[0039] Alcohol-soluble acrylate resin: 25 parts;

[0040] Anhydrous ethanol: 15 parts;

[0041] Polymethacrylate ammonium salt dispersant: 5 parts;

[0042] Polyether modified silicone leveling agent: 8 parts;

[0043] Polyether modified silicone defoamer: 6 parts;

[0044] Associative polyurethane thickener: 5 parts;

[0045] Benzotriazole ultraviolet absorber: 10 parts;

[0046] Sodium tetraborate: 2 parts;

[0047] Mixed phosphate: 5 parts;

[0048] 2 parts of potassium hydrogen phthalate;

[0049] The metal elements in the high entropy material powder include at least three of iron, nickel, cobalt, copper, palladium, manganese, zinc, and chromium, and the atomic ratios of the metal elements are equal;

[0050] The mixed phosphate is composed of the following raw materials in weight percentage: 40% zinc phosphate; 40% calcium phosphate; 20% sodium tripolyphosphate;

[0051] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, dispersing the titanium dioxide powder under 80kHz ultrasonication for 30 minutes, stirring the mixture at 60-80°C for 2-3 hours, and drying the mixture; wherein the mass of the silane coupling agent is 3% of the mass of the ethanol solution of the silane coupling agent; and the mass of the titanium dioxide powder is 10% of the mass of the ethanol solution of the silane coupling agent. The silane coupling agent can form an organic film on the surface of the titanium dioxide, thereby enhancing its compatibility with organic matter in the coating system and improving dispersion stability.

[0052] In order to achieve better results, preferably, the high entropy material powder is prepared by the following method: mixing various metal salts or complexes containing a single metal element in an equiatomic ratio of the metal elements to form a metal salt mixture, ultrasonically mixing the metal salt mixture with an ethanol solution for 2 hours, and freeze-drying to obtain a mixed salt; spreading the mixed salt evenly between two pieces of carbon paper, applying a 500A current shock to reduce and alloy the metal salt in situ, collecting and cleaning to obtain the high entropy material powder; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%; the frequency of the ultrasound is 80kHz.

[0053] Preferably, the particle size of the titanium dioxide powder is 5-50 nm.

[0054] In order to achieve better effects, preferably, the particle size of the titanium dioxide powder is 20-30 nm.

[0055] Preferably, the alcohol-soluble acrylic resin is composed of the following components by mass percentage: anhydrous ethanol: 35%, azobisisobutyronitrile: 22%, methyl methacrylate: 13%, butyl acrylate: 15%, and butyl methacrylate: 15%;

[0056] The preparation method of the alcohol-soluble acrylate resin is specifically performed as follows:

[0057] (1) Add all the anhydrous ethanol to a 500 ml three-necked flask, add half the amount of azobisisobutyronitrile, and heat the three-necked flask to 85-88 ° C. and control the rotation speed to 800-810 rpm;

[0058] (2) Mix methyl methacrylate, butyl acrylate, butyl methacrylate, and the other half of azobisisobutyronitrile, and add the mixed mixture into a 120 ml constant pressure burette;

[0059] (3) titrating the mixed solution in the constant pressure burette into the three-necked flask at a uniform rate, controlling the titration time to be 50-60 min. After the titration is completed, reacting at a constant temperature for 5-6 h, and discharging the material to obtain an alcohol-soluble acrylate resin.

[0060] The method for preparing the high entropy coating for architectural glass coating comprises the following steps:

[0061] S1. Mix 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high-entropy material powder, and anhydrous ethanol in a high-speed disperser. Then, disperse the mixture in a ball mill to a 1000-3000 mesh size. Transfer the mixture to an ultrasonic generator. Add the coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant. Continue dispersing the mixture in the ultrasonic generator at 80 kHz for 1-2 hours to prepare a high-entropy material slurry.

[0062] S2. Add the high-entropy material slurry to the alcohol-soluble acrylic resin and stir at 800-900 r / min for 15-20 minutes. Then, add the polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener, and benzotriazole UV absorber and stir at 1200-1300 r / min for 10-15 minutes to prepare a primary mixed slurry. Transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 200-800 r / min for 30-40 minutes.

[0063] The polycarboxylate polymer dispersant used in this invention is designed to enhance the synergistic dispersion of titanium dioxide and the high-entropy material. Specifically, a polymethacrylate ammonium salt dispersant with a molecular weight of 5,000-10,000 is used. This dispersant comprises a long chain structure formed by polymerizing methacrylic acid monomers, which imparts a strong steric hindrance to the dispersant. In the coating system, these long chains form a thick adsorption layer on the surfaces of the high-entropy nanoparticles and titanium dioxide particles. When the particles approach each other, the repulsive force between the adsorption layers prevents particle aggregation, ensuring uniform and stable dispersion of the particles throughout the system.

[0064] To overcome the effect of titanium dioxide on the coating's leveling properties, the present invention uses a polyether-modified silicone leveling agent, which has enhanced leveling and surface activity. This leveling agent reduces the coating's surface tension, allowing it to spread more evenly on the glass surface, ensuring the coating's smoothness and gloss, while also maintaining the self-cleaning properties of titanium dioxide.

[0065] The phosphate composition in this invention is reasonable. Zinc phosphate, through its chemical activity, forms a chemical bond between the coating and the glass surface, enhancing the coating's adhesion. This allows the high-entropy coating to adhere more firmly to the glass, resisting daily friction and environmental erosion, and extending the coating's service life. Calcium phosphate also modifies the coating's hardness and wear resistance to a certain extent. Sodium tripolyphosphate has excellent dispersibility, helping to more evenly disperse high-entropy material powders, coated titanium dioxide powders, and other materials within the coating system.

[0066] The polyether-modified silicone defoamer of the present invention combines the efficient defoaming properties of silicone with the good compatibility of polyether, can quickly eliminate microbubbles, and avoid the risk of shrinkage holes in traditional silicone defoamers. At the same time, because the coating needs to adapt to changes in temperature and humidity, the polyether-modified silicone remains stable over a wide temperature range.

[0067] The associative polyurethane thickener in this invention exhibits shear-thinning properties, improving the fluidity of the coating during application while preventing pigment settling upon standing, meeting the uniformity requirements of architectural glass coatings. It also exhibits excellent compatibility with alcohol-soluble acrylate resin systems, avoiding delamination or turbidity caused by inappropriate thickener selection. Regarding aging resistance, the polyurethane thickener inherently exhibits good hydrolysis and weathering resistance, enhancing long-term stability.

[0068] Compared with the prior art, the advantages of the present invention are:

[0069] 1. High entropy material (HEM) powder leverages a unique multi-principal element synergistic effect to form a highly disordered yet uniform solid solution structure at the atomic scale. Lattice distortion enhances UV and infrared radiation blocking capabilities, effectively reducing indoor temperature rise and imparting excellent thermal insulation to the coating. Titanium dioxide coating also contributes to thermal insulation, working synergistically with the HEM powder to further enhance the overall insulation effect, resulting in superior thermal insulation performance for the finished glass.

[0070] 2. The addition of high-entropy material powder imparts excellent adhesion, wear resistance, and hardness to the coating. The unique structure of the high-entropy alloy imparts high mechanical strength to the coating, enabling it to withstand external forces such as friction and scratching during actual use, thereby extending the coating's service life.

[0071] 3. The high mixing entropy effect of high-entropy material powder enhances the environmental adaptability of the coating, enabling it to maintain stable performance under frequently changing temperature and humidity conditions, effectively improving the anti-aging performance and reducing problems such as coating aging and deterioration caused by environmental factors.

[0072] 4. The organic film on the coated titanium dioxide surface enhances its compatibility with organic matter in the coating system. Furthermore, titanium dioxide itself possesses photocatalytic self-cleaning properties. Under light, it can decompose organic surface dirt, keeping the glass surface clean. The presence of high-entropy materials may also indirectly promote this self-cleaning property.

[0073] The high-entropy material for architectural glass coatings of the present invention can comprehensively solve the deficiencies of existing coatings and has important practical significance and broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 The optical images of the glass with the coatings of Example 1 of the present invention and Comparative Example 1 when droplets are loaded on the glass surface;

[0075] Figure 2 A high-angle annular dark field image and its corresponding energy dispersion spectrum image taken with a transmission electron microscope of the high-entropy material powder of Example 2 of the present invention;

[0076] Figure 3 The transmittance of the glass sprayed with the high entropy material coating of Example 1 of the present invention and the glass sprayed with the coating of Comparative Example 2 at different wavelengths. DETAILED DESCRIPTION

[0077] The present invention will be further described below with reference to the embodiments, but the protection scope of the present invention is not limited thereto.

[0078] The alcohol-soluble acrylic resin described in the following examples is composed of the following components by mass percentage: anhydrous ethanol: 35%, azobisisobutyronitrile: 22%, methyl methacrylate: 13%, butyl acrylate: 15%, and butyl methacrylate: 15%;

[0079] The preparation method of the alcohol-soluble acrylate resin is as follows:

[0080] (1) Add all the anhydrous ethanol to a 500 ml three-necked flask, add half the amount of azobisisobutyronitrile, and heat the three-necked flask to 85-88 ° C. and control the rotation speed to 800-810 rpm;

[0081] (2) Mix methyl methacrylate, butyl acrylate, butyl methacrylate and the other half of azobisisobutyronitrile, and add the mixed mixture into a 120 ml constant pressure burette;

[0082] (3) titrating the mixed solution in the constant pressure burette into the three-necked flask at a uniform rate, controlling the titration time to be 50-60 min. After the titration is completed, reacting at a constant temperature for 5-6 h, and discharging the material to obtain an alcohol-soluble acrylate resin. Example 1

[0083] A high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: 30 parts of high entropy material powder;

[0084] Coated titanium dioxide powder: 10 parts;

[0085] Alcohol-soluble acrylate resin: 25 parts;

[0086] Anhydrous ethanol: 15 parts;

[0087] Polymethacrylate ammonium salt dispersant: 5 parts;

[0088] Polyether modified silicone leveling agent: 8 parts;

[0089] Polyether modified silicone defoamer: 6 parts;

[0090] Associative polyurethane thickener: 5 parts;

[0091] Benzotriazole ultraviolet absorber: 10 parts;

[0092] Sodium tetraborate: 2 parts;

[0093] Mixed phosphate: 5 parts; the mixed phosphate is composed of the following raw materials in percentage by weight: zinc phosphate 40%; calcium phosphate 40%; sodium tripolyphosphate 20%;

[0094] 2 parts of potassium hydrogen phthalate;

[0095] The metal elements in the high entropy material powder include iron, nickel, cobalt, copper, and palladium, and the atomic ratios of the metal elements are equal;

[0096] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, dispersing the titanium dioxide powder under 80kHz ultrasonic conditions for 30 minutes, stirring the mixture at 60°C for 2 hours, and drying the mixture to obtain the coated titanium dioxide powder; wherein the mass of the silane coupling agent is 3% of the mass of the ethanol solution of the silane coupling agent; the mass of the titanium dioxide powder is 10% of the mass of the ethanol solution of the silane coupling agent; and the particle size of the titanium dioxide powder is 20 nm.

[0097] The high entropy material powder is prepared by the following method: five salts, namely ferric chloride, nickel chloride, cobalt chloride, copper chloride and palladium chloride, are mixed in an equiatomic ratio to form a metal salt mixture, the metal salt mixture is ultrasonically mixed with an ethanol solution for 2 hours, and the mixed salt FeNiCoCuPt is obtained after freeze-drying; the mixed salt FeNiCoCuPt is evenly spread between two pieces of carbon paper, a 500A current shock is applied to reduce and alloy the metal salts in situ, and the high entropy material (HEM) powder is collected and cleaned; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%, and the frequency of the ultrasound is 80kHz.

[0098] The method for preparing the high entropy coating for architectural glass coating comprises the following steps:

[0099] S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high-entropy material powder, and anhydrous ethanol are mixed in a high-speed disperser. The mixture is then dispersed in a ball mill to a 2000-mesh size and transferred to an ultrasonic generator. The coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant are then added. The mixture is then dispersed in an ultrasonic generator at 80 kHz for one hour to prepare a high-entropy material slurry for later use. This step-by-step dispersion method ensures that the high-entropy nanoparticles and titanium dioxide are fully dispersed separately, preventing interference between the two during the dispersion process and ensuring their respective dispersion effects and performance.

[0100] S2. Add the high-entropy material slurry to the alcohol-soluble acrylic resin and stir at 800 r / min for 15 minutes. Then, add the polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener, and benzotriazole UV absorber and stir at 1200 r / min for 10 minutes to prepare a primary mixed slurry. Transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 800 r / min for 30 minutes to ensure sufficient reaction and uniform mixing. Example 2

[0101] A high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: high entropy material powder: 25 parts;

[0102] Coated titanium dioxide powder: 10 parts;

[0103] Alcohol-soluble acrylate resin: 30 parts;

[0104] Anhydrous ethanol: 10 parts;

[0105] Polymethacrylate ammonium salt dispersant: 5 parts;

[0106] Polyether modified silicone leveling agent: 7 parts;

[0107] Polyether modified silicone defoamer: 5 parts;

[0108] Associative polyurethane thickener: 3 parts;

[0109] Benzotriazole ultraviolet absorber: 8 parts;

[0110] Sodium tetraborate: 2 parts;

[0111] Mixed phosphate: 5 parts; the mixed phosphate is composed of the following raw materials in percentage by weight: 30% zinc phosphate; 40% calcium phosphate; 30% sodium tripolyphosphate;

[0112] 2 parts of potassium hydrogen phthalate;

[0113] The metal elements in the high entropy material powder include manganese, iron, cobalt, nickel and copper, and the atomic ratios of the metal elements are equal;

[0114] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, subjecting the titanium dioxide powder to ultrasonic dispersion at 60 kHz for 60 minutes, stirring and reacting the solution at 80° C. for 3 hours, and drying the solution to obtain the coated titanium dioxide powder; wherein the mass of the silane coupling agent is 5% of the mass of the ethanol solution of the silane coupling agent; the mass of the titanium dioxide powder is 12% of the mass of the ethanol solution of the silane coupling agent; and the particle size of the titanium dioxide powder is 10 nm.

[0115] The high entropy material powder is prepared by the following method: manganese acetate, iron acetate, cobalt acetate, nickel acetate and copper acetate are mixed in an equiatomic ratio to form a metal salt mixture, the metal salt mixture is ultrasonically mixed with an ethanol solution for 2 hours, and the mixed salt MnFeCoNiCu is obtained after freeze-drying; the mixed salt MnFeCoNiCu is evenly spread between two pieces of carbon paper, a 500A current shock is applied to reduce and alloy the metal salts in situ, and the high entropy material (HEM) powder is collected and cleaned; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%, and the frequency of the ultrasound is 80kHz.

[0116] The method for preparing the high entropy coating for architectural glass coating comprises the following steps:

[0117] S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high-entropy material powder, and anhydrous ethanol are mixed in a high-speed disperser. The mixture is then dispersed in a ball mill to a 1000-mesh size and transferred to an ultrasonic generator. The coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant are then added. The mixture is then dispersed in an ultrasonic generator at 80 kHz for 2 hours to prepare a high-entropy material slurry for later use. This step-by-step dispersion method ensures that the high-entropy nanoparticles and titanium dioxide are fully dispersed separately, preventing interference between the two during the dispersion process and ensuring their respective dispersion effects and performance.

[0118] S2. Add the high-entropy material slurry to the alcohol-soluble acrylic resin and stir at 900 r / min for 20 minutes. Then, add the polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener, and benzotriazole UV absorber and stir at 1300 r / min for 15 minutes to prepare a primary mixed slurry. Transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 200 r / min for 40 minutes to ensure sufficient reaction and uniform mixing. Example 3

[0119] A high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: high entropy material powder: 27 parts;

[0120] Coated titanium dioxide powder: 12 parts;

[0121] Alcohol-soluble acrylate resin: 20 parts;

[0122] Anhydrous ethanol: 13 parts;

[0123] Polymethacrylate ammonium salt dispersant: 7 parts;

[0124] Polyether modified silicone leveling agent: 6 parts;

[0125] Polyether modified silicone defoamer: 4 parts;

[0126] Associative polyurethane thickener: 4 parts;

[0127] Benzotriazole ultraviolet absorber: 9 parts;

[0128] Sodium tetraborate: 1 part;

[0129] Mixed phosphate: 4 parts; the mixed phosphate is composed of the following raw materials in percentage by weight: 50% zinc phosphate; 20% calcium phosphate; 20% sodium tripolyphosphate;

[0130] 4 parts of potassium hydrogen phthalate;

[0131] The metal elements in the high entropy material powder include manganese, iron, cobalt, nickel and zinc, and the atomic ratio of each metal element is equal;

[0132] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, subjecting the mixture to ultrasonic dispersion at 70 kHz for 40 minutes, stirring the mixture at 70° C. for reaction for 2 hours, and drying the mixture to obtain the coated titanium dioxide powder; wherein the mass of the silane coupling agent is 4% of the mass of the ethanol solution of the silane coupling agent; the mass of the titanium dioxide powder is 11% of the mass of the ethanol solution of the silane coupling agent; and the particle size of the titanium dioxide powder is 30 nm.

[0133] The high entropy material powder is prepared by the following method: manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate and zinc nitrate are mixed in an equiatomic ratio to form a metal salt mixture, the metal salt mixture is ultrasonically mixed with an ethanol solution for 2 hours, and the mixed salt MnFeCoNiZn is obtained after freeze-drying; the mixed salt MnFeCoNiZn is evenly spread between two pieces of carbon paper, a 500A current shock is applied to reduce and alloy the metal salts in situ, and the high entropy material (HEM) powder is collected and cleaned; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%, and the frequency of the ultrasound is 80kHz.

[0134] The method for preparing the high entropy coating for architectural glass coating comprises the following steps:

[0135] S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high-entropy material powder, and anhydrous ethanol are mixed in a high-speed disperser. The mixture is then dispersed in a ball mill to a 3000-mesh size and transferred to an ultrasonic generator. The coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant are then added. The mixture is then dispersed in an ultrasonic generator at 80 kHz for 2 hours to prepare a high-entropy material slurry for later use. This step-by-step dispersion method ensures that the high-entropy nanoparticles and titanium dioxide are fully dispersed separately, preventing interference between the two during the dispersion process and ensuring their respective dispersion effects and performance.

[0136] S2. Add the high-entropy material slurry to the alcohol-soluble acrylic resin and stir at 800 r / min for 18 minutes. Then, add the polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener, and benzotriazole UV absorber and stir at 1200 r / min for 15 minutes to prepare a primary mixed slurry. Transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 600 r / min for 35 minutes to ensure sufficient reaction and uniform mixing. Example 4

[0137] A high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: high entropy material powder: 28 parts;

[0138] Coated titanium dioxide powder: 13 parts;

[0139] Alcohol-soluble acrylate resin: 22 parts;

[0140] Anhydrous ethanol: 12 parts;

[0141] Polymethacrylate ammonium salt dispersant: 3 parts;

[0142] Polyether modified silicone leveling agent: 6 parts;

[0143] Polyether modified silicone defoamer: 5 parts;

[0144] Associative polyurethane thickener: 4 parts;

[0145] Benzotriazole ultraviolet absorber: 10 parts;

[0146] Sodium tetraborate: 3 parts;

[0147] Mixed phosphate: 5 parts; the mixed phosphate is composed of the following raw materials in percentage by weight: 50% zinc phosphate; 40% calcium phosphate; 10% sodium tripolyphosphate;

[0148] 3 parts of potassium hydrogen phthalate;

[0149] The metal elements in the high entropy material powder include chromium, iron, cobalt, nickel and zinc, and the atomic ratios of the metal elements are equal;

[0150] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, dispersing the titanium dioxide powder under 80kHz ultrasonic conditions for 30 minutes, stirring the mixture at 60°C for 2 hours, and drying the mixture to obtain the coated titanium dioxide powder; wherein the mass of the silane coupling agent is 3% of the mass of the ethanol solution of the silane coupling agent; the mass of the titanium dioxide powder is 10% of the mass of the ethanol solution of the silane coupling agent; and the particle size of the titanium dioxide powder is 50 nm.

[0151] The high entropy material powder is prepared by the following method: five salts of chromium acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and zinc acetylacetonate are mixed in an equiatomic ratio to form a metal salt mixture, the metal salt mixture is ultrasonically mixed with an ethanol solution for 2 hours, and the mixed salt CrFeNiCoZn is obtained after freeze-drying; the mixed salt CrFeNiCoZn is evenly spread between two pieces of carbon paper, a 500A current shock is applied to reduce and alloy the metal salts in situ, and the high entropy material (HEM) powder is collected and cleaned; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%, and the frequency of the ultrasound is 80kHz.

[0152] The method for preparing the high entropy coating for architectural glass coating comprises the following steps:

[0153] S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high-entropy material powder, and anhydrous ethanol are mixed in a high-speed disperser. The mixture is then dispersed in a ball mill to a 1000-mesh size and transferred to an ultrasonic generator. The coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant are then added. The mixture is then dispersed in an ultrasonic generator at 80 kHz for 2 hours to prepare a high-entropy material slurry for later use. This step-by-step dispersion method ensures that the high-entropy nanoparticles and titanium dioxide are fully dispersed separately, preventing interference between the two during the dispersion process and ensuring their respective dispersion effects and performance.

[0154] S2. Add the high-entropy material slurry to the alcohol-soluble acrylic resin and stir at 800 r / min for 15 minutes. Then, add the polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener, and benzotriazole UV absorber and stir at 1200 r / min for 10 minutes to prepare a primary mixed slurry. Transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 500 r / min for 35 minutes to ensure sufficient reaction and uniform mixing. Example 5

[0155] A high entropy coating for architectural glass coating is composed of the following raw materials in parts by weight: 30 parts of high entropy material powder;

[0156] Coated titanium dioxide powder: 10 parts;

[0157] Alcohol-soluble acrylate resin: 20 parts;

[0158] Anhydrous ethanol: 10 parts;

[0159] Polymethacrylate ammonium salt dispersant: 5 parts;

[0160] Polyether modified silicone leveling agent: 6 parts;

[0161] Polyether modified silicone defoamer: 4 parts;

[0162] Associative polyurethane thickener: 5 parts;

[0163] Benzotriazole ultraviolet absorber: 8 parts;

[0164] Sodium tetraborate: 2 parts;

[0165] Mixed phosphate: 5 parts; the mixed phosphate is composed of the following raw materials in percentage by weight: zinc phosphate 40%; calcium phosphate 30%; sodium tripolyphosphate 30%;

[0166] 2 parts of potassium hydrogen phthalate;

[0167] The metal elements in the high entropy material powder include chromium, iron, and cobalt, and the atomic ratios of the metal elements are equal;

[0168] The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, subjecting the mixture to ultrasonic dispersion at 70 kHz for 50 minutes, stirring the mixture at 80° C. for reaction for 3 hours, and drying the mixture to obtain the coated titanium dioxide powder; wherein the mass of the silane coupling agent is 3% of the mass of the ethanol solution of the silane coupling agent; the mass of the titanium dioxide powder is 10% of the mass of the ethanol solution of the silane coupling agent; and the particle size of the titanium dioxide powder is 5 nm.

[0169] The high entropy material powder is prepared by the following method: three salts of chromium acetylacetonate, iron acetylacetonate, and cobalt acetylacetonate are mixed in an equiatomic ratio to form a metal salt mixture, the metal salt mixture is ultrasonically mixed with an ethanol solution for 2 hours, and the mixed salt CrFeCo is obtained after freeze-drying; the mixed salt CrFeCo is evenly spread between two pieces of carbon paper, a 500A current shock is applied to reduce and alloy the metal salts in situ, and the high entropy material (HEM) powder is collected and cleaned; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%, and the frequency of the ultrasound is 80kHz.

[0170] The method for preparing the high entropy coating for architectural glass coating comprises the following steps:

[0171] S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high-entropy material powder, and anhydrous ethanol are mixed in a high-speed disperser. The mixture is then dispersed in a ball mill to a 2000-mesh size and transferred to an ultrasonic generator. The coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant are then added. The mixture is then dispersed in an ultrasonic generator at 80 kHz for 2 hours to prepare a high-entropy material slurry for later use. This step-by-step dispersion method ensures that the high-entropy nanoparticles and titanium dioxide are fully dispersed separately, preventing interference between the two during the dispersion process and ensuring their respective dispersion effects and performance.

[0172] S2. Add the high-entropy material slurry to the alcohol-soluble acrylic resin and stir at 900 r / min for 20 minutes. Then, add the polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener, and benzotriazole UV absorber and stir at 1300 r / min for 10 minutes to prepare a primary mixed slurry. Transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 400 r / min for 40 minutes to ensure sufficient reaction and uniform mixing.

[0173] Comparative Example 1

[0174] A building glass coating is composed of the following raw materials in parts by weight: 10 parts of coated titanium dioxide powder, 25 parts of alcohol-soluble acrylate resin, 15 parts of anhydrous ethanol, 5 parts of polymethacrylate ammonium salt dispersant, 8 parts of polyether-modified organic silicone leveling agent, 6 parts of polyether-modified silicone defoamer, 5 parts of associative polyurethane thickener, 10 parts of benzotriazole ultraviolet absorber, 2 parts of sodium tetraborate, 5 parts of mixed phosphate, and 2 parts of potassium hydrogen phthalate; the mixed phosphate is composed of the following raw materials in the following weight percentages: 40% zinc phosphate; 40% calcium phosphate; and 20% sodium tripolyphosphate.

[0175] The production method of the coated titanium dioxide powder is the same as that in Example 1.

[0176] The preparation method of the above-mentioned architectural glass coating comprises the following steps:

[0177] S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant and anhydrous ethanol are sent to a high-speed disperser for mixing, and then dispersed to 2000 mesh in a ball mill and transferred to an ultrasonic generator. Then, the coated titanium dioxide powder and the remaining dispersant are added, and the mixture is continued to be dispersed in the ultrasonic generator at a frequency of 80 kHz for 1 hour to obtain a slurry for stand-by use.

[0178] S2. Add the prepared slurry to an alcohol-soluble acrylic resin and stir at 800 r / min for 15 minutes to uniformly mix the ingredients. Then add a polyether-modified silicone leveling agent, a polyether-modified silicone defoamer, an associative polyurethane thickener, and a benzotriazole ultraviolet absorber, increase the stirring speed to 1200 r / min, stir for 10 minutes, and strengthen the mixing effect to obtain a pre-mixed slurry. Transfer the pre-mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 800 r / min for 30 minutes to ensure that the system is fully reacted and uniformly mixed to obtain an architectural glass coating.

[0179] Comparative Example 2

[0180] A building glass coating is composed of the following raw materials in parts by weight: 30 parts of high-entropy material powder, 25 parts of alcohol-soluble acrylate resin, 15 parts of anhydrous ethanol, 5 parts of polymethacrylate ammonium salt dispersant, 8 parts of polyether-modified organic silicone leveling agent, 6 parts of polyether-modified silicone defoamer, 5 parts of associative polyurethane thickener, 10 parts of benzotriazole ultraviolet absorber, 2 parts of sodium tetraborate, 5 parts of mixed phosphate, and 2 parts of potassium hydrogen phthalate; the mixed phosphate is composed of the following raw materials in the following weight percentages: 40% zinc phosphate; 40% calcium phosphate; and 20% sodium tripolyphosphate.

[0181] The high-entropy material is prepared by the following method: five salts, namely, ferric chloride, nickel chloride, cobalt chloride, copper chloride and palladium chloride, are mixed in an equiatomic ratio of metal elements to form a metal salt mixture, the metal salt mixture is ultrasonically mixed with an ethanol solution for 2 hours, and the mixed salt FeNiCoCuPt is obtained after freeze-drying; the mixed salt FeNiCoCuPt is evenly spread between two pieces of carbon paper, a 500A current shock is applied to reduce and alloy the metal salts in situ, and the high-entropy material powder is collected and cleaned; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%, and the frequency of the ultrasound is 80kHz.

[0182] The method for preparing the coating for architectural glass coating comprises the following steps:

[0183] S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high entropy material powder, and anhydrous ethanol are sent to a high-speed disperser for mixing, and then dispersed to 2000 mesh in a ball mill and transferred to an ultrasonic generator. Continue to disperse in the ultrasonic generator at a frequency of 80 kHz for 1 hour to prepare a slurry for stand-by use.

[0184] S2, the prepared slurry is added to an alcohol-soluble acrylic resin, first stirred at a speed of 800r / min for 15 minutes to make the components preliminarily mixed. Then add polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener and benzotriazole ultraviolet absorber, increase the stirring speed to 1200r / min, stir for 10 minutes, strengthen the mixing effect, and prepare a pre-mixed slurry. The pre-mixed slurry is transferred to a magnetic stirrer and sodium tetraborate, mixed phosphate and potassium hydrogen phthalate are added, and stirred at 800r / min for 30 minutes to ensure that the system is fully reacted and mixed to obtain a coating for architectural glass.

[0185] In order to verify the performance of the coating for architectural glass coating of the present invention, the products of Example 1 and Comparative Example 1 were applied to the glass surface. The specific construction process was as follows: (1) glass cleaning agent was evenly sprayed on the glass surface to be coated with the architectural glass thermal insulation coating, the glass was cleaned, and the cleaning agent was washed off with clean water, and then the water on the glass surface was wiped clean with a microfiber towel to keep the glass clean and dry;

[0186] (2) Put the architectural glass paint into the coating spray gun, and use the coating spray gun to evenly spray the architectural glass paint on the clean glass surface; spray from the left to the right of the glass, and spray twice;

[0187] (3) After spraying, place the glass with architectural glass coating in a ventilated place and let it stand for 2-3 days under natural conditions to fix and air dry;

[0188] (4) Clean the air-dried glass surface with clean water and detergent, and then wipe it with a soft cloth.

[0189] Optical images of droplets were taken on the glass surfaces with the coatings of Example 1 and Comparative Example 1, respectively. Figure 1 As shown in the figure, the coating of Comparative Example 1 has significant differences from Example 1 in terms of wettability and surface tension, which in turn affects its practical application effect on architectural glass. The self-cleaning performance is deteriorated, and the contact angle of water droplets on the coating surface is reduced, making it difficult to roll off. At the same time, since the coating of Comparative Example 1 does not contain high-entropy material powder, it lacks the excellent properties brought by high-entropy alloys, and its thermal insulation, wear resistance, hardness, and aging resistance are also significantly reduced.

[0190] The high entropy material powder in Example 2 was photographed under a transmission electron microscope. The photographic results are as follows: Figure 2 As shown in the figure, the five metals are evenly distributed, which can maximize the performance of the glass coating.

[0191] In order to verify the light transmittance of the coating, the glass with the coating of Example 1 and Comparative Example 2 was measured for light transmittance at different wavelengths. The results are as follows: Figure 3 As shown in the figure, the coating of the present invention has a high light transmittance and good light transmittance. The light scattering and absorption properties of titanium dioxide contribute to the overall optical performance of the coating, resulting in good light transmittance. In addition, titanium dioxide has the property of photocatalytic self-cleaning. Comparative Example 2 does not contain this material. Under long-term light exposure, the coating of Comparative Example 2 is more likely to accumulate dirt, resulting in a decrease in the cleanliness of the glass surface and a decrease in light transmittance.

Claims

1. A high entropy coating for architectural glass coating, characterized in that: The method is composed of the following raw materials in parts by weight: high entropy material powder: 27-30 parts; Coated titanium dioxide powder: 10-12 parts; Alcohol-soluble acrylate resin: 22-25 parts; Anhydrous ethanol: 13-15 parts; Polymethacrylate ammonium salt dispersant: 4-6 parts; Polyether modified silicone leveling agent: 6-8 parts; Polyether modified silicone defoamer: 4-6 parts; Associative polyurethane thickener: 3-5 parts; Benzotriazole ultraviolet absorber: 8-10 parts; Sodium tetraborate: 2-3 parts; Mixed phosphate: 4-5 parts; 2-3 parts of potassium hydrogen phthalate; The metal elements in the high entropy material powder include at least three of iron, nickel, cobalt, copper, palladium, manganese, zinc, and chromium, and the atomic ratios of the metal elements are equal; The mixed phosphate is composed of the following raw materials in weight percentage: zinc phosphate 40-50%; calcium phosphate 30-40%; sodium tripolyphosphate 10-20%; The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, dispersing the titanium dioxide powder under ultrasonication at 70-80 kHz for 30-40 minutes, stirring the mixture at 60-80° C. for reaction for 2-3 hours, and drying the mixture; wherein the mass of the silane coupling agent is 3%-4% of the mass of the ethanol solution of the silane coupling agent; the mass of the titanium dioxide powder is 10-11% of the mass of the ethanol solution of the silane coupling agent; and the particle size of the titanium dioxide powder is 20-30 nm. The high-entropy material powder is prepared by the following method: mixing metal salts or complexes containing a single metal element in an equiatomic ratio of the metal elements to form a metal salt mixture, ultrasonically mixing the metal salt mixture with an ethanol solution for 2 hours, and freeze-drying to obtain a mixed salt; evenly spreading the mixed salt between two pieces of carbon paper, applying a 500A current shock to in-situ reduce and alloy the metal salts, and collecting and cleaning to obtain the high-entropy material powder; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, the mass fraction of ethanol in the ethanol solution is 70%, and the frequency of the ultrasound is 80kHz.

2. The high entropy coating for architectural glass coating according to claim 1, characterized in that: The method is composed of the following raw materials in parts by weight: high entropy material powder: 30 parts; Coated titanium dioxide powder: 10 parts; Alcohol-soluble acrylate resin: 25 parts; Anhydrous ethanol: 15 parts; Polymethacrylate ammonium salt dispersant: 5 parts; Polyether modified silicone leveling agent: 8 parts; Polyether modified silicone defoamer: 6 parts; Associative polyurethane thickener: 5 parts; Benzotriazole ultraviolet absorber: 10 parts; Sodium tetraborate: 2 parts; Mixed phosphate: 5 parts; 2 parts of potassium hydrogen phthalate; The metal elements in the high entropy material powder include at least three of iron, nickel, cobalt, copper, palladium, manganese, zinc, and chromium, and the atomic ratios of the metal elements are equal; The mixed phosphate is composed of the following raw materials in weight percentage: 40% zinc phosphate; 40% calcium phosphate; 20% sodium tripolyphosphate; The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, dispersing the titanium dioxide powder under 80kHz ultrasonication for 30 minutes, stirring the mixture at 60-80°C for reaction for 2-3 hours, and drying the mixture; wherein the mass of the silane coupling agent is 3% of the mass of the ethanol solution of the silane coupling agent; and the mass of the titanium dioxide powder is 10% of the mass of the ethanol solution of the silane coupling agent.

3. The method for preparing a high entropy coating for architectural glass coating according to any one of claims 1-2, characterized in that: The following steps are involved: S1. Mix 70% of the total mass of the polymethacrylate ammonium salt dispersant, the high-entropy material powder, and anhydrous ethanol in a high-speed disperser. Then, disperse the mixture in a ball mill to a size of 1000-3000 mesh. Transfer the mixture to an ultrasonic generator, then add the coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant. Continue dispersing the mixture in the ultrasonic generator at 80 kHz for 1-2 hours to prepare a high-entropy material slurry. S2. Add the high-entropy material slurry to the alcohol-soluble acrylic resin and stir at 800-900 r / min for 15-20 minutes. Then, add the polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener, and benzotriazole UV absorber and stir at 1200-1300 r / min for 10-15 minutes to prepare a primary mixed slurry. Transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, and stir at 200-800 r / min for 30-40 minutes.

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