High-entropy coating for building glass coating and preparation method of high-entropy coating

Abstract

The invention belongs to the field of coatings, and discloses a high-entropy coating for a building glass coating and a preparation method of the high-entropy coating, and the high-entropy coating is prepared from the following raw materials in parts by weight: 25-30 parts of high-entropy material powder; 10 to 15 parts of coated titanium dioxide powder; 20 to 30 parts of alcohol soluble acrylate resin; 10 to 15 parts of absolute ethyl alcohol; 3-7 parts of a polymethylacrylic acid ammonium salt dispersing agent; 6-8 parts of a polyether modified organosilicon leveling agent; 4-6 parts of a polyether modified silicone defoaming agent; 3 to 5 parts of an associated polyurethane thickening agent; 8 to 10 parts of a benzotriazole ultraviolet light absorber; 1 to 4 parts of sodium tetraborate; 4-5 parts of mixed phosphate; and 1 to 4 parts of potassium hydrogen phthalate. The high-entropy coating for the building glass coating can comprehensively overcome the defects of an existing coating, and has important practical significance and wide 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] In the field of construction, architectural glass is widely used in places such as residential buildings, office buildings, and gymnasiums. It not only affects the beauty of buildings, but is also closely related to the functionality of buildings. As people's requirements for building environmental comfort and energy saving continue to increase, architectural glass coating technology has become a research hotspot. Architectural glass coating technology aims to give glass a variety of excellent properties, such as heat insulation, wear resistance, and anti-condensation and icing, thereby improving the overall performance and user experience of the building.

[0003] Traditionally, architectural glass protection and maintenance uses methods such as thermal insulation film, ordinary thermal insulation paint and manual cleaning. Thermal insulation film is to paste a layer of film with thermal insulation function on the surface of glass to reduce heat transfer; ordinary thermal insulation paint uses the thermal insulation components in the paint to form a thermal insulation layer on the surface of the glass to achieve a certain thermal insulation effect; manual cleaning is to wipe the glass manually regularly to keep the glass clean and reduce the impact of dirt on the performance of the glass.

[0004] As an emerging branch of coating technology, high entropy coatings, with their unique multi-principal synergistic effect, form a highly disordered and uniform solid solution structure at the atomic scale, giving them excellent physical and chemical properties, including high stability, UV resistance, heat insulation, corrosion resistance and self-cleaning properties. This high mixing entropy effect enhances the environmental adaptability of the coating, enabling it to maintain stable performance under frequently changing temperature and humidity conditions, while improving the blocking ability of ultraviolet and infrared bands through lattice distortion, thereby reducing indoor temperature rise. In addition, the superhydrophobicity of the coating effectively prevents condensation, frost and ice, ensuring the safety and normal use of glass buildings. However, there are relatively few literatures on the use of high entropy materials in architectural glass coatings in the prior art, and there is an urgent need to develop a high entropy material for architectural glass coatings. Summary of the invention

[0005] The purpose of the present invention is to provide a high entropy coating for architectural glass coating and a preparation method of the high entropy coating.

[0006] To achieve the above object, the present invention adopts the following technical solution: A high entropy coating for architectural glass coating, comprising the following raw materials in parts by weight: 25-30 parts of high entropy material powder; Coated titanium dioxide powder: 10-15 parts; Alcohol-soluble acrylic resin: 20-30 parts; Anhydrous ethanol: 10-15 parts; Ammonium polymethacrylate dispersant: 3 - 7 parts; Polyether modified silicone leveling agent: 6 - 8 parts; Polyether modified silicone defoaming agent: 4 - 6 parts; Associative polyurethane thickener: 3 - 5 parts; Benzotriazole ultraviolet absorber: 8 - 10 parts; Sodium tetraborate: 1 - 4 parts; Mixed phosphate: 4 - 5 parts; Potassium hydrogen phthalate 1 - 4 parts; 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 by weight percentage: zinc phosphate 30 - 50%; calcium phosphate 20 - 40%; sodium tripolyphosphate 10 - 30%; The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder to an ethanol solution containing a silane coupling agent, ultrasonic dispersing for 30 - 60 minutes at 60 - 80 kHz, then stirring and reacting at 60 - 80 °C for 2 - 3 hours, and drying; wherein the mass of the silane coupling agent is 3% - 5% of the mass of the ethanol solution of the silane coupling agent; the mass of the titanium dioxide powder is 10 - 12% of the mass of the ethanol solution of the silane coupling agent.

[0007] Preferably, a high-entropy coating for architectural glass coatings 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; Absolute ethanol: 13 - 15 parts; Ammonium polymethacrylate dispersant: 4 - 6 parts; Polyether modified silicone leveling agent: 6 - 8 parts; Polyether modified silicone defoaming agent: 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; Potassium hydrogen phthalate 2 - 3 parts; 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 by 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 into an ethanol solution containing a silane coupling agent, performing ultrasonic dispersion at 70 - 80 kHz for 30 - 40 minutes, then stirring and reacting at 60 - 80 °C for 2 - 3 hours, and drying; 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.

[0008] Preferably, a high-entropy coating for building glass coatings 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; Absolute ethanol: 15 parts; Polymethacrylic acid 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; Potassium hydrogen phthalate: 2 parts; 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 percentages: zinc phosphate 40%; calcium phosphate 40%; sodium tripolyphosphate 20%; The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder into an ethanol solution containing a silane coupling agent, performing ultrasonic dispersion at 80 kHz for 30 minutes, then stirring and reacting at 60 - 80 °C for 2 - 3 hours, and drying; 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; the silane coupling agent can form an organic film on the surface of titanium dioxide, enhancing its compatibility with the organic substances in the coating system and improving the dispersion stability; For better results, preferably, the high-entropy material powder is prepared by the following method: Mix various metal salts or complexes containing single metal elements in an equiatomic ratio of metal elements to form a metal salt mixture. Ultrasonically mix the metal salt mixture with an ethanol solution for 2 hours, and obtain a mixed salt after freeze-drying. Evenly spread the mixed salt between two pieces of carbon paper, apply a current shock of 500 A to in-situ reduce and alloy the metal salt, and collect and wash to obtain the high-entropy material powder. The mass ratio of the metal salt mixture to the ethanol solution is 1:4, and the mass fraction of ethanol in the ethanol solution is 70%. The frequency of the ultrasonic wave is 80 kHz.

[0009] Preferably, the particle size of the titanium dioxide powder is 5 - 50 nm.

[0010] For better results, preferably, the particle size of the titanium dioxide powder is 20 - 30 nm.

[0011] Preferably, the alcohol-soluble acrylate resin is composed of the following components by mass percentage: absolute ethanol: 35%, azobisisobutyronitrile: 22%, methyl methacrylate: 13%, butyl acrylate: 15%, butyl methacrylate: 15%; The preparation method of the alcohol-soluble acrylate resin is specifically operated as follows: (1) Add all the absolute ethanol into a 500 ml three-necked flask, add half of the amount of azobisisobutyronitrile, heat the three-necked flask to 85 - 88 °C, and control the rotation speed at 800 - 810 rpm; (2) Mix methyl methacrylate, butyl acrylate, butyl methacrylate and the other half of azobisisobutyronitrile evenly, and add the evenly mixed mixture into a 120 ml constant pressure burette; (3) Slowly titrate the mixture in the constant pressure burette into the three-necked flask at a constant speed, control the titration time within 50 - 60 min. After the titration is completed, carry out a constant temperature reaction for 5 - 6 h, and discharge to obtain the alcohol-soluble acrylate resin.

[0012] The preparation method of the above high-entropy coating for architectural glass includes the following steps: S1. Send 70% of the total mass of the polymethacrylic acid ammonium salt dispersant, the high-entropy material powder, and absolute ethanol to a high-speed disperser for mixing, then disperse it to 1000 - 3000 meshes by a ball mill and transfer it to an ultrasonic generator. Then add the coated titanium dioxide powder and the remaining polymethacrylic acid ammonium salt dispersant, and continue to disperse in the ultrasonic generator at a frequency of 80 kHz for 1 - 2 hours to prepare the high-entropy material slurry for use; S2. Add the high-entropy material slurry into the alcohol-soluble acrylate resin, stir at a speed of 800-900 r / min for 15-20 minutes, then add polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener and benzotriazole ultraviolet absorber, and stir at 1200-1300 r / min for 10-15 minutes to obtain a preliminary mixed slurry; transfer the preliminary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphate and potassium hydrogen phthalate, and stir at 200-800 r / min for 30-40 minutes, then it is ready.

[0013] In the present invention, polycarboxylate polymer dispersants are selected to improve the synergistic dispersion of titanium dioxide and high-entropy materials. Specifically, it is an ammonium polymethacrylate dispersant with a molecular weight of 5000-10000. This dispersant has a long-chain structure polymerized from methacrylic acid monomers, and this long chain endows the dispersant with good steric hindrance effect. In the coating system, the long chain can form an adsorption layer with a certain thickness on the surfaces of high-entropy nanoparticles and titanium dioxide particles. When the particles approach each other, the repulsive force between the adsorption layers prevents the particles from agglomerating, enabling the particles to be evenly and stably dispersed in the system.

[0014] In order to overcome the influence of titanium dioxide on the leveling property of the coating, a polyether-modified silicone leveling agent with better leveling effect and surface activity is selected in the present invention. This leveling agent can reduce the surface tension of the coating, make the coating spread more evenly on the glass surface, ensure the flatness and gloss of the coating, and at the same time does not affect the self-cleaning performance of titanium dioxide.

[0015] In the present invention, the phosphate composition is reasonable. Zinc phosphate can form chemical bonds between the coating and the glass surface through its own chemical activity, enhance the adhesion of the coating, make the high-entropy coating adhere more firmly to the glass, resist daily friction and environmental erosion, and extend the service life of the coating. Calcium phosphate can adjust the hardness and wear resistance of the coating to a certain extent. Sodium tripolyphosphate has excellent dispersion performance and can help high-entropy material powder, titanium dioxide powder for coating, etc. to be more evenly dispersed in the coating system.

[0016] In the present invention, the polyether-modified silicone defoamer has both the high defoaming efficiency of silicone and the good compatibility of polyether, can quickly eliminate microbubbles, avoid the risk of cratering of traditional silicone defoamers, and at the same time, since the coating needs to adapt to temperature and humidity changes, the polyether-modified silicone remains stable in a wide temperature range.

[0017] In the present invention, the associative polyurethane thickener has the shear-thinning property, can improve the fluidity of the coating during construction, and at the same time prevent pigment sedimentation during standing, meeting the requirements of the architectural glass coating for uniformity. It has excellent compatibility with the alcohol-soluble acrylate resin system, avoiding delamination or turbidity caused by improper selection of thickeners. In terms of anti-aging, the polyurethane thickener itself has good hydrolysis resistance and weather resistance, which can improve the long-term stability.

[0018] Compared with the prior art, the advantages of the present invention are as follows: 1. Due to the unique multi-principal element synergistic effect, the high entropy material (HEM) powder forms a highly disordered and uniform solid solution structure at the atomic scale, enhancing the barrier ability to ultraviolet and infrared bands through lattice distortion, effectively reducing indoor temperature rise, and endowing the coating with excellent heat insulation performance. The coated titanium dioxide also contributes to heat insulation to a certain extent, and synergistically with the HEM powder, further improves the overall heat insulation effect, making the glass after construction have excellent heat insulation performance.

[0019] 2. The addition of the high entropy material powder makes the coating have good adhesion, abrasion resistance and hardness. The special structure of the high entropy alloy endows the coating with high mechanical strength, enabling it to resist external forces such as friction and scratching during actual use and extending the service life of the coating.

[0020] 3. The high mixing entropy effect of the 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.

[0021] 4. The organic film on the surface of the coated titanium dioxide enhances its compatibility with the organic substances in the coating system, and at the same time, titanium dioxide itself has the property of photocatalytic self-cleaning. Under light irradiation, it can decompose the organic dirt on the surface and keep the glass surface clean. The presence of the high entropy material may also indirectly promote the exertion of this self-cleaning performance.

[0022] The high entropy material for the building glass coating of the present invention can comprehensively solve the deficiencies of the existing coatings, and has important practical significance and broad application prospects. Description of the Drawings

[0023] Figure 1 Optical image of droplets loaded on the glass surface of the glass with the coatings of Example 1 and Comparative Example 1 of the present invention; Figure 2 High-angle annular dark-field image taken by transmission electron microscope and its corresponding energy-dispersive spectrum image of the high entropy material powder of Example 2 of the present invention; Figure 3 Transmittance of different wavelengths of the glass sprayed with the high entropy material coating of Example 1 of the present invention and the glass sprayed with the coating in Comparative Example 2. Detailed Embodiments

[0024] The following further illustrates the present invention with reference to the embodiments, but the protection scope of the present invention is not limited thereto.

[0025] The alcohol-soluble acrylate resin described in the following examples is composed of the following components by mass percentage: absolute ethanol: 35%, azobisisobutyronitrile: 22%, methyl methacrylate: 13%, butyl acrylate: 15%, butyl methacrylate: 15%; The preparation method of the alcohol-soluble acrylate resin is as follows: (1) Add all the absolute ethanol into a 500 ml three-necked flask, add half of the amount of azobisisobutyronitrile, heat the three-necked flask to 85 - 88 °C, and control the rotation speed to 800 - 810 rpm; (2) Mix methyl methacrylate, butyl acrylate, butyl methacrylate and the other half of azobisisobutyronitrile evenly, and add the evenly mixed mixture into a 120 ml constant pressure burette; (3) Slowly titrate the mixed solution in the constant pressure burette into the three-necked flask, control the titration time within 50 - 60 min. After the titration is completed, carry out a constant temperature reaction for 5 - 6 h, and discharge the material to obtain the alcohol-soluble acrylate resin. Example 1

[0026] A high-entropy coating for architectural glass coatings 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; Absolute ethanol: 15 parts; Polymethacrylic acid ammonium salt dispersant: 5 parts; Polyether-modified silicone leveling agent: 8 parts; Polyether-modified silicone defoaming agent: 6 parts; Associative polyurethane thickener: 5 parts; Benzotriazole ultraviolet absorber: 10 parts; Sodium tetraborate: 2 parts; Mixed phosphate: 5 parts; the mixed phosphate is composed of the following raw materials by weight percentage: zinc phosphate 40%; calcium phosphate 40%; sodium tripolyphosphate 20%; Potassium hydrogen phthalate: 2 parts; 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; The coated titanium dioxide powder is prepared by the following method: Add titanium dioxide powder into an ethanol solution containing a silane coupling agent, disperse it by ultrasonic wave at 80 kHz for 30 minutes, then stir and react at 60 °C for 2 hours, and obtain the coated titanium dioxide powder after drying; 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; the particle size of the titanium dioxide powder is 20 nm.

[0027] The high-entropy material powder is prepared by the following method: Mix five salts, namely ferric chloride, nickel chloride, cobalt chloride, copper chloride, and palladium chloride, in an equal atomic ratio to form a metal salt mixture. Ultrasonically mix the metal salt mixture with an ethanol solution for 2 hours, and then obtain the mixed salt FeNiCoCuPt through freeze-drying. Evenly spread the mixed salt FeNiCoCuPt between two pieces of carbon paper, apply a current impact of 500 A to in-situ reduce and alloy the metal salt, and collect and wash to obtain the high-entropy material (HEM) powder. The mass ratio of the metal salt mixture to the ethanol solution is 1:4, and the mass fraction of ethanol in the ethanol solution is 70%. The frequency of the ultrasonic wave is 80 kHz.

[0028] The preparation method of the above high-entropy coating for architectural glass includes the following steps: S1. Send 70% of the total mass of the ammonium polymethacrylate dispersant, the high-entropy material powder, and absolute ethanol to a high-speed disperser for mixing, then disperse it to 2000 mesh through a ball mill and transfer it to an ultrasonic generator. Then add the titanium dioxide powder for coating and the remaining ammonium polymethacrylate dispersant, and continue to disperse at a frequency of 80 kHz in the ultrasonic generator for 1 hour to obtain the high-entropy material slurry for use. The step-by-step dispersion method can fully disperse the high-entropy nanoparticles and titanium dioxide respectively, avoid interference between the two during the dispersion process, and ensure the dispersion effect and performance of each; S2. Add the high-entropy material slurry to the alcohol-soluble acrylate resin, stir at a speed of 800 r / min for 15 minutes, then add the polyether-modified silicone leveling agent, polyether-modified silicone defoaming agent, associative polyurethane thickener, and benzotriazole ultraviolet absorber, and stir at 1200 r / min for 10 minutes to obtain the preliminary mixed slurry. Transfer the preliminary 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 full reaction and uniform mixing of the system. Example 2

[0029] A high-entropy coating for architectural glass is composed of the following raw materials in parts by weight: High-entropy material powder: 25 parts; Titanium dioxide powder for coating: 10 parts; Alcohol-soluble acrylate resin: 30 parts; Absolute ethanol: 10 parts; Ammonium polymethacrylate dispersant: 5 parts; Polyether-modified silicone leveling agent: 7 parts; Polyether-modified silicone defoaming agent: 5 parts; Associative polyurethane thickener: 3 parts; Benzotriazole ultraviolet absorber: 8 parts; Sodium tetraborate: 2 parts; Mixed phosphate: 5 parts; the mixed phosphate is composed of the following raw materials in weight percentages: zinc phosphate 30%; calcium phosphate 40%; sodium tripolyphosphate 30%; Potassium hydrogen phthalate: 2 parts; 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; The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder into an ethanol solution containing a silane coupling agent, ultrasonically dispersing for 60 minutes at 60 kHz, then stirring and reacting at 80 °C for 3 hours, and drying 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; the particle size of the titanium dioxide powder is 10 nm.

[0030] The high-entropy material powder is prepared by the following method: mixing five salts of manganese acetate, iron acetate, cobalt acetate, nickel acetate, and copper acetate in an equal atomic ratio to form a metal salt mixture, ultrasonically mixing the metal salt mixture with an ethanol solution for 2 hours, and obtaining a mixed salt MnFeCoNiCu after freeze-drying; evenly spreading the mixed salt MnFeCoNiCu between two pieces of carbon paper, applying a current impact of 500 A to in-situ reduce and alloy the metal salt, and collecting and cleaning to obtain the high-entropy material (HEM) 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 ultrasonic wave is 80 kHz.

[0031] The preparation method of the above high-entropy coating for building glass includes the following steps: S1. Send 70% of the total mass of the ammonium polymethacrylate dispersant, the high-entropy material powder, and absolute ethanol to a high-speed disperser for mixing, then disperse to 1000 meshes by a ball mill and transfer to an ultrasonic generator, and then add the coated titanium dioxide powder and the remaining ammonium polymethacrylate dispersant, and continue to disperse in the ultrasonic generator at a frequency of 80 kHz for 2 hours to obtain a high-entropy material slurry for use; the step-by-step dispersion method can fully disperse the high-entropy nanoparticles and titanium dioxide respectively, avoid mutual interference during the dispersion process, and ensure the dispersion effect and performance of each; S2. Add the high-entropy material slurry into the alcohol-soluble acrylate resin, stir at a speed of 900 r / min for 20 minutes, then add a polyether-modified silicone leveling agent, a polyether-modified silicone defoaming agent, an associative polyurethane thickener, and a benzotriazole ultraviolet absorber, stir at 1300 r / min for 15 minutes to obtain a preliminary mixed slurry; transfer the preliminary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, stir at 200 r / min for 40 minutes to ensure that the system reacts fully and is mixed evenly, then it is ready. Example 3

[0032] A high-entropy coating for architectural glass coatings is composed of the following raw materials in parts by weight: high-entropy material powder: 27 parts; Coated titanium dioxide powder: 12 parts; Alcohol-soluble acrylate resin: 20 parts; Absolute ethanol: 13 parts; Polymethacrylic acid ammonium salt dispersant: 7 parts; Polyether-modified silicone leveling agent: 6 parts; Polyether-modified silicone defoaming agent: 4 parts; Associative polyurethane thickener: 4 parts; Benzotriazole ultraviolet absorber: 9 parts; Sodium tetraborate: 1 part; Mixed phosphates: 4 parts; the mixed phosphates are composed of the following raw materials in weight percentages: zinc phosphate 50%; calcium phosphate 20%; sodium tripolyphosphate 20%; Potassium hydrogen phthalate: 4 parts; The metal elements in the high-entropy material powder include manganese, iron, cobalt, nickel, and zinc, and the atomic ratios of the metal elements are equal; The coated titanium dioxide powder is prepared by the following method: Add titanium dioxide powder into an ethanol solution containing a silane coupling agent, ultrasonically disperse at 70 kHz for 40 minutes, then stir and react at 70 °C for 2 hours, and obtain the coated titanium dioxide powder after drying; 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; the particle size of the titanium dioxide powder is 30 nm.

[0033] The high-entropy material powder is prepared by the following method: Mix five salts, namely manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, and zinc nitrate, in an equal atomic ratio to form a metal salt mixture. Ultrasonically mix the metal salt mixture with an ethanol solution for 2 hours, and then obtain the mixed salt MnFeCoNiZn through freeze-drying. Evenly spread the mixed salt MnFeCoNiZn between two pieces of carbon paper, apply a current impact of 500 A to in-situ reduce and alloy the metal salt, and collect and wash to obtain the high-entropy material (HEM) powder. The mass ratio of the metal salt mixture to the ethanol solution is 1:4, and the mass fraction of ethanol in the ethanol solution is 70%. The frequency of the ultrasonic wave is 80 kHz.

[0034] The preparation method of the above high-entropy coating for architectural glass includes the following steps: S1. Send 70% of the total mass of the ammonium polymethacrylate dispersant, the high-entropy material powder, and absolute ethanol to a high-speed disperser for mixing, then disperse it to 3000 mesh through a ball mill and transfer it to an ultrasonic generator. Then add the coated titanium dioxide powder and the remaining ammonium polymethacrylate dispersant, and continue to disperse in the ultrasonic generator at a frequency of 80 kHz for 2 hours to obtain the high-entropy material slurry for use. The step-by-step dispersion method can fully disperse the high-entropy nanoparticles and titanium dioxide respectively, avoid interference between the two during the dispersion process, and ensure their respective dispersion effects and properties. S2. Add the high-entropy material slurry to the alcohol-soluble acrylate resin, stir at a speed of 800 r / min for 18 minutes, then add a polyether-modified silicone leveling agent, a polyether-modified silicone defoaming agent, an associative polyurethane thickener, and a benzotriazole ultraviolet absorber, and stir at 1200 r / min for 15 minutes to obtain a preliminary mixed slurry. Transfer the preliminary 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 that the system reacts fully and is mixed evenly. Example 4

[0035] A high-entropy coating for architectural glass is composed of the following raw materials in parts by weight: High-entropy material powder: 28 parts; Coated titanium dioxide powder: 13 parts; Alcohol-soluble acrylate resin: 22 parts; Absolute ethanol: 12 parts; Ammonium polymethacrylate dispersant: 3 parts; Polyether-modified silicone leveling agent: 6 parts; Polyether-modified silicone defoaming agent: 5 parts; Associative polyurethane thickener: 4 parts; Benzotriazole ultraviolet absorber: 10 parts; Sodium tetraborate: 3 parts; Mixed phosphate: 5 parts; the mixed phosphate consists of the following raw materials by weight percentage: zinc phosphate 50%; calcium phosphate 40%; sodium tripolyphosphate 10%; Potassium hydrogen phthalate: 3 parts; 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; The coated titanium dioxide powder is prepared by the following method: adding titanium dioxide powder into an ethanol solution containing a silane coupling agent, ultrasonically dispersing for 30 minutes at 80 kHz, then stirring and reacting at 60 °C for 2 hours, and drying 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; the particle size of the titanium dioxide powder is 50 nm.

[0036] The high-entropy material powder is prepared by the following method: mixing chromium acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and zinc acetylacetonate five salts in an equal atomic ratio to form a metal salt mixture, ultrasonically mixing the metal salt mixture with an ethanol solution for 2 hours, and obtaining a mixed salt CrFeNiCoZn after freeze-drying; spreading the mixed salt CrFeNiCoZn evenly between two pieces of carbon paper, applying a current impact of 500 A to in-situ reduce and alloy the metal salt, and collecting and cleaning to obtain the high-entropy material (HEM) 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 ultrasonic wave is 80 kHz.

[0037] The preparation method of the above high-entropy coating for building glass includes the following steps: S1. Send 70% of the total mass of the ammonium polymethacrylate dispersant, the high-entropy material powder, and anhydrous ethanol to a high-speed disperser for mixing, then disperse to 1000 meshes by a ball mill and transfer to an ultrasonic generator, and then add the coated titanium dioxide powder and the remaining ammonium polymethacrylate dispersant, and continue to disperse at a frequency of 80 kHz in the ultrasonic generator for 2 hours to obtain a high-entropy material slurry for use; the step-by-step dispersion method can make the high-entropy nanoparticles and titanium dioxide be fully dispersed respectively, avoid mutual interference during the dispersion process, and ensure their respective dispersion effects and performances; S2. Add the high-entropy material slurry into the alcohol-soluble acrylate resin, stir at a speed of 800 r / min for 15 minutes, then add a polyether-modified silicone leveling agent, a polyether-modified silicone defoaming agent, an associative polyurethane thickener, and a benzotriazole ultraviolet absorber, stir at 1200 r / min for 10 minutes to obtain a preliminary mixed slurry; transfer the preliminary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphates, and potassium hydrogen phthalate, stir at 500 r / min for 35 minutes to ensure that the system reacts fully and is mixed evenly, and that's it. Example 5

[0038] A high-entropy coating for architectural glass coatings consists 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: 20 parts; Absolute ethanol: 10 parts; Ammonium polymethacrylate dispersant: 5 parts; Polyether-modified silicone leveling agent: 6 parts; Polyether-modified silicone defoaming agent: 4 parts; Associative polyurethane thickener: 5 parts; Benzotriazole ultraviolet absorber: 8 parts; Sodium tetraborate: 2 parts; Mixed phosphates: 5 parts; The mixed phosphates are composed of the following raw materials in weight percentages: Zinc phosphate 40%; Calcium phosphate 30%; Sodium tripolyphosphate 30%; Potassium hydrogen phthalate 2 parts; The metal elements in the high-entropy material powder include chromium, iron, and cobalt, and the atomic ratios of the metal elements are equal; The coated titanium dioxide powder is prepared by the following method: Add titanium dioxide powder into an ethanol solution containing a silane coupling agent, ultrasonically disperse at 70 kHz for 50 minutes, then stir and react at 80 °C for 3 hours, and obtain the coated titanium dioxide powder after drying; where 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; the particle size of the titanium dioxide powder is 5 nm.

[0039] The high-entropy material powder is prepared by the following method: Chromium acetylacetonate, iron acetylacetonate, and cobalt acetylacetonate are mixed in an equal atomic ratio to form a metal salt mixture. The metal salt mixture is ultrasonically mixed with an ethanol solution for 2 hours, and then a mixed salt CrFeCo is obtained after freeze-drying. The mixed salt CrFeCo is evenly spread between two pieces of carbon paper, and a current of 500 A is applied for impact to in-situ reduce and alloy the metal salt, and the high-entropy material (HEM) powder is collected and washed. The mass ratio of the metal salt mixture to the ethanol solution is 1:4, and the mass fraction of ethanol in the ethanol solution is 70%. The frequency of the ultrasonic wave is 80 kHz.

[0040] The preparation method of the above high-entropy coating for architectural glass includes the following steps: S1. 70% of the total mass of the ammonium polymethacrylate dispersant, the high-entropy material powder, and absolute ethanol are sent to a high-speed disperser for mixing, and then dispersed to 2000 meshes by a ball mill and transferred to an ultrasonic generator. Then, titanium dioxide powder for coating and the remaining ammonium polymethacrylate dispersant are added, and dispersion continues in the ultrasonic generator at a frequency of 80 kHz for 2 hours to obtain a high-entropy material slurry for use. The step-by-step dispersion method can fully disperse the high-entropy nanoparticles and titanium dioxide respectively, avoid mutual interference during the dispersion process, and ensure the dispersion effect and performance of each; S2. The high-entropy material slurry is added to the alcohol-soluble acrylate resin and stirred at a speed of 900 r / min for 20 minutes. Then, a polyether-modified silicone leveling agent, a polyether-modified silicone defoaming agent, an associative polyurethane thickener, and a benzotriazole ultraviolet absorber are added, and stirring is carried out at 1300 r / min for 10 minutes to obtain a preliminarily mixed slurry. The preliminarily mixed slurry is transferred to a magnetic stirrer, and sodium tetraborate, mixed phosphate, and potassium hydrogen phthalate are added, and stirring is carried out at 400 r / min for 40 minutes to ensure that the system reacts fully and is mixed evenly.

[0041] Comparative Example 1 An architectural glass coating is composed of the following raw materials in parts by weight: 10 parts of titanium dioxide powder for coating, 25 parts of alcohol-soluble acrylate resin, 15 parts of absolute ethanol, 5 parts of ammonium polymethacrylate dispersant, 8 parts of polyether-modified silicone leveling agent, 6 parts of polyether-modified silicone defoaming agent, 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 weight percentages: 40% of zinc phosphate; 40% of calcium phosphate; 20% of sodium tripolyphosphate.

[0042] The production method of the titanium dioxide powder for coating is the same as that in Example 1.

[0043] The preparation method of the above architectural glass coating includes the following steps: S1. Send 70% of the total mass of the ammonium polymethacrylate dispersant and absolute ethanol to a high-speed disperser for mixing, then disperse them to 2000 mesh through a ball mill and transfer them into an ultrasonic generator. Then add the coated titanium dioxide powder and the remaining dispersant, and continue to disperse in the ultrasonic generator at a frequency of 80 kHz for 1 hour to obtain a slurry for use.

[0044] S2. Add the prepared slurry to the alcohol-soluble acrylate resin, first stir at a speed of 800 r / min for 15 minutes to preliminarily mix all components evenly. Then add a polyether-modified silicone leveling agent, a polyether-modified silicone defoaming agent, an associative polyurethane thickener, and a benzotriazole ultraviolet absorber, increase the stirring speed to 1200 r / min, and stir for 10 minutes to strengthen the mixing effect to obtain a preliminarily mixed slurry. Transfer the preliminarily mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphate, and potassium hydrogen phthalate, and stir at 800 r / min for 30 minutes to ensure that the system reacts fully and is mixed evenly to obtain a building glass coating.

[0045] Comparative Example 2 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 absolute ethanol, 5 parts of ammonium polymethacrylate dispersant, 8 parts of polyether-modified silicone leveling agent, 6 parts of polyether-modified silicone defoaming agent, 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 weight percentages: 40% of zinc phosphate; 40% of calcium phosphate; 20% of sodium tripolyphosphate.

[0046] Among them, the high-entropy material is prepared by the following method: Mix five salts of ferric chloride, nickel chloride, cobalt chloride, copper chloride, and palladium chloride in an equiatomic ratio of metal elements to form a metal salt mixture. Ultrasonically mix the metal salt mixture with an ethanol solution for 2 hours, and obtain a mixed salt FeNiCoCuPt after freeze-drying; evenly spread the mixed salt FeNiCoCuPt between two pieces of carbon paper, apply a current impact of 500 A to in-situ reduce and alloy the metal salt, and collect and wash to obtain the high-entropy material powder; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, and the mass fraction of ethanol in the ethanol solution is 70%; the frequency of the ultrasonic wave is 80 kHz.

[0047] The preparation method of the above-mentioned coating for building glass coatings includes the following steps: S1. Send 70% of the total mass of the ammonium polymethacrylate dispersant, the high-entropy material powder, and absolute ethanol to a high-speed disperser for mixing, then disperse them to 2000 mesh through a ball mill and transfer them into an ultrasonic generator, and continue to disperse in the ultrasonic generator at a frequency of 80 kHz for 1 hour to obtain a slurry for use.

[0048] S2. Add the prepared slurry into the alcohol-soluble acrylate resin. First, stir at a speed of 800 r / min for 15 minutes to preliminarily mix all components evenly. Then add polyether-modified silicone leveling agent, polyether-modified silicone defoamer, associative polyurethane thickener and benzotriazole ultraviolet absorber, increase the stirring speed to 1200 r / min, and stir for 10 minutes to strengthen the mixing effect and obtain the preliminary mixed slurry. Transfer the preliminary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphate and potassium hydrogen phthalate, and stir at 800 r / min for 30 minutes to ensure that the system reacts fully and is mixed evenly, and obtain the architectural glass coating.

[0049] To verify the performance of the coating of the present invention for architectural glass coatings, the products in Example 1 and Comparative Example 1 were applied to the glass surface. The specific construction process is as follows: (1) Evenly spray the glass cleaner on the glass surface to be coated with the architectural glass heat-insulating coating, clean the glass, wash off the cleaner with clean water, and then wipe the water on the glass surface with an ultra-fine fiber towel to keep the glass clean and dry; (2) Load the architectural glass coating into the coating spray gun, and evenly spray the architectural glass coating on the wiped glass surface with the coating spray gun; When spraying, spray from the left side to the right side of the glass, and spray twice; (3) After spraying, place the glass with the architectural glass coating in a ventilated place and let it stand for 2 - 3 days under natural conditions for fixation and air drying; (4) Clean the air-dried glass surface with clean water and cleaner, and then wipe it with a soft cloth.

[0050] Optical images of the loaded droplets were taken on the glass surfaces with the coatings of Example 1 and Comparative Example 1 respectively. The results are as Figure 1 shown. It can be seen from the figure that there are obvious differences between the coating of Comparative Example 1 and that of Example 1 in terms of wettability, surface tension, etc., which in turn affect its actual application effect on architectural glass. The self-cleaning performance becomes worse, the contact angle of water droplets on the coating surface becomes smaller, and it is difficult to roll off. At the same time, since the high-entropy material powder is not added to the coating in Comparative Example 1 and the excellent properties brought by the high-entropy alloy are lacking, the heat insulation, wear resistance, hardness and anti-aging performance will also decrease significantly.

[0051] The high-entropy material powder in Example 2 was photographed under a transmission electron microscope. The photographing results are as Figure 2 shown. It can be seen from the figure that the five metals show a uniform distribution state, which can maximize the performance of the glass coating.

[0052] To verify the light transmittance of the coating, the light transmittance of the glasses with the coatings of Example 1 and Comparative Example 2 was measured at different wavelengths. The results are asFigure 3 As shown, it can be seen from the results in the figure that the coating of the present invention has a relatively high light transmittance and good light transmission. Since the scattering and absorption characteristics of titanium dioxide contribute to the overall optical performance of the coating, the light transmission is good. In addition, titanium dioxide has the property of photocatalytic self-cleaning. In Comparative Example 2, this material is not present. Under long-term light irradiation, the coating in Comparative Example 2 is more likely to accumulate dirt, the cleanliness of the glass surface decreases, and further the light transmittance decreases.

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: 25-30 parts; Coated titanium dioxide powder: 10-15 parts; Alcohol-soluble acrylic resin: 20-30 parts; Anhydrous ethanol: 10-15 parts; Polymethacrylate ammonium salt dispersant: 3-7 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: 1-4 parts; Mixed phosphate: 4-5 parts; 1-4 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: 30-50% zinc phosphate; 20-40% calcium phosphate; 10-30% 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, performing ultrasonic dispersion at 60-80kHz for 30-60 minutes, stirring and reacting at 60-80°C for 2-3 hours, and drying; 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.

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: 27-30 parts; Coated titanium dioxide powder: 10-12 parts; Alcohol-soluble acrylic 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: 40-50% zinc phosphate; 30-40% calcium phosphate; 10-20% 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, performing ultrasonic dispersion at 70-80kHz for 30-40 minutes, stirring and reacting at 60-80°C for 2-3 hours, and drying; 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.

3. A high entropy coating for architectural glass coating according to claim 2, characterized in that: The method is composed of the following raw materials in parts by weight: 30 parts of high entropy material powder; Coated titanium dioxide powder: 10 parts; Alcohol-soluble acrylic 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, performing 80kHz ultrasonic dispersion for 30 minutes, stirring and reacting at 60-80°C for 2-3 hours, and drying; 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.

4. A high entropy coating for architectural glass coating according to claim 3, characterized in that: The high entropy material powder is prepared by the following method: mixing various metal salts or complexes containing a single metal element according to 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 obtaining a mixed salt after freeze-drying; evenly spreading the mixed salt between two pieces of carbon paper, applying a 500A current shock to reduce and alloy the metal salt in situ, and collecting and washing to obtain the high entropy material powder; the mass ratio of the metal salt mixture to the ethanol solution is 1:4, and the mass fraction of ethanol in the ethanol solution is 70%; the frequency of the ultrasound is 80kHz.

5. The high entropy coating for architectural glass coating according to claim 3, characterized in that: The particle size of the titanium dioxide powder is 5-50 nm.

6. The high entropy coating for architectural glass coating according to claim 5, characterized in that: The particle size of the titanium dioxide powder is 20-30 nm.

7. A method for preparing a high entropy coating for architectural glass coating according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1. 70% of the total mass of the polymethacrylate ammonium salt dispersant, high entropy material powder and anhydrous ethanol are sent to a high-speed disperser for mixing, and then dispersed to 1000-3000 meshes in a ball mill and transferred to an ultrasonic generator, and then the coated titanium dioxide powder and the remaining polymethacrylate ammonium salt dispersant are added, and the dispersion is continued in the ultrasonic generator at a frequency of 80kHz for 1-2 hours to obtain a high entropy material slurry for standby use; S2. Add the high entropy material slurry to the alcohol-soluble acrylic resin, stir at a speed of 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 ultraviolet absorber, stir at 1200-1300 r / min for 10-15 minutes to prepare the primary mixed slurry; transfer the primary mixed slurry to a magnetic stirrer, add sodium tetraborate, mixed phosphate and potassium hydrogen phthalate, and stir at 200-800 r / min for 30-40 minutes.

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