Heat-insulating anti-ultraviolet coating material for glass and preparation method of heat-insulating anti-ultraviolet coating material

Abstract

The invention discloses a heat-insulating anti-ultraviolet coating material for glass and a preparation method thereof, and relates to the technical field of building coatings. The coating material comprises the following raw materials in parts by weight: 50-65 parts of fluorinated acrylate copolymer emulsion, 5-10 parts of aluminum oxide ceramic fiber, 15-20 parts of composite hollow glass beads, 5-15 parts of composite nanoparticles, 30-45 parts of deionized water, 4 parts of a coalescing agent, 1-2 parts of a dispersing agent, 1-2 parts of a defoaming agent, 0.1 part of a thickening agent and 0.8 part of a flatting agent. The composite hollow glass beads are formed by attaching modified nano TiO2 to the surfaces of hollow glass beads; the alumina ceramic fiber is ytterbium silicate modified alumina ceramic fiber; the composite nano particles are zirconium oxide composite tin antimony oxide nano particles and cesium tungsten bronze nano particles; the material prepared by the invention is good in heat insulation property, has strong capability of absorbing radiation in ultraviolet and near-infrared regions, and is a high-performance environment-friendly energy-saving building material.

Description

Technical Field

[0001] The present invention relates to the technical field of architectural coatings, and in particular to a heat-insulating and anti-ultraviolet coating material for glass and a preparation method thereof. Background Art

[0002] In the construction and automotive industries, glass, a key light-transmitting material, has a direct impact on indoor comfort and energy consumption due to its optical and thermal properties. Ordinary glass lacks effective barrier properties against near-infrared radiation (780-2500nm) and near-ultraviolet radiation (300-400nm) within the solar spectrum. Research indicates that the near-infrared portion of solar radiation accounts for as much as 53%, contributing to indoor heat accumulation and rising cooling energy consumption (accounting for 40% of modern building energy consumption). Meanwhile, while ultraviolet radiation only accounts for approximately 5%, it can significantly fade and age indoor fabrics, furniture, and artwork, posing a potential threat to human skin and eye health.

[0003] Existing technologies often use transparent conductive oxide nanoparticles to impart high light transmittance and strong absorption of ultraviolet and near-infrared radiation to coatings. However, these materials suffer from low shielding in the short-wave near-infrared region and mediocre overall performance. Therefore, there is a need to develop a broad-spectrum, ultraviolet and near-infrared, strong shielding and thermal insulation coating. The core of this invention lies in precisely controlling the material's spectral response, giving glass the advantage of "insulating heat without blocking light," resulting in a high-performance, environmentally friendly, and energy-saving building material. Summary of the Invention

[0004] The purpose of the present invention is to provide a heat-insulating and anti-ultraviolet coating material for glass and a preparation method thereof, so as to solve the following technical problems: The transparent conductive oxide nanoparticles used in the existing technology have the disadvantages of low shielding rate in the short-wave near-infrared region and average overall performance.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A heat-insulating and anti-ultraviolet coating material for glass and a preparation method thereof, comprising the following raw materials in parts by weight: 50-65 parts of a fluorine-containing acrylate copolymer emulsion, 5-10 parts of alumina ceramic fibers, 15-20 parts of composite hollow glass microspheres, 5-15 parts of composite nanoparticles, 30-45 parts of deionized water, 4 parts of a film-forming aid, 1-2 parts of a dispersant, 1-2 parts of a defoaming agent, 0.1 part of a thickener, and 0.8 part of a leveling agent; the composite hollow glass microspheres are hollow glass microspheres with modified nano-TiO2 attached to their surfaces; the alumina ceramic fibers are ytterbium silicate-modified alumina ceramic fibers; and the composite nanoparticles are zirconium oxide, tin oxide antimony nanoparticles, and cesium tungsten bronze nanoparticles.

[0006] As a further embodiment of the present invention, the fluorinated acrylate copolymer emulsion comprises the following raw materials in parts by weight: 40-60 parts by weight of propylene glycol methyl ether, 25-35 parts by weight of butyl acrylate, 40-45 parts by weight of methyl methacrylate, 30-50 parts by weight of acrylic acid, 2 parts by weight of azobisisobutyronitrile, and 25-35 parts by weight of N,N-dimethylethanolamine. The preparation method of the fluorinated acrylate copolymer emulsion comprises the following steps: Propylene glycol methyl ether was added to a reaction flask, which was filled with nitrogen and heated to 110°C. Butyl acrylate, methyl methacrylate, acrylic acid, and azobisisobutyronitrile were mixed to obtain a mixture, which was added dropwise to the reaction flask at 110°C for 2.5-3 hours. After reacting for 4-6 hours, the mixture was cooled to 60°C, N,N-dimethylethanolamine was added, and stirred for 1 hour to obtain a fluorinated acrylate copolymer emulsion.

[0007] As a further embodiment of the present invention: the film-forming aid is any one or more of propylene glycol methyl ether, propylene glycol butyl ether, and alcohol ester twelve; The dispersant is ammonium polyacrylate; The defoaming agent is polyether modified silicone oil; The thickener is a nonionic polyurethane associative thickener HEUR; The leveling agent is long-chain alkyl silicone oil.

[0008] As a further solution of the present invention: the preparation method of the composite hollow glass microspheres comprises the following steps: A1: Add vinyltrimethoxysilane to an ethanol aqueous solution, adjust the pH to 5.0-7.0 with acetic acid, add hollow glass microspheres and nano-TiO2 powder, stir at 70°C for 6-8 hours, and dry to obtain nano-TiO2 surface-modified hollow glass microspheres; A2: Treat the nano-TiO2 surface-modified hollow glass microspheres with HNO3 acid for 1-2 hours, filter out the solid components, mix with heptadecafluorodecyltriethoxysilane and ethanol aqueous solution, and react at 60-80°C in a nitrogen atmosphere for 6 hours. Wash with anhydrous ethanol and dry to obtain composite hollow glass microspheres.

[0009] As a further embodiment of the present invention: the concentration of the ethanol aqueous solution in A1 is 90 vol%, and the addition ratio of vinyltrimethoxysilane, ethanol aqueous solution, hollow glass microspheres, and nano-TiO2 powder is 1-2 g:100 mL:5-10 g:8-15 g; The concentration of HNO3 in A2 is 5wt%, the concentration of ethanol aqueous solution is 90vol%, and the addition ratio of nano-TiO2 surface-modified hollow glass microspheres, HNO3, heptadecafluorodecyltriethoxysilane, and ethanol aqueous solution is 0.5-1g:15mL:1-2g:30mL.

[0010] As a further embodiment of the present invention, the method for preparing the composite nanoparticles comprises the following steps: B1: SnCl4·5H2O, SbCl3, ZrOCl2·8H2O, and ethanol were mixed and ultrasonicated until completely dissolved. NH4OH was added dropwise to form a white precipitate. H2O2 solution was added, stirred for 30 minutes, and then allowed to stand for 8 hours. The precipitate was washed until the presence of chloride ions could no longer be detected with silver nitrate solution. The precipitate was dispersed in water, the pH was adjusted to 8.5-9.5 with NH4OH, and the mixture was transferred to a reaction flask and heated at 220–240°C for 12 hours. After cooling, the powder was dispersed in deionized water to obtain a composite tin oxide antimony nanoparticle dispersion. B2: WCl6 powder, CsOH·H2O powder, and anhydrous ethanol were mixed, acetic acid was added, and the mixture was kept at 200°C for 24 hours. After the reaction, the mixture was cooled, the precipitate was collected by centrifugation, washed with ethanol, and dried; silane coupling agent KH570 and deionized water were added and ball milled for 4 hours to obtain cesium tungsten bronze nanoparticle dispersion; B3: Mix equal volumes of composite antimony tin oxide nanoparticle dispersion and cesium tungsten bronze nanoparticle dispersion, slowly add butanol, sonicate for 10-30 minutes, centrifuge to obtain a precipitate, wash with anhydrous ethanol, and dry to obtain composite nanoparticles.

[0011] As a further embodiment of the present invention: the concentration of the H2O2 solution in B1 is 30 wt %, the addition ratio of SnCl4·5H2O, SbCl3, ZrOCl2·8H2O, ethanol, and H2O2 solution is 2.8-3.0 g: 0.2-0.3 g: 2.2-2.6 g: 40 mL: 0.5-0.6 mL, and the solid content of the composite tin oxide antimony nanoparticle dispersion is 4%; The addition ratio of WCl6 powder, CsOH·H2O powder, anhydrous ethanol, acetic acid, and silane coupling agent KH570 in B2 is 0.4-0.5g: 0.08-0.11g: 20mL: 10mL: 0.05g, and the solid content of cesium tungsten bronze nanoparticle dispersion is 4%; The amount of butanol added in B3 is 5% of the total volume of the composite antimony tin oxide nanoparticle dispersion and the cesium tungsten bronze nanoparticle dispersion.

[0012] As a further embodiment of the present invention, the method for preparing the alumina ceramic fiber comprises the following steps: C1: Yb2O3 powder and SiO2 powder are mixed and sintered to obtain composite powder; polyvinyl alcohol is dissolved in hot water to obtain a polyvinyl alcohol aqueous solution; C2: polyvinyl alcohol aqueous solution, aluminum isopropoxide, composite powder, and polydimethylsiloxane are mixed and stirred for 2-4 hours to obtain a spinning solution, and the spinning solution is spun and dried to obtain alumina ceramic fibers.

[0013] As a further embodiment of the present invention: the concentration of the polyvinyl alcohol aqueous solution in C1 is 12-16 wt %, and the added mass ratio of Yb2O3 powder and SiO2 powder is 75-85:10-14; In C2, the added mass ratio of polyvinyl alcohol aqueous solution, aluminum isopropoxide, composite powder, and polysiloxane is 25-60:30-40:40-50:5-10.

[0014] As a further embodiment of the present invention: a method for preparing a heat-insulating and anti-ultraviolet coating material for glass comprises the following steps: S1: Alumina ceramic fibers, composite hollow glass microspheres, composite nanoparticles, deionized water, dispersant, and leveling agent are mixed, stirred for 5-10 minutes, and ultrasonicated for 20-30 minutes to obtain a filler slurry; S2: Put the fluorinated acrylic copolymer emulsion, filler slurry, film-forming aid, and thickener into a ball mill and mill them for 1-2 hours, then add a defoaming agent and mill them for 1 hour to obtain a heat-insulating and anti-ultraviolet coating material for glass.

[0015] Beneficial effects of the present invention: (1) The present invention adds alumina ceramic fiber, the main component of which is α-Al2O 3， The Al-O bond energy in its lattice is high and the crystal phase is stable. It has the advantages of outstanding high-temperature resistance, low thermal conductivity and good chemical stability. Ytterbium silicate is a rare earth silicate material with good phase stability and a thermal expansion coefficient that matches that of the matrix. It has good chemical compatibility with alumina and has the characteristics of high melting point, low hardness, good thermal stability and low thermal expansion coefficient. Ytterbium silicate modified alumina ceramic fiber has good interfacial compatibility and can significantly improve the thermal insulation performance of the coating.

[0016] (2) The present invention also adds composite hollow glass microspheres. The outer shell of the hollow glass microspheres is soda lime borosilicate and the interior is closed and hollow, which has the advantages of high thermal insulation and high heat resistance. Nano-TiO2 is coated on the surface of the hollow glass microspheres using silicone, and then the nano-TiO2 is modified with fluorosilicone to improve the coating's absorption of ultraviolet radiation without affecting the light transmittance.

[0017] (3) The application utilizes zirconium oxide composite tin oxide antimony nanoparticles to be compounded with cesium tungsten bronze nanoparticles to obtain composite nanoparticles, the tin oxide antimony nanoparticles are of rutile structure, tin dioxide is the main body, trivalent antimony and pentavalent antimony are doped into the tin dioxide to replace tetravalent tin to generate a positive charge center and electrons, thereby greatly improving the free carrier concentration, and the band gap is 3.0-3.2 eV, so that the nanoparticles have high transparency, excellent near-infrared (1500-2500 nm) and ultraviolet absorption performance and high physical and chemical stability, the zirconium oxide composite tin oxide antimony nanoparticles bring high heat insulation and thermal stability; the tungsten oxide has almost no response to the near-infrared, but after being doped with alkali metal ions Cs, the tungsten oxide is endowed with rich free carriers, so that the tungsten oxide can absorb near-infrared light and has high light transmittance; the introduction of the cesium tungsten bronze nanoparticles makes up for the shortcoming of poor short-wave near-infrared (780-1500 nm) absorption of the tin oxide antimony nanoparticles, and the composite of the cesium tungsten bronze nanoparticles and the tin oxide antimony nanoparticles can play a synergistic effect of plasmonic resonance absorption, thereby improving the shielding property to the near-infrared and ultraviolet radiation. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0019] The preparation method of the fluorine-containing acrylate copolymer emulsion in Embodiment 1 comprises the following steps: 50 g of propylene glycol methyl ether is added to a reaction bottle, nitrogen is filled, and heating is performed until the temperature reaches 110 DEG C; 30 g of butyl acrylate, 40 g of methyl methacrylate, 40 g of acrylic acid and 2 g of azobisisobutyronitrile are mixed to obtain a mixture, the mixture is added dropwise to the reaction bottle at a temperature of 110 DEG C and a dropwise adding time of 3 h, and after reaction for 5 h, the temperature is lowered to 60 DEG C, 30 g of N,N-dimethylethanolamine is added, and stirring is performed for 1 h to obtain the fluorine-containing acrylate copolymer emulsion.

[0020] The preparation method of the composite hollow glass microbead in Embodiment 2 comprises the following steps: A1: 1.5 g of vinyltrimethoxysilane is added to 100 mL of 90 vol% ethanol aqueous solution, acetic acid is used to adjust the pH to 6, 7.5 g of hollow glass microbeads and 12.5 g of nano-TiO2 powder are added, stirring is performed at 70 DEG C for 8 h, and drying is performed to obtain a hollow glass microbead semi-finished product; A2: 0.8 g of the semi-finished hollow glass microspheres was treated with 15 mL of 5 wt% HNO3 acid for 1.5 h. The solid component was filtered out and mixed with 1.5 g of heptafluorodecyltriethoxysilane and 30 mL of 90 vol% ethanol aqueous solution. The mixture was kept warm at 70°C under a nitrogen atmosphere for 6 h. The mixture was washed with anhydrous ethanol and dried to obtain composite hollow glass microspheres.

[0021] Example 3 The preparation method of composite nanoparticles comprises the following steps: B1: Mix 2.9g SnCl4·5H2O, 0.25g SbCl3, 2.4g ZrOCl2·8H2O, and 40mL ethanol and sonicate until completely dissolved. Add NH4OH dropwise to form a white precipitate. Add 0.55mL 30wt% H2O2, stir for 30min, and let stand for 8h. Wash the precipitate until no chloride ions can be detected with silver nitrate solution. Disperse the precipitate in water, adjust the pH to 9.0 with NH4OH, transfer to a reaction flask, and heat at 230°C for 12h. After cooling, disperse the powder in deionized water to obtain a composite antimony tin oxide nanoparticle dispersion. B2: 4.5 g WCl6 powder, 0.9 g CsOH·H2O powder, and 20 mL anhydrous ethanol were mixed, 10 mL acetic acid was added, and the mixture was kept at 200°C for 24 h. After the reaction, the mixture was cooled, the precipitate was collected by centrifugation, washed with ethanol, and dried. 0.05 g silane coupling agent KH570 was added and the mixture was ball-milled for 4 h to obtain a cesium tungsten bronze nanoparticle dispersion. B3: 50 mL each of 4 wt% composite antimony tin oxide nanoparticle dispersion and 4 wt% cesium tungsten bronze nanoparticle dispersion were mixed, 5 mL of butanol was slowly added dropwise, and ultrasonication was performed for 20 min; the precipitate was obtained by centrifugation, washed with anhydrous ethanol, and dried to obtain composite nanoparticles.

[0022] Example 4 The preparation method of alumina ceramic fiber comprises the following steps: C1: 80g Yb2O3 powder and 12g SiO2 powder were mixed and sintered to obtain composite powder; polyvinyl alcohol was dissolved in hot water to obtain a 14wt% polyvinyl alcohol aqueous solution; C2: 45 g of polyvinyl alcohol aqueous solution, 35 g of aluminum isopropoxide, 45 g of composite powder, and 8 g of polysiloxane were mixed and stirred for 3 h to obtain a spinning solution, and the spinning solution was spun and dried to obtain alumina ceramic fibers.

[0023] Example 5 A heat-insulating and anti-ultraviolet coating material for glass comprises the following raw materials in parts by weight: 50 parts of fluorinated acrylate copolymer emulsion, 5 parts of alumina ceramic fiber, 15 parts of composite hollow glass microspheres, 5 parts of composite nanoparticles, 30 parts of deionized water, 4 parts of film-forming aid, 1 part of dispersant, 1 part of defoaming agent, 0.1 part of thickener, and 0.8 part of leveling agent; the fluorinated acrylate copolymer emulsion is prepared by the method in Example 1, the composite hollow glass microspheres are prepared by the method in Example 2, the composite nanoparticles are prepared by the method in Example 3, and the alumina ceramic fiber is prepared by the method in Example 4. The preparation method of the heat-insulating and anti-ultraviolet coating material for glass comprises the following steps: S1: 5 g alumina ceramic fiber, 15 g composite hollow glass microspheres, 5 g composite nanoparticles, 30 g deionized water, 1 g polyacrylate ammonium salt, and 0.8 g long-chain alkyl silicone oil were mixed, stirred for 5 min, and ultrasonicated for 20 min to obtain a filler slurry; S2: 50 g of fluorinated acrylate copolymer emulsion, filler slurry, 4 g of propylene glycol methyl ether, and 0.1 g of nonionic polyurethane associative thickener HEUR were placed in a ball mill and ball-milled for 1 h. Then, 1 g of polyether-modified silicone oil was added and ball-milled for 1 h to obtain a heat-insulating and anti-UV coating material for glass.

[0024] Example 6 A heat-insulating and anti-ultraviolet coating material for glass comprises the following raw materials in parts by weight: 58 parts of fluorinated acrylate copolymer emulsion, 8 parts of alumina ceramic fiber, 18 parts of composite hollow glass microspheres, 10 parts of composite nanoparticles, 38 parts of deionized water, 4 parts of film-forming aid, 2 parts of dispersant, 2 parts of defoaming agent, 0.1 part of thickener, and 0.8 part of leveling agent; the fluorinated acrylate copolymer emulsion is prepared by the method in Example 1, the composite hollow glass microspheres are prepared by the method in Example 2, the composite nanoparticles are prepared by the method in Example 3, and the alumina ceramic fiber is prepared by the method in Example 4. The preparation method of the heat-insulating and anti-ultraviolet coating material for glass comprises the following steps: S1: 8 g of alumina ceramic fiber, 18 g of composite hollow glass microspheres, 10 g of composite nanoparticles, 38 g of deionized water, 2 g of polyacrylate ammonium salt, and 0.8 g of long-chain alkyl silicone oil were mixed, stirred for 8 min, and ultrasonicated for 25 min to obtain a filler slurry; S2: 58 g of fluorinated acrylate copolymer emulsion, filler slurry, 4 g of propylene glycol methyl ether, and 0.1 g of nonionic polyurethane associative thickener HEUR were placed in a ball mill and ball-milled for 2 h. 2 g of polyether-modified silicone oil was then added and ball-milled for 1 h to obtain a heat-insulating and anti-UV coating material for glass.

[0025] Example 7 A heat-insulating and anti-UV coating material for glass comprises the following raw materials in parts by weight: 65 parts of fluorinated acrylate copolymer emulsion, 10 parts of alumina ceramic fiber, 20 parts of composite hollow glass microspheres, 15 parts of composite nanoparticles, 45 parts of deionized water, 4 parts of film-forming aid, 2 parts of dispersant, 2 parts of defoaming agent, 0.1 part of thickener, and 0.8 part of leveling agent; the fluorinated acrylate copolymer emulsion is prepared by the method in Example 1, the composite hollow glass microspheres are prepared by the method in Example 2, the composite nanoparticles are prepared by the method in Example 3, and the alumina ceramic fiber is prepared by the method in Example 4. The preparation method of the heat-insulating and anti-UV coating material for glass comprises the following steps: S1: 10g alumina ceramic fiber, 20g composite hollow glass microspheres, 15g composite nanoparticles, 45g deionized water, 2g polyacrylate ammonium salt, and 2g long-chain alkyl silicone oil were mixed, stirred for 10min, and ultrasonicated for 30min to obtain a filler slurry; S2: 65 g of fluorinated acrylate copolymer emulsion, filler slurry, 4 g of propylene glycol methyl ether, and 0.1 g of nonionic polyurethane associative thickener HEUR were placed in a ball mill and ball-milled for 2 h. 2 g of polyether-modified silicone oil was then added and ball-milled for 1 h to obtain a heat-insulating and anti-UV coating material for glass.

[0026] Comparative Example 1 A heat-insulating and anti-UV coating material for glass includes the following raw materials in parts by weight: 58 parts of fluorinated acrylate copolymer emulsion, 18 parts of composite hollow glass microspheres, 10 parts of composite nanoparticles, 38 parts of deionized water, 4 parts of film-forming aid, 2 parts of dispersant, 2 parts of defoaming agent, 0.1 part of thickener, and 0.8 part of leveling agent; the fluorinated acrylate copolymer emulsion is prepared by the method in Example 1, the composite hollow glass microspheres are prepared by the method in Example 2, and the composite nanoparticles are prepared by the method in Example 3. The preparation method of the heat-insulating and anti-UV coating material for glass includes the following steps: S1: 18 g of composite hollow glass microspheres, 10 g of composite nanoparticles, 38 g of deionized water, 2 g of polyacrylate ammonium salt, and 0.8 g of long-chain alkyl silicone oil were mixed, stirred for 8 min, and ultrasonicated for 25 min to obtain a filler slurry; S2: 58 g of fluorinated acrylate copolymer emulsion, filler slurry, 4 g of propylene glycol methyl ether, and 0.1 g of nonionic polyurethane associative thickener HEUR were placed in a ball mill and ball-milled for 2 h. 2 g of polyether-modified silicone oil was then added and ball-milled for 1 h to obtain a heat-insulating and anti-UV coating material for glass.

[0027] A glass heat insulation anti-ultraviolet coating material includes the following raw materials by weight: 58 parts of a fluorine-containing acrylic ester copolymer emulsion, 8 parts of alumina ceramic fiber, 10 parts of composite nanoparticles, 38 parts of deionized water, 4 parts of a film-forming aid, 2 parts of a dispersing agent, 2 parts of a defoaming agent, 0.1 part of a thickening agent, and 0.8 parts of a leveling agent; the fluorine-containing acrylic ester copolymer emulsion is prepared by the method in Example 1, the composite nanoparticles are prepared by the method in Example 3, the alumina ceramic fiber is prepared by the method in Example 4, and the preparation method of the glass heat insulation anti-ultraviolet coating material includes the following steps: S1: 8g of alumina ceramic fiber, 10g of composite nanoparticles, 38g of deionized water, 2g of polyacrylic acid ammonium salt, and 0.8g of long-chain alkyl silicone oil are mixed, stirred for 8min, and ultrasonically treated for 25min to obtain a filler slurry; S2: 58g of the fluorine-containing acrylic ester copolymer emulsion, the filler slurry, 4g of propylene glycol methyl ether, and 0.1g of non-ionic polyurethane associated thickening agent HEUR are placed in a ball mill and ball-milled for 2h, and then 2g of polyether-modified silicone oil is added and ball-milled for 1h to obtain the glass heat insulation anti-ultraviolet coating material.

[0028] A glass heat insulation anti-ultraviolet coating material includes the following raw materials by weight: 58 parts of a fluorine-containing acrylic ester copolymer emulsion, 8 parts of alumina ceramic fiber, 10 parts of composite nanoparticles, 38 parts of deionized water, 4 parts of a film-forming aid, 2 parts of a dispersing agent, 2 parts of a defoaming agent, 0.1 part of a thickening agent, and 0.8 parts of a leveling agent; the fluorine-containing acrylic ester copolymer emulsion is prepared by the method in Example 1, the composite nanoparticles are prepared by the method in Example 3, the alumina ceramic fiber is prepared by the method in Example 4, and the preparation method of the glass heat insulation anti-ultraviolet coating material includes the following steps: S1: 8g of alumina ceramic fiber, 18g of composite hollow glass microbeads, 38g of deionized water, 2g of polyacrylic acid ammonium salt, and 0.8g of long-chain alkyl silicone oil are mixed, stirred for 8min, and ultrasonically treated for 25min to obtain a filler slurry; S2: 58g of the fluorine-containing acrylic ester copolymer emulsion, the filler slurry, 4g of propylene glycol methyl ether, and 0.1g of non-ionic polyurethane associated thickening agent HEUR are placed in a ball mill and ball-milled for 2h, and then 2g of polyether-modified silicone oil is added and ball-milled for 1h to obtain the glass heat insulation anti-ultraviolet coating material.

[0029] Performance detection: 1. Thermal Insulation: In accordance with GB / T 29501-2013 "Thermal Insulating Coated Glass," Examples 5-7 and Comparative Examples 1-3 were each coated on a 35 cm × 35 cm × 6 mm monolithic glass substrate to produce a sample. The sample was placed in a test apparatus, simulating vertical solar irradiation conditions. Under specified wind speed, temperature, and irradiation conditions, the 35 cm × 35 cm × 6 mm reference specimen and the sample were continuously irradiated. The air temperature in the test chamber was measured, and the temperature difference was calculated. A temperature greater than or equal to 7°C was considered acceptable. The results are shown in Table 1.

[0030] 2. Heat Resistance: According to GB / T 1735-2009, "Determination of Heat Resistance of Paints and Varnishes," Examples 5-7 and Comparative Examples 1-3 were each coated on a 35 cm × 35 cm × 6 mm single-piece glass substrate to prepare a sample. The sample was placed in a high-temperature furnace and baked at 650°C for 24 h. The sample was removed and cooled to room temperature, and the coating film was inspected for cracking or peeling. The results are shown in Table 1.

[0031] Table 1 Statistical table of thermal conductivity and heat resistance of samples obtained in Examples 5-7 and Comparative Examples 1-3

[0032] As can be seen from Table 2, Examples 5-7 and Comparative Example 3 have excellent thermal properties; Comparative Example 1 lacks alumina ceramic fibers, which causes the thermal insulation temperature difference between the inside and outside of the sample to decrease, and the thermal insulation performance is reduced to a certain extent; Comparative Example 2 lacks composite hollow glass microspheres, resulting in a significant decrease in thermal insulation and heat resistance.

[0033] 3. Light transmittance, infrared transmittance, and ultraviolet transmittance: According to GB / T 2680-2021 "Architectural glass — Determination of visible light transmittance, direct solar transmittance, total solar transmittance, ultraviolet transmittance, and related window glass parameters," Examples 5-7 and Comparative Examples 1-3 were respectively coated on a 50 mm × 50 mm × 6 mm monolithic glass substrate to prepare samples. Under CIE D65 standard illumination conditions and with the CIE standard viewing function as the receiving condition, the light transmittance, infrared transmittance, and ultraviolet transmittance were measured as the ratio of the transmitted luminous flux to the incident luminous flux within the visible light spectrum (380-780 nm), infrared spectrum (780–2500 nm), and ultraviolet spectrum (300-400 nm). A light transmittance greater than or equal to 60% and an ultraviolet transmittance less than or equal to 10% were considered acceptable. The results are shown in Table 2.

[0034] Table 2 Statistical table of sample data obtained from Examples 5-7 and Comparative Examples 1-3

[0035] As can be seen from Table 2, Comparative Example 3 has almost no infrared and ultraviolet absorption due to the lack of composite nanoparticles, and its light transmittance is also lower than that of Examples 5-7 and Comparative Examples 1-2; Comparative Example 2 does not contain composite hollow glass microspheres, and its anti-ultraviolet ability is slightly lower than that of Examples 5-7 and Comparative Example 1.

[0036] The embodiments of the present invention are described in detail above, but the contents described are only preferred embodiments of the present invention and should not be considered to limit the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A heat-insulating and anti-ultraviolet coating material for glass, characterized in that: The thermal insulation and anti-ultraviolet coating material for glass includes the following raw materials in parts by weight: 50-65 parts of fluorine-containing acrylate copolymer emulsion, 5-10 parts of alumina ceramic fiber, 15-20 parts of composite hollow glass microspheres, 5-15 parts of composite nanoparticles, 30-45 parts of deionized water, 4 parts of film-forming aid, 1-2 parts of dispersant, 1-2 parts of defoaming agent, 0.1 part of thickener, and 0.8 part of leveling agent; the composite hollow glass microspheres are hollow glass microspheres with modified nano-TiO2 attached to the surface; the alumina ceramic fiber is ytterbium silicate-modified alumina ceramic fiber; and the composite nanoparticles are zirconium oxide, tin oxide antimony nanoparticles, and cesium tungsten bronze nanoparticles.

2. The heat-insulating and anti-ultraviolet coating material for glass according to claim 1, characterized in that: The fluorinated acrylate copolymer emulsion comprises the following raw materials in parts by weight: 40-60 parts by weight of propylene glycol methyl ether, 25-35 parts by weight of butyl acrylate, 40-45 parts by weight of methyl methacrylate, 30-50 parts by weight of acrylic acid, 2 parts by weight of azobisisobutyronitrile, and 25-35 parts by weight of N,N-dimethylethanolamine. The preparation method of the fluorinated acrylate copolymer emulsion comprises the following steps: Propylene glycol methyl ether was added to a reaction flask, which was filled with nitrogen and heated to 110°C. Butyl acrylate, methyl methacrylate, acrylic acid, and azobisisobutyronitrile were mixed to obtain a mixture, which was added dropwise to the reaction flask at 110°C for 2.5-3 hours. After reacting for 4-6 hours, the mixture was cooled to 60°C, N,N-dimethylethanolamine was added, and stirred for 1 hour to obtain a fluorinated acrylate copolymer emulsion.

3. The heat-insulating and anti-ultraviolet coating material for glass according to claim 1, characterized in that: The film-forming aid is any one or more of propylene glycol methyl ether, propylene glycol butyl ether, and alcohol ester twelve; The dispersant is ammonium polyacrylate; The defoaming agent is polyether modified silicone oil; The thickener is a nonionic polyurethane associative thickener HEUR; The leveling agent is long-chain alkyl silicone oil.

4. The heat-insulating and anti-ultraviolet coating material for glass according to claim 1, characterized in that: The preparation method of the composite hollow glass microspheres comprises the following steps: A1: Add vinyltrimethoxysilane to an ethanol aqueous solution, adjust the pH to 5.0-7.0 with acetic acid, add hollow glass microspheres and nano-TiO2 powder, stir at 70°C for 6-8 hours, and dry to obtain nano-TiO2 surface-modified hollow glass microspheres; A2: Treat the nano-TiO2 surface-modified hollow glass microspheres with HNO3 acid for 1-2 hours, filter out the solid components, mix with heptadecafluorodecyltriethoxysilane and ethanol aqueous solution, and react at 60-80°C in a nitrogen atmosphere for 6 hours. Wash with anhydrous ethanol and dry to obtain composite hollow glass microspheres.

5. The heat-insulating and anti-ultraviolet coating material for glass according to claim 4, characterized in that: The concentration of ethanol aqueous solution in A1 is 90 vol%, and the addition ratio of vinyltrimethoxysilane, ethanol aqueous solution, hollow glass microspheres, and nano-TiO2 powder is 1-2 g:100 mL:5-10 g:8-15 g; The concentration of HNO3 in A2 is 5wt%, the concentration of ethanol aqueous solution is 90vol%, and the addition ratio of nano-TiO2 surface-modified hollow glass microspheres, HNO3, heptadecafluorodecyltriethoxysilane, and ethanol aqueous solution is 0.5-1g:15mL:1-2g:30mL.

6. The heat-insulating and anti-ultraviolet coating material for glass according to claim 1, characterized in that: The preparation method of the composite nanoparticles comprises the following steps: B1: SnCl4·5H2O, SbCl3, ZrOCl2·8H2O, and ethanol were mixed and ultrasonicated until completely dissolved. NH4OH was added dropwise to form a white precipitate. H2O2 solution was added, stirred for 30 minutes, and then allowed to stand for 8 hours. The precipitate was washed until the presence of chloride ions could no longer be detected with silver nitrate solution. The precipitate was dispersed in water, the pH was adjusted to 8.5-9.5 with NH4OH, and the mixture was transferred to a reaction flask and heated at 220–240°C for 12 hours. After cooling, the powder was dispersed in deionized water to obtain a composite tin oxide antimony nanoparticle dispersion. B2: WCl6 powder, CsOH·H2O powder, and anhydrous ethanol were mixed, acetic acid was added, and the mixture was kept at 200℃ for 24 hours. After the reaction, the mixture was cooled, the precipitate was collected by centrifugation, washed with ethanol, and dried. Silane coupling agent KH570 and deionized water were added and ball milled for 4 hours to obtain cesium tungsten bronze nanoparticle dispersion; B3: Mix equal volumes of composite antimony tin oxide nanoparticle dispersion and cesium tungsten bronze nanoparticle dispersion, slowly add butanol, and sonicate for 10-30 minutes; centrifuge to obtain a precipitate, wash with anhydrous ethanol, and dry to obtain composite nanoparticles.

7. The heat-insulating and anti-ultraviolet coating material for glass according to claim 6, characterized in that: The concentration of H2O2 solution in B1 is 30wt%, and the addition ratio of SnCl4·5H2O, SbCl3, ZrOCl2·8H2O, ethanol, and H2O2 solution is 2.8-3.0g:0.2-0.3g:2.2-2.6g:40mL:0.5-0.6mL. The solid content of composite tin oxide antimony nanoparticle dispersion is 4%; The addition ratio of WCl6 powder, CsOH·H2O powder, anhydrous ethanol, acetic acid, and silane coupling agent KH570 in B2 is 0.4-0.5g: 0.08-0.11g: 20mL: 10mL: 0.05g, and the solid content of cesium tungsten bronze nanoparticle dispersion is 4%; The amount of butanol added in B3 is 5% of the total volume of the composite antimony tin oxide nanoparticle dispersion and the cesium tungsten bronze nanoparticle dispersion.

8. The heat-insulating and anti-ultraviolet coating material for glass according to claim 1, characterized in that: The preparation method of the alumina ceramic fiber comprises the following steps: C1: Yb2O3 powder and SiO2 powder are mixed and sintered to obtain composite powder; polyvinyl alcohol is dissolved in hot water to obtain a polyvinyl alcohol aqueous solution; C2: polyvinyl alcohol aqueous solution, aluminum isopropoxide, composite powder, and polydimethylsiloxane are mixed and stirred for 2-4 hours to obtain a spinning solution, and the spinning solution is spun and dried to obtain alumina ceramic fibers.

9. The heat-insulating and anti-ultraviolet coating material for glass according to claim 1, characterized in that: The concentration of polyvinyl alcohol aqueous solution in C1 is 12-16wt%, and the mass ratio of Yb2O3 powder and SiO2 powder added is 75-85:10-14; In C2, the added mass ratio of polyvinyl alcohol aqueous solution, aluminum isopropoxide, composite powder, and polysiloxane is 25-60:30-40:40-50:5-10.

10. The method for preparing a heat-insulating and anti-ultraviolet coating material for glass according to any one of claims 1 to 9, characterized in that: The steps include: S1: Alumina ceramic fibers, composite hollow glass microspheres, composite nanoparticles, deionized water, dispersant, and leveling agent are mixed, stirred for 5-10 minutes, and ultrasonicated for 20-30 minutes to obtain a filler slurry; S2: Put the fluorinated acrylic copolymer emulsion, filler slurry, film-forming aid, and thickener into a ball mill and mill them for 1-2 hours, then add a defoaming agent and mill them for 1 hour to obtain a heat-insulating and anti-ultraviolet coating material for glass.

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