Organic-inorganic hybrid coating and its use in the production of surface coatings for architectural decorative materials

Abstract

The application belongs to the technical field of polymer coating, and particularly relates to an organic-inorganic hybrid coating and application thereof in preparation of a surface coating of building decoration materials. The organic-inorganic hybrid coating mainly comprises photocuring resin, photocuring monomer, epoxy resin, modified diamond nanosheet, modified zirconium oxide coated aluminum oxide and photoinitiator. The photocuring resin, photocuring monomer and epoxy resin endow the coating with good toughness and rigidity, and the modified diamond nanosheet and modified zirconium oxide coated aluminum oxide serve as wear-resistant fillers to endow the coating with good wear resistance. The organic-inorganic hybrid coating has strong adhesion strength to the building material substrate, and has high gloss, gloss uniformity, scratch resistance, wear resistance and impact resistance, can replace the traditional sintered glaze layer, reduce energy consumption and improve product quality, and can be used as a coating for surface decoration of building decoration materials to replace the traditional glaze layer.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polymer coating, and particularly relates to an organic-inorganic hybrid coating and application thereof in preparation of a surface coating of building decoration materials. BACKGROUND

[0002] The existing glazed ceramic tile is formed by applying glaze on the surface of a building substrate and then firing at high temperature and high pressure, and is generally prepared by roll coating and film pressing technology. The glazed ceramic tile is composed of a body and a glaze on the surface, and the body is divided into two types of earthenware clay and porcelain clay. The back of the earthenware clay fired is red, and the back of the porcelain clay fired is gray white. The surface of the glazed tile can be made into various patterns and designs, and the color and pattern are more abundant than those of polished tiles. Because the surface is glaze, the wear resistance is poorer than that of the polished tile. According to the gloss, the glazed tile can be divided into two types of glossy glazed tile and matte glazed tile. The glazed tile is the most common tile in decoration, and is widely used in wall and floor decoration due to the rich color and pattern and strong stain resistance.

[0003] However, the glazed ceramic tile is extremely hard and brittle because it is an inorganic material. In addition, the tolerance of the substrate during preparation of the glazed ceramic tile is required to be less than or equal to 0.3 mm. Even so, the surface quality of the product is poor and the yield is low after roll coating and film pressing firing, and the wear resistance of the high-gloss wallboard is insufficient. The root cause of the above problems lies in that the glaze layer of the inorganic material has high hardness, but poor toughness and impact resistance, resulting in that the wear resistance and surface quality cannot meet the use requirements. Therefore, it is urgent to provide a coating for surface decoration of building decoration materials which can replace the traditional glaze layer. SUMMARY

[0004] In view of the above problems, the present application provides an organic-inorganic hybrid coating and application thereof in preparation of a surface coating of building decoration materials, which is used to solve the problems of high hardness, brittleness, poor wear resistance and surface quality of the existing glazed ceramic tile.

[0005] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0006] An organic-inorganic hybrid coating mainly consists of photocuring resin, photocuring monomer, epoxy resin, modified diamond nanosheet, modified zirconium oxide coated aluminum trioxide and photoinitiator; the modified diamond nanosheet and the modified zirconium oxide coated aluminum trioxide are prepared by modifying the diamond nanosheet and the zirconium oxide coated aluminum trioxide with a branched multivalent olefin quaternary ammonium salt silane coupling agent; the preparation method of the zirconium oxide coated aluminum trioxide is as follows: first, the nanometer aluminum trioxide, water, polyethylene glycol phosphate quaternary ammonium salt, zirconium oxychloride and aluminum chloride are mixed and reacted to obtain an intermediate, and then the intermediate, water, polyethylene glycol phosphate quaternary ammonium salt and zirconium oxychloride are mixed and reacted to obtain the zirconium oxide coated aluminum trioxide; the structure of the branched multivalent olefin quaternary ammonium salt silane coupling agent is as follows:

[0007] ;

[0008] The structure of the polyethylene glycol phosphate quaternary ammonium salt is as follows:

[0009] .

[0010] Preferably, the method for preparing the intermediate is as follows: mixing nano-aluminum oxide, water and polyethylene glycol phosphate quaternary ammonium salt to obtain a nano-aluminum oxide dispersion; then adding a mixed solution of zirconium oxychloride and aluminum chloride, and adjusting the pH of the reaction system to 8.5-9 with ammonia water, and incubating at 60-65℃ for 2-3h, and then washing the obtained solid after solid-liquid separation to obtain the intermediate; the mass of the polyethylene glycol phosphate quaternary ammonium salt is 1-3% of the mass of the nano-aluminum oxide, and the mass fraction of the nano-aluminum oxide in the nano-aluminum oxide dispersion is 6-8%; the total mass fraction of zirconium oxychloride and aluminum chloride in the mixed solution of zirconium oxychloride and aluminum chloride is 4-6%, and the mass ratio of zirconium oxychloride to aluminum chloride is 2-3:4-5; the mass ratio of the nano-aluminum oxide in the nano-aluminum oxide dispersion to the mass of zirconium oxychloride in the mixed solution of zirconium oxychloride and aluminum chloride is 1.5-2.5:1.

[0011] Preferably, the method for preparing the intermediate is as follows: mixing nano-aluminum oxide, water and polyethylene glycol phosphate quaternary ammonium salt to obtain a nano-aluminum oxide dispersion; then adding a mixed solution of zirconium oxychloride and aluminum chloride, and adjusting the pH of the reaction system to 8.5-9 with ammonia water, and incubating at 60-65℃ for 2-3h, and then washing the obtained solid after solid-liquid separation to obtain the intermediate; the mass of the polyethylene glycol phosphate quaternary ammonium salt is 1-3% of the mass of the nano-aluminum oxide, and the mass fraction of the nano-aluminum oxide in the nano-aluminum oxide dispersion is 6-8%; the total mass fraction of zirconium oxychloride and aluminum chloride in the mixed solution of zirconium oxychloride and aluminum chloride is 4-6%, and the mass ratio of zirconium oxychloride to aluminum chloride is 2-3:4-5; the mass ratio of the nano-aluminum oxide in the nano-aluminum oxide dispersion to the mass of zirconium oxychloride in the mixed solution of zirconium oxychloride and aluminum chloride is 1.5-2.5:1.

[0012] Preferably, the average particle size of the nano-aluminum oxide is 10-20nm.

[0013] Preferably, the preparation method of the modified zirconium oxide coated aluminum oxide is as follows: mixing branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and zirconium oxide coated aluminum oxide at 90-95℃ for 9-12h to obtain modified zirconium oxide coated aluminum oxide; the mass ratio of the branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and zirconium oxide coated aluminum oxide is 8-10:25-35:70-90:3-5.

[0014] Preferably, the preparation method of the modified diamond nanosheet is as follows: the branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and diamond nanosheet are mixed and reacted at 90-95 DEG C for 9-12h to obtain the modified diamond nanosheet; the mass ratio of the branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and diamond nanosheet is 8-10:25-35:70-90:4-6.

[0015] Preferably, the average flake diameter of the diamond nanosheet is 50-80nm.

[0016] Preferably, the photocuring monomer is composed of 2-acrylic acid-2-[[(butylamino)- carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate, the photocuring resin is aliphatic polyurethane acrylate; the epoxy resin is epoxy resin E51; the organic-inorganic hybrid coating further comprises a release aid, and the release aid is isooctanol phosphate.

[0017] Preferably, the photocuring resin and photocuring monomer constitute a photocuring mixture, and the mass ratio of the photocuring mixture, epoxy resin, modified diamond nanosheet, modified zirconia-coated aluminum oxide, photoinitiator and release aid is 50-60:20-30:5-8:10-15:3-5:0.5-1; the mass ratio of aliphatic polyurethane acrylate, 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate is 50-65:10-15:7-10:18-20.

[0018] The application of the organic-inorganic hybrid coating as described above in the preparation of a surface coating of building decoration materials.

[0019] The organic-inorganic hybrid coating and the application of the organic-inorganic hybrid coating in the preparation of a surface coating of building decoration materials have the following beneficial effects:

[0020] (1) The application improves the combination strength and coating uniformity of zirconium oxide on the surface of aluminum oxide by coating zirconium oxide and aluminum oxide precursors on the surface of nano-aluminum oxide as a transition layer, then coating zirconium oxide precursors again, and finally obtaining zirconium oxide coated aluminum oxide by calcination, thereby improving the overall strength and integrity of zirconium oxide coated aluminum oxide, avoiding the falling off or damage of zirconium oxide on the surface of the particles when rubbed, and affecting the overall performance of the coating. And the application synthesizes polyethylene glycol phosphate quaternary ammonium salt, which has a branched structure, contains a large number of quaternary ammonium salt groups, phosphate and alcohol ether structures, has excellent surface activity, can improve the dispersibility of nano-aluminum oxide, and can also improve the uniformity of the distribution of zirconium oxide and aluminum oxide precursors, and promote the uniform approach of the precursors to the surface of nano-aluminum oxide, thereby improving the coating uniformity of the zirconium oxide and aluminum oxide transition layer and the pure zirconium oxide layer.

[0021] (2) The application further improves the dispersibility of zirconium oxide coated aluminum oxide and diamond nanosheet in the organic resin matrix and the combination strength with the coating by synthesizing branched multi-olefin quaternary ammonium salt silane coupling agent and using the silane coupling agent for surface modification of zirconium oxide coated aluminum oxide and diamond nanosheet; wherein the branched multi-olefin quaternary ammonium salt silane coupling agent is chemically bonded to the surface of the solid particles through a siloxane structure, and the quaternary ammonium salt groups and adamantane structure on the coupling agent improve the dispersion uniformity and uniform arrangement of the solid particles in the organic resin system through surface activity and steric hindrance effect. In the curing stage, the double bond on the coupling agent crosslinks with the light-cured resin monomer, further improving the combination strength between the solid particles and the resin coating and the arrangement order in the coating. Finally, the organic-inorganic hybrid coating of the application is a dual-curing system, and the curing is divided into a pre-light curing stage and a post-thermal curing stage, which cooperate with each other to improve the comprehensive performance of the coating.

[0022] (3) The organic-inorganic hybrid coating of the application has strong adhesion strength to the building material substrate, and has high gloss, gloss uniformity, scratch resistance, wear resistance and impact resistance, which can replace the traditional sintered glaze layer, reduce energy consumption and improve product quality.

[0023] (4) The application realizes 1.2mm substrate defect filling (12 times of film pressing process) by a hot pressing assisted double curing process, and the prepared coating reaches EN16094 B2 level wear resistance, the bottom elastic network guarantees 1.5m drop ball without cracking, and the replication mirror surface precision (Ra≤0.01μm) is realized, which can effectively improve the wear resistance and surface quality of the glazed ceramic tile. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The nuclear magnetic hydrogen spectrum of the polyethylene glycol phosphate quaternary ammonium salt prepared in the embodiments of the application;

[0025] Figure 2 NMR spectrum of branched polyolefin silane coupling agent prepared in Example 1 of the present application;

[0026] Figure 3 NMR spectrum of branched polyolefin quaternary ammonium salt silane coupling agent prepared in Example 1 of the present application;

[0027] Figure 4 Appearance of coating prepared on surface of marble substrate using organic-inorganic hybrid coating of Example 1. DETAILED DESCRIPTION

[0028] In order to make the skilled in the art better understand the technical solutions, the following detailed description of the present application is described in conjunction with the examples, the description of this part is only exemplary and explanatory, should not have any limit on the protection scope of the present application.

[0029] The preparation method of polyethylene glycol phosphate quaternary ammonium salt used in the following examples is as follows:

[0030] (1) A 35% by mass bromoacetyl chloride solution in dichloromethane was added dropwise to a 40% by mass polyethylene glycol (PEG400) solution in dichloromethane under stirring at 0°C, followed by adding triethylamine, and the reaction was stirred at room temperature for 6 h. The filtrate was obtained by filtration and distilled under reduced pressure to obtain brominated polyethylene glycol. The molar ratio of bromoacetyl chloride, polyethylene glycol and triethylamine was 1:1:1.3.

[0031] (2) Brominated polyethylene glycol, triisopentylamine and ethyl acetate were added to a reaction kettle, heated to 80°C, and stirred to reflux for 10 h. The product was obtained by distillation under reduced pressure. The molar ratio of brominated polyethylene glycol and triisopentylamine was 1:1.1, and the mass of ethyl acetate was 1.5 times the sum of the masses of brominated polyethylene glycol and triisopentylamine.

[0032] (3) A 25% by mass phosphorus oxychloride solution in dichloromethane was added dropwise to a 35% by mass quaternary ammonium salt polyethylene glycol solution in dichloromethane under stirring at -5°C, followed by adding triethylamine, and the reaction was stirred at room temperature for 6 h. The filtrate was obtained by filtration and distilled under reduced pressure to obtain a concentrated solution. The concentrated solution was purified by column chromatography using petroleum ether, ethyl acetate and dichloromethane (6:2:1 by volume) as eluent to obtain polyethylene glycol phosphate quaternary ammonium salt. The molar ratio of phosphorus oxychloride, quaternary ammonium salt polyethylene glycol and triethylamine was 1:3:3.2. The NMR spectrum of polyethylene glycol phosphate quaternary ammonium salt is shown in Figure 1 , and the chemical structure is as follows:

[0033] .

[0034] One, the specific implementation of the organic-inorganic hybrid coating of the present application is as follows:

[0035] Example 1

[0036] The organic-inorganic hybrid coating of the present example is prepared by a method comprising the following steps:

[0037] (1) Nanometer alumina trihydrate with an average particle size of 10 nm, water and a dispersing agent are added into a stirring kettle, stirred uniformly to obtain a nanometer alumina trihydrate dispersion liquid; then a mixed solution of zirconium oxychloride and aluminum chloride is added into the stirring kettle under stirring, stirred uniformly, and then the pH of the materials in the stirring kettle is adjusted to 9 with ammonia water, heated to 60℃, and kept for 2h of reaction, after the reaction is completed, filtered, and the filter cake is repeatedly washed with distilled water until no chloride ion is detected in the filtrate, and finally washed with anhydrous alcohol to obtain an intermediate; wherein the dispersing agent is polyethylene glycol phosphate quaternary ammonium salt, the mass of the dispersing agent is 1% of the mass of the nanometer alumina trihydrate, and the mass fraction of the nanometer alumina trihydrate in the nanometer alumina trihydrate dispersion liquid is 6%; the total mass fraction of zirconium oxychloride and aluminum chloride in the mixed solution of zirconium oxychloride and aluminum chloride is 4%, and the mass ratio of zirconium oxychloride to aluminum chloride is 2:4; the mass ratio of the nanometer alumina trihydrate in the nanometer alumina trihydrate dispersion liquid to the zirconium oxychloride in the mixed solution of zirconium oxychloride and aluminum chloride is 1.5:1.

[0038] (2) The intermediate, water and a dispersing agent are added into a stirring kettle, stirred uniformly to obtain an intermediate dispersion liquid; then a zirconium oxychloride solution is added into the stirring kettle under stirring, stirred uniformly, and then the pH of the materials in the stirring kettle is adjusted to 9 with ammonia water, heated to 60℃, and kept for 5h of reaction, after the reaction is completed, filtered, and the filter cake is repeatedly washed with distilled water until no chloride ion is detected in the filtrate, and finally washed with anhydrous alcohol, dried, and then calcined in a muffle furnace at 500℃ for 5h to obtain zirconia-coated alumina trihydrate; wherein the dispersing agent is polyethylene glycol phosphate quaternary ammonium salt, the mass of the dispersing agent is 1% of the mass of the intermediate, and the mass fraction of the intermediate in the intermediate dispersion liquid is 8%; the mass fraction of zirconium oxychloride in the zirconium oxychloride solution is 7%; the mass ratio of the intermediate in the intermediate dispersion liquid to the zirconium oxychloride in the zirconium oxychloride solution is 4:1.

[0039] (3) 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, 2-(2-aminoethylmercapto) ethanol, triethylamine and toluene are added into a reaction kettle, heated to 75℃, stirred for 6h of reaction, cooled to room temperature to obtain reaction liquid A;

[0040] A reaction kettle was charged with 1-(3-hydroxypropyl)-4-methylpiperazine and toluene in a mass ratio of 3:2, and stirred uniformly, then cooled to -5℃, a 25% by mass phosphorus trichloride toluene solution was added dropwise into the reaction kettle, then triethylamine was added, stirred at room temperature for 3h, filtered, and the filtrate was collected to obtain reaction liquid B;

[0041] Reaction liquid B was added to reaction liquid A, stirred at room temperature for 5h, filtered, and the filtrate was distilled under reduced pressure to remove the solvent, to obtain a concentrated liquid, which was purified by column chromatography to obtain the branched polyolefin silane coupling agent; the molar ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, 2-(2-aminoethylmercapto)ethanol, 1-(3-hydroxypropyl)-4-methylpiperazine and phosphorus trichloride was 4:2:1:1; when preparing reaction liquid A, the molar ratio of 2-(2-aminoethylmercapto)ethanol and triethylamine was 1:1.2, and the mass of toluene was 1.5 times the sum of the masses of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and 2-(2-aminoethylmercapto)ethanol; when preparing reaction liquid B, the molar ratio of 1-(3-hydroxypropyl)-4-methylpiperazine and triethylamine was 1:1.2, and the mass of toluene was 90% of the mass of 1-(3-hydroxypropyl)-4-methylpiperazine; the eluent used in the column chromatography purification was a mixed solvent composed of petroleum ether, ethyl acetate and dichloromethane in a volume ratio of 6:3:1. The nuclear magnetic resonance hydrogen spectrum of the branched polyolefin silane coupling agent is shown in Figure 2 , and the chemical structure is as follows:

[0042] .

[0043] (4) A reaction kettle was charged with the branched polyolefin silane coupling agent, brominated hydrocarbon and ethyl acetate, heated to 75℃, stirred to reflux for 12h, distilled under reduced pressure to remove the solvent, to obtain a concentrated liquid, which was purified by column chromatography to obtain the branched polyolefin quaternary ammonium salt silane coupling agent; the molar ratio of the branched polyolefin silane coupling agent and the brominated hydrocarbon was 1:4.8, and the mass of the ethyl acetate was 1.8 times the sum of the masses of the branched polyolefin silane coupling agent and the brominated hydrocarbon; the brominated hydrocarbon was 1-(2-bromoethyl)adamantane; the nuclear magnetic resonance hydrogen spectrum of the branched polyolefin quaternary ammonium salt silane coupling agent is shown in Figure 3 , and the chemical structure is as follows:

[0044] .

[0045] (5) branched multi-olefin quaternary ammonium salt silane coupling agent, water and ethanol are added into a stirring kettle, stirred uniformly, heated to 90℃, then the zirconium oxide coated with aluminum oxide is added into the stirring kettle, stirred and refluxed for 9h, cooled to room temperature, then filtered, the filter cake is washed with ethanol, dried to obtain the modified zirconium oxide coated with aluminum oxide; wherein the mass ratio of branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and zirconium oxide coated with aluminum oxide is 8:25:70:3.

[0046] (6) branched multi-olefin quaternary ammonium salt silane coupling agent, water and ethanol are added into a stirring kettle, stirred uniformly, heated to 90℃, then the diamond nanosheet with an average flake diameter of 50nm is added into the stirring kettle, stirred and refluxed for 9h, cooled to room temperature, then filtered, the filter cake is washed with ethanol, dried to obtain the modified diamond nanosheet; wherein the mass ratio of branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and diamond nanosheet is 8:25:70:4.

[0047] (7) aliphatic polyurethane diacrylate, 2-acrylic acid-2-[[(butylamino)- carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate are added into a stirring kettle, stirred uniformly to obtain a photocuring mixture; wherein the mass ratio of aliphatic polyurethane diacrylate, 2-acrylic acid-2-[[(butylamino)- carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate is 50:10:7:18, the preparation method of aliphatic polyurethane diacrylate is as follows: polytetrahydrofuran ether diol PTME650, isophorone diisocyanate and dibutyl tin dilaurate are added into a reaction kettle, heated to 80℃, stirred for 5h, then hydroxyethyl acrylate is added, heated to 90℃, then continue to stir for 2h, cooled to room temperature to obtain aliphatic polyurethane diacrylate, the molar ratio of polytetrahydrofuran ether diol PTME650, isophorone diisocyanate and hydroxyethyl acrylate is 1:2:2, the mass of dibutyl tin dilaurate is 0.03% of the sum of the mass of polytetrahydrofuran ether diol PTME650 and isophorone diisocyanate.

[0048] (8) the photocuring mixture, epoxy resin, modified diamond nanosheet, modified zirconium oxide coated with aluminum oxide, photoinitiator TPO and release aid are added into a stirring kettle, stirred uniformly to obtain an organic-inorganic hybrid coating; wherein the epoxy resin is epoxy resin E51, the release aid is isooctanol phosphate, the mass ratio of photocuring mixture, epoxy resin, modified diamond nanosheet, modified zirconium oxide coated with aluminum oxide, photoinitiator TPO and release aid is 50:20:5:10:3:0.5.

[0049] Example 2

[0050] The organic-inorganic hybrid coating of the present embodiment is prepared by a method comprising the following steps:

[0051] (1) Put nano-aluminum oxide with an average particle size of 15 nm, water and a dispersing agent into a stirring kettle, stir uniformly to obtain a nano-aluminum oxide dispersion; then put a mixed solution of zirconium oxychloride and aluminum chloride into the stirring kettle under stirring, stir uniformly, adjust the pH of the materials in the stirring kettle to 9 with ammonia water, heat to 62°C, keep warm for 2.5 h, filter after the reaction is completed, repeatedly wash the filter cake with distilled water until no chloride ion is detected in the filtrate, finally wash with anhydrous alcohol, to obtain an intermediate; wherein the dispersing agent is polyethylene glycol phosphate quaternary ammonium salt, the mass of the dispersing agent is 2% of the mass of the nano-aluminum oxide, the mass fraction of the nano-aluminum oxide in the nano-aluminum oxide dispersion is 7%; the total mass fraction of zirconium oxychloride and aluminum chloride in the mixed solution of zirconium oxychloride and aluminum chloride is 5%, the mass ratio of zirconium oxychloride to aluminum chloride is 2.5:4.5; the mass ratio of the nano-aluminum oxide in the nano-aluminum oxide dispersion to the zirconium oxychloride in the mixed solution of zirconium oxychloride and aluminum chloride is 2:1.

[0052] (2) Put the intermediate, water and a dispersing agent into a stirring kettle, stir uniformly to obtain an intermediate dispersion; then put a zirconium oxychloride solution into the stirring kettle under stirring, stir uniformly, adjust the pH of the materials in the stirring kettle to 9 with ammonia water, heat to 62°C, keep warm for 6 h, filter after the reaction is completed, repeatedly wash the filter cake with distilled water until no chloride ion is detected in the filtrate, finally wash with anhydrous alcohol, dry, then calcine in a muffle furnace at 520°C for 4 h to obtain zirconium oxide coated aluminum oxide; wherein the dispersing agent is polyethylene glycol phosphate quaternary ammonium salt, the mass of the dispersing agent is 2% of the mass of the intermediate, the mass fraction of the intermediate in the intermediate dispersion is 9%; the mass fraction of the zirconium oxychloride in the zirconium oxychloride solution is 8%; the mass ratio of the intermediate in the intermediate dispersion to the zirconium oxychloride in the zirconium oxychloride solution is 5:1.

[0053] (3) Put 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, 2-(2-aminoethylmercapto) ethanol, triethylamine and toluene into a reaction kettle, heat to 78°C, stir for 7 h, cool to room temperature to obtain reaction liquid A;

[0054] Put 1-(3-hydroxypropyl)-4-methylpiperazine and toluene with a mass ratio of 3:2 into a reaction kettle, stir uniformly, then cool to -2°C, drop a toluene solution of phosphorus trichloride with a mass fraction of 28% into the reaction kettle, then add triethylamine, stir for 4 h at room temperature, filter, collect the filtrate to obtain reaction liquid B;

[0055] The reaction liquid B is added dropwise into the reaction liquid A, the reaction is stirred at room temperature for 6 hours, the filtrate is distilled under reduced pressure to remove the solvent, a concentrated liquid is obtained, the concentrated liquid is purified by column chromatography to obtain a branched multi-olefin silane coupling agent; wherein the molar ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, 2-(2-aminoethylmercapto) ethanol, 1-(3-hydroxypropyl)-4-methyl piperazine and phosphorus trichloride is 4:2:1:1; when preparing the reaction liquid A, the molar ratio of 2-(2-aminoethylmercapto) ethanol and triethylamine is 1:1.3, and the mass of toluene is 1.7 times the sum of the masses of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and 2-(2-aminoethylmercapto) ethanol; when preparing the reaction liquid B, the molar ratio of 1-(3-hydroxypropyl)-4-methyl piperazine and triethylamine is 1:1.2, and the mass of toluene is 100% of the mass of 1-(3-hydroxypropyl)-4-methyl piperazine; the eluent used in the purification by column chromatography is a mixed solvent composed of petroleum ether, ethyl acetate and dichloromethane in a volume ratio of 6:3:1.

[0056] (4) The branched multi-olefin silane coupling agent, brominated hydrocarbon and ethyl acetate are added into a reaction kettle, heated to 78°C, stirred and refluxed for 13 hours, distilled under reduced pressure to remove the solvent, a concentrated liquid is obtained, the concentrated liquid is purified by column chromatography to obtain a branched multi-olefin quaternary ammonium salt silane coupling agent; wherein the molar ratio of the branched multi-olefin silane coupling agent and the brominated hydrocarbon is 1:5, the mass of the ethyl acetate is 2 times the sum of the masses of the branched multi-olefin silane coupling agent and the brominated hydrocarbon, the brominated hydrocarbon is 1-(2-bromoethyl) adamantane, and the chemical structure of the branched multi-olefin quaternary ammonium salt silane coupling agent is as follows:

[0057] .

[0058] (5) The branched multi-olefin quaternary ammonium salt silane coupling agent, water and ethanol are added into a stirring kettle, stirred uniformly, heated to 92°C, then the zirconium oxide coated with aluminum oxide is added into the stirring kettle, stirred and refluxed for 11 hours, cooled to room temperature, filtered, the filter cake is washed with ethanol, dried to obtain modified zirconium oxide coated with aluminum oxide; wherein the mass ratio of the branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and zirconium oxide coated with aluminum oxide is 9:30:80:4.

[0059] (6) The branched multi-olefin quaternary ammonium salt silane coupling agent, water and ethanol are added into a stirring kettle, stirred uniformly, heated to 93°C, then the diamond nanosheet with an average flake diameter of 70 nm is added into the stirring kettle, stirred and refluxed for 10 hours, cooled to room temperature, filtered, the filter cake is washed with ethanol, dried to obtain modified diamond nanosheet; wherein the mass ratio of the branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and diamond nanosheet is 9:29:80:5.

[0060] (7) adding aliphatic polyurethane diacrylate, 2-acrylic acid-2-[[(butylamino)- carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate into a stirring kettle, stirring uniformly to obtain a photocuring mixture; wherein the mass ratio of aliphatic polyurethane diacrylate, 2-acrylic acid-2-[[(butylamino)- carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate is 58:12:8:19, the preparation method of aliphatic polyurethane diacrylate is as follows: adding polytetrahydrofuran ether diol PTME650, isophorone diisocyanate and dibutyl tin dilaurate into a reaction kettle, heating to 82℃, stirring for 6h, then adding hydroxyethyl acrylate, heating to 90℃ and continuing to stir for 2h, cooling to room temperature to obtain aliphatic polyurethane diacrylate, the molar ratio of polytetrahydrofuran ether diol PTME650, isophorone diisocyanate and hydroxyethyl acrylate is 1:2:2, the mass of dibutyl tin dilaurate is 0.05% of the sum of the mass of polytetrahydrofuran ether diol PTME650 and isophorone diisocyanate.

[0061] (8) adding the photocuring mixture, epoxy resin, modified diamond nanosheet, modified zirconia coated aluminum oxide, photoinitiator TPO and release aid into a stirring kettle, stirring uniformly to obtain an organic-inorganic hybrid coating; wherein the epoxy resin is epoxy resin E51, the release aid is isooctanol phosphate, the mass ratio of the photocuring mixture, epoxy resin, modified diamond nanosheet, modified zirconia coated aluminum oxide, photoinitiator TPO and release aid is 55:25:7:12:4:0.8.

[0062] Example 3

[0063] The organic-inorganic hybrid coating of the present embodiment is prepared by a method comprising the following steps:

[0064] (1) adding nano-aluminum oxide with an average particle size of 20 nm, water and a dispersing agent into a stirring kettle, stirring uniformly to obtain a nano-aluminum oxide dispersion liquid; then adding a mixed solution of zirconium oxychloride and aluminum chloride into the stirring kettle under stirring, stirring uniformly, adjusting the pH of the materials in the stirring kettle to 9 with ammonia water, heating to 65℃, and keeping the temperature for 3h, after the reaction, filtering, and repeatedly washing the filter cake with distilled water until no chloride ion is detected in the filtrate, finally washing with anhydrous alcohol, to obtain an intermediate; wherein the dispersing agent is polyethylene glycol phosphate quaternary ammonium salt, the mass of the dispersing agent is 3% of the mass of the nano-aluminum oxide, the mass fraction of the nano-aluminum oxide in the nano-aluminum oxide dispersion liquid is 8%; the total mass fraction of zirconium oxychloride and aluminum chloride in the mixed solution of zirconium oxychloride and aluminum chloride is 6%, the mass ratio of zirconium oxychloride to aluminum chloride is 3:5; the mass ratio of the nano-aluminum oxide in the nano-aluminum oxide dispersion liquid to the zirconium oxychloride in the mixed solution of zirconium oxychloride and aluminum chloride is 2.5:1.

[0065] (2) adding the intermediate, water and a dispersing agent into a stirring kettle, stirring uniformly to obtain an intermediate dispersion liquid; then adding a zirconium oxychloride solution into the stirring kettle under stirring, stirring uniformly, adjusting the pH of the materials in the stirring kettle to 9 with ammonia water, heating to 65℃, and keeping the temperature for 7h, after the reaction, filtering, and repeatedly washing the filter cake with distilled water until no chloride ion is detected in the filtrate, finally washing with anhydrous alcohol, drying, and then calcining in a muffle furnace at 550℃ for 3h to obtain zirconium oxide coated aluminum oxide; wherein the dispersing agent is polyethylene glycol phosphate quaternary ammonium salt, the mass of the dispersing agent is 3% of the mass of the intermediate, the mass fraction of the intermediate in the intermediate dispersion liquid is 10%; the mass fraction of the zirconium oxychloride in the zirconium oxychloride solution is 9%; the mass ratio of the intermediate in the intermediate dispersion liquid to the zirconium oxychloride in the zirconium oxychloride solution is 6:1.

[0066] (3) adding 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, 2-(2-aminoethylmercapto) ethanol, triethylamine and toluene into a reaction kettle, heating to 80℃, stirring for 8h, and cooling to room temperature to obtain reaction liquid A;

[0067] adding 1-(3-hydroxypropyl)-4-methylpiperazine and toluene with a mass ratio of 3:2 into a reaction kettle, stirring uniformly, and then cooling to 0℃, adding a 30% mass fraction of phosphorus trichloride toluene solution dropwise into the reaction kettle, and then adding triethylamine, stirring at room temperature for 5h, filtering, and collecting the filtrate to obtain reaction liquid B;

[0068] The reaction liquid B is added dropwise into the reaction liquid A, the reaction is stirred at room temperature for 7h, the filtrate is distilled under reduced pressure to remove the solvent, a concentrated liquid is obtained, the concentrated liquid is purified by column chromatography to obtain the branched multi-olefin silane coupling agent; wherein the molar ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, 2-(2-aminoethylmercapto) ethanol, 1-(3-hydroxypropyl)-4-methyl piperazine and phosphorus trichloride is 4:2:1:1; when preparing the reaction liquid A, the molar ratio of 2-(2-aminoethylmercapto) ethanol and triethylamine is 1:1.4, and the mass of toluene is 2 times the sum of the mass of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and the mass of 2-(2-aminoethylmercapto) ethanol; when preparing the reaction liquid B, the molar ratio of 1-(3-hydroxypropyl)-4-methyl piperazine and triethylamine is 1:1.3, and the mass of toluene is 120% of the mass of 1-(3-hydroxypropyl)-4-methyl piperazine; the eluent used in the purification by column chromatography is a mixed solvent composed of petroleum ether, ethyl acetate and dichloromethane with a volume ratio of 6:3:1.

[0069] (4) The branched multi-olefin silane coupling agent, brominated hydrocarbon and ethyl acetate are added into a reaction kettle, heated to 80℃, stirred and refluxed for 15h, distilled under reduced pressure to remove the solvent, a concentrated liquid is obtained, the concentrated liquid is purified by column chromatography to obtain the branched multi-olefin quaternary ammonium salt silane coupling agent; wherein the molar ratio of the branched multi-olefin silane coupling agent and the brominated hydrocarbon is 1:5.2, the mass of the ethyl acetate is 2.2 times the sum of the mass of the branched multi-olefin silane coupling agent and the mass of the brominated hydrocarbon, the brominated hydrocarbon is 1-(2-bromoethyl) adamantane, and the chemical structure of the branched multi-olefin quaternary ammonium salt silane coupling agent is as follows:

[0070] .

[0071] (5) The branched multi-olefin quaternary ammonium salt silane coupling agent, water and ethanol are added into a stirring kettle, stirred uniformly, heated to 95℃, then the zirconium oxide coated with aluminum oxide is added into the stirring kettle, stirred and refluxed for 12h, cooled to room temperature, filtered, the filter cake is washed with ethanol, dried to obtain the modified zirconium oxide coated with aluminum oxide; wherein the mass ratio of the branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and zirconium oxide coated with aluminum oxide is 10:35:90:5.

[0072] (6) The branched multi-olefin quaternary ammonium salt silane coupling agent, water and ethanol are added into a stirring kettle, stirred uniformly, heated to 95℃, then the diamond nanosheet with an average flake diameter of 80nm is added into the stirring kettle, stirred and refluxed for 12h, cooled to room temperature, filtered, the filter cake is washed with ethanol, dried to obtain the modified diamond nanosheet; wherein the mass ratio of the branched multi-olefin quaternary ammonium salt silane coupling agent, water, ethanol and diamond nanosheet is 10:35:90:6.

[0073] (7) adding aliphatic polyurethane diacrylate, 2-acrylic acid-2-[[(butylamino)- carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate into a stirring kettle, stirring uniformly to obtain a photocuring mixture; wherein the mass ratio of aliphatic polyurethane diacrylate, 2-acrylic acid-2-[[(butylamino)- carbonyl]oxy]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate is 65:15:10:20, the preparation method of aliphatic polyurethane diacrylate is as follows: adding polytetrahydrofuran ether diol PTME650, isophorone diisocyanate and dibutyl tin dilaurate into a reaction kettle, heating to 85℃, stirring for 7h, then adding hydroxyethyl acrylate, heating to 90℃ and continuing to stir for 3h, and then cooling to room temperature to obtain aliphatic polyurethane diacrylate, the molar ratio of polytetrahydrofuran ether diol PTME650, isophorone diisocyanate and hydroxyethyl acrylate is 1:2:2, and the mass of dibutyl tin dilaurate is 0.06% of the sum of the mass of polytetrahydrofuran ether diol PTME650 and isophorone diisocyanate.

[0074] (8) adding the photocuring mixture, epoxy resin, modified diamond nanosheet, modified zirconia coated aluminum oxide, photoinitiator TPO and release aid into a stirring kettle, stirring uniformly to obtain an organic-inorganic hybrid coating; wherein the epoxy resin is epoxy resin E51, the release aid is isooctanol phosphate, and the mass ratio of the photocuring mixture, epoxy resin, modified diamond nanosheet, modified zirconia coated aluminum oxide, photoinitiator TPO and release aid is 60:30:8:15:5:1.

[0075] Comparative Example 1

[0076] The difference between the organic-inorganic hybrid coating of the present comparative example and the organic-inorganic hybrid coating of Example 1 is that the organic-inorganic hybrid coating of the present comparative example omits step (1) during preparation, and directly replaces the intermediate in step (2) with the nanometer aluminum oxide in step (1).

[0077] Comparative Example 2

[0078] The difference between the organic-inorganic hybrid coating of the present comparative example and the organic-inorganic hybrid coating of Example 1 is that the dispersant in step (1) and step (2) during preparation of the organic-inorganic hybrid coating of the present comparative example is dodecyl trimethyl ammonium bromide.

[0079] Comparative Example 3

[0080] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that the preparation method of the polyethylene glycol phosphate ester quaternary ammonium salt in Step (1) and Step (2) in the preparation of the organic-inorganic hybrid coating of the present comparative example replaces triisopentylamine with triamylamine in Step (2).

[0081] Comparative Example 4

[0082] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that the mass ratio of zirconium oxychloride and aluminum chloride in Step (1) in the preparation of the organic-inorganic hybrid coating of the present comparative example is 1:4.

[0083] Comparative Example 5

[0084] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that the mass ratio of zirconium oxychloride and aluminum chloride in Step (1) in the preparation of the organic-inorganic hybrid coating of the present comparative example is 4:4.

[0085] Comparative Example 6

[0086] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that the modified diamond nanosheet in Step (8) in the preparation of the organic-inorganic hybrid coating of the present comparative example is replaced with the diamond nanosheet in Step (6), and the modified zirconium oxide coated di aluminum trioxide is replaced with the zirconium oxide coated di aluminum trioxide in Step (5).

[0087] Comparative Example 7

[0088] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that the branched polyolefin quaternary ammonium salt silane coupling agent in Step (5) and Step (6) in the preparation of the organic-inorganic hybrid coating of the present comparative example is replaced with 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane.

[0089] Comparative Example 8

[0090] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that 1-(3-hydroxypropyl)-4-methylpiperazine is replaced with N,N-dimethylaminoethyl-N-methylaminoethanol in Step (3) in the preparation of the organic-inorganic hybrid coating of the present comparative example.

[0091] Comparative Example 9

[0092] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that 2-(2-aminoethoxyl)ethanol is used instead of 2-(2-aminoethylmercapto)ethanol in step (3) during preparation of the organic-inorganic hybrid coating.

[0093] Comparative Example 10

[0094] The organic-inorganic hybrid coating of the present comparative example differs from the organic-inorganic hybrid coating of Example 1 only in that 2-bromoethylcyclohexane is used instead of 2-bromoethylcyclohexane in step (4) during preparation of the organic-inorganic hybrid coating.

[0095] II. Application of the organic-inorganic hybrid coating of the present application in preparing a surface coating of a building decoration material

[0096] Example 4

[0097] This example takes a marble building decoration material and the organic-inorganic hybrid coating of Example 1 as examples. The application of the organic-inorganic hybrid coating of this example in preparing a surface coating of a building decoration material comprises the following steps: the organic-inorganic hybrid coating is spray coated on the surface of the marble substrate to form a coating film with a thickness of 100 μm, then the coating film is irradiated and light cured using ultraviolet light, the light cured coating film is then hot pressed using a mirror surface steel plate (the Ra of the steel plate is ≤0.01 μm), and finally the hot pressed coating film is heat cured to obtain a cured coating; wherein the roughness of the surface of the marble substrate is 1.0 mm; the energy density of the ultraviolet light used for light curing is 300 mJ / cm 2 , and the time is 25 s; the temperature during hot pressing is 120 °C, the pressure is 4 MPa, and the time is 15 s; the temperature for heat curing is 150 °C, and the time is 30 min. The release aid in the coating can ensure that the steel plate and the coating film can be smoothly separated after hot pressing, without affecting the appearance quality of the coating. The appearance of the coating prepared on the surface of the marble substrate using the organic-inorganic hybrid coating of Example 1 is shown in Figure 4 .

[0098] Effect Example

[0099] In order to evaluate the comprehensive performance of the organic-inorganic hybrid coatings of each example and comparative example, the organic-inorganic hybrid coatings of each example and comparative example were respectively prepared into coatings according to the method of Example 4, and then the adhesion, gloss, gloss uniformity, scratch resistance, micro-scratch grade, wear resistance and impact resistance of the coatings were tested. Among them, the adhesion was tested according to the provisions in standard ASTM-D-4541 “pull-off adhesion test”; the gloss was measured by a gloss meter, and the measurement angle was 20° when measuring; the test method of gloss uniformity was as follows: the gloss of 15 positions on the coating was measured by a gloss meter, and then the maximum value of the difference of the gloss of the 15 positions was calculated, which represented the gloss uniformity; the test method of scratch resistance was as follows: 0# steel wool was used to rub back and forth on the surface of the coating at a constant speed, and the number of rubs required for the first obvious scratch on the surface of the coating was used as the evaluation index of scratch resistance, and a force of 1 kg was applied to the steel wool perpendicular to the surface of the coating during testing; the micro-scratch grade was tested and rated according to the provisions in standard BS EN 16094-2012 “laminated wood flooring. Micro-scratch test method”; the wear resistance was tested by an Akron abrasion tester under the same conditions, and the test result was represented by the amount of abrasion; the impact resistance was tested according to the provisions in standard GB / T1732-1993 “paint film impact resistance test method”. When testing the performance of each coating, each sample was repeated for 3 times, and the average value of the test results of 3 times was taken as the final test result.

[0100] The test results of the adhesion, gloss, gloss uniformity, scratch resistance, micro-scratch grade, wear resistance and impact resistance of the coatings prepared from the organic-inorganic hybrid coatings of each example and comparative example are shown in Table 1.

[0101]

[0102] It can be seen from the test results in Table 1 that the organic-inorganic hybrid coating has strong adhesion strength on the building material substrate, and has high gloss, gloss uniformity, scratch resistance, wear resistance and impact resistance. This is because the zirconium oxide coated aluminum trioxide is obtained by coating the precursor of zirconium oxide and aluminum oxide on the surface of nano-aluminum trioxide as a transition layer, then coating the precursor of zirconium oxide again, and finally calcining, so as to improve the bonding strength and coating uniformity of zirconium oxide on the surface of aluminum trioxide, and further improve the overall strength and integrity of the zirconium oxide coated aluminum trioxide, so as to avoid the falling off or damage of the zirconium oxide on the surface of the particles when rubbed, and affect the overall performance of the coating. And the branched polyethylene glycol phosphate quaternary ammonium salt is synthesized, which has a branched structure, contains a large number of quaternary ammonium salt groups, phosphate and alcohol ether structures, has excellent surface activity, can improve the dispersibility of nano-aluminum trioxide, and can improve the uniformity of the distribution of the precursor of zirconium oxide and aluminum oxide, and promote the precursor to uniformly approach the surface of nano-aluminum trioxide, and further improve the coating uniformity of the transition layer of zirconium oxide and aluminum oxide and the coating uniformity of the pure zirconium oxide layer. Secondly, the branched multi-olefin quaternary ammonium salt silane coupling agent is synthesized, and the surface of the zirconium oxide coated aluminum trioxide and the diamond nanosheet is modified by using the silane coupling agent, so as to further improve the dispersibility of the zirconium oxide coated aluminum trioxide and the diamond nanosheet in the organic resin matrix and the bonding strength with the coating; wherein the branched multi-olefin quaternary ammonium salt silane coupling agent is chemically bonded to the surface of the solid particles through the siloxane structure, and the quaternary ammonium salt groups and adamantane structures on the coupling agent improve the dispersibility and uniform arrangement of the solid particles in the organic resin system through surface activity and steric hindrance effect. In the curing stage, the double bond on the coupling agent reacts with the light-cured resin monomer to further improve the bonding strength between the solid particles and the resin coating and the arrangement order in the coating. Finally, the organic-inorganic hybrid coating is a dual-curing system, and the curing is divided into a pre-light curing stage and a post-thermal curing stage, and the two stages cooperate with each other to improve the hardness, flexibility and comprehensive performance of the coating, and realize the replacement of the traditional sintered glaze layer.

[0103] As can be seen from Example 1 and Comparative Example 1, when the transition layer of the precursor of zirconium oxide and aluminum oxide is omitted, due to the difference in surface structure and poor affinity, the coating uniformity and coating strength of the zirconium oxide layer on the surface of nano-aluminum trioxide are defective, resulting in deviation of the overall strength and wear resistance of the coated particles.

[0104] As can be seen from Example 1 and Comparative Examples 2-3, using a traditional quaternary ammonium salt dispersant or changing the branched structure in the dispersant to a straight chain structure, the dispersing effect of the dispersant on the nano-aluminum trioxide and the dispersing effect of the precursor are poor, which affects the quality of the coating layer and causes the performance of the coating to deteriorate.

[0105] It can be seen from the example 1 and the comparative examples 4-5 that the ratio of the precursors of zirconium oxide and aluminum oxide in the transition layer also affects the overall performance of the coated particles, and when the precursor of zirconium oxide in the transition layer is too much, the affinity and bonding strength with the inner layer of aluminum oxide become weak; and when the precursor of aluminum oxide in the transition layer is too much, the affinity and bonding strength with the outer layer of zirconium oxide become weak.

[0106] It can be seen from the example 1 and the comparative example 6 that when the unmodified wear-resistant particles are used, the dispersion and the bonding strength of the wear-resistant particles with the coating are poor due to the lack of quaternary ammonium salt and double bond groups on the surface, which affects the comprehensive performance of the coating.

[0107] It can be seen from the example 1 and the comparative examples 7-10 that when the unbranched silane coupling agent is used, the dispersion of the wear-resistant particles is poor due to the lack of quaternary ammonium salt and large steric adamantane structure, which affects the performance of the coating; and when the coupling agent lacks piperazine ring, sulfide bond or adamantane ring, the dispersion uniformity, ordered arrangement and compaction of the wear-resistant particles during the later curing are affected, which leads to poor comprehensive performance of the coating.

[0108] It can be seen from the above results that the organic-inorganic hybrid coating has a higher gloss, which is higher than 92~98GU of the traditional high-gloss wallboard and 90~95GU of the traditional glazed ceramic tile, the micro-scratch level is equivalent to that of the traditional glazed ceramic tile, and higher than the B5 level of the traditional high-gloss wallboard, the drop ball impact performance is higher than 0.5m of the traditional high-gloss wallboard and the traditional glazed ceramic tile, and the substrate tolerance tolerance (≤1.0mm) is significantly greater than that of the traditional high-gloss wallboard (≤0.2mm) and the traditional glazed ceramic tile (≤0.3mm).

[0109] It should be noted that in this paper, the terms: include, contain and any other variants are intended to cover non-exclusive inclusion, so that the process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or includes elements inherent to such process, method, article or device. The principle and implementation of the technical scheme of the present application are described by specific examples in this paper, and the above examples are only used to help understand the method and its core idea. The above described is only the preferred embodiment of the present application, it should be pointed out that due to the limitation of language expression, there are infinite specific structures, for ordinary skilled in the art, without departing from the principle of the present application, can make some improvement, decoration or change, or combine the above technical features in appropriate way, these improvements, decoration, change or combination, or without improvement, the concept and technical scheme of the present application are directly applied to other occasions, all should be regarded as the protection scope of the present application.

Claims

1. An organic-inorganic hybrid coating, characterized in that, The main components include a photocurable resin, a photocurable monomer, an epoxy resin, modified diamond nanosheets, modified zirconia-coated alumina, and a photoinitiator. The modified diamond nanosheets and modified zirconia-coated alumina are prepared by modifying the diamond nanosheets and zirconia-coated alumina with a branched polyolefin quaternary ammonium salt silane coupling agent. The zirconia-coated alumina is prepared by the following method: first, nano-alumina, water, polyethylene glycol phosphate quaternary ammonium salt, zirconium oxychloride, and aluminum chloride are mixed and reacted to obtain an intermediate. The mass ratio of zirconium oxychloride to aluminum chloride added during the preparation of the intermediate is 2-3:4-5. Then, the intermediate, water, polyethylene glycol phosphate quaternary ammonium salt, and zirconium oxychloride are mixed and reacted to obtain zirconia-coated alumina. The structure of the branched polyolefin quaternary ammonium salt silane coupling agent is as follows: ； The structure of the polyethylene glycol phosphate quaternary ammonium salt is as follows: 。 2. The organic-inorganic hybrid coating according to claim 1, characterized in that, The intermediate is prepared as follows: nano-alumina, water and polyethylene glycol phosphate quaternary ammonium salt are mixed to obtain a nano-alumina dispersion; then a mixed solution of zirconium oxychloride and aluminum chloride is added, and the pH of the reaction system is adjusted to 8.5~9 with ammonia water. The reaction is kept at 60~65℃ for 2~3h. After solid-liquid separation, the obtained solid is washed to obtain the intermediate. The mass of polyethylene glycol phosphate quaternary ammonium salt is 1-3% of the mass of nano-alumina, and the mass fraction of nano-alumina in the nano-alumina dispersion is 6-8%; the total mass fraction of zirconium oxychloride and aluminum chloride in the mixed solution is 4-6%; the mass ratio of nano-alumina in the nano-alumina dispersion to the mass of zirconium oxychloride in the mixed solution is 1.5-2.5:

1.

3. The organic-inorganic hybrid coating according to claim 1, characterized in that, The method for preparing zirconia-coated alumina using an intermediate is as follows: The intermediate, water, and polyethylene glycol phosphate quaternary ammonium salt are mixed to obtain an intermediate dispersion; then, a zirconium oxychloride solution is added, and the pH of the reaction system is adjusted to 8.5–9 with ammonia. The reaction is carried out at 60–65°C for 5–7 hours. After solid-liquid separation, the obtained solid is washed, dried, and calcined to obtain zirconia-coated alumina. The mass of polyethylene glycol phosphate quaternary ammonium salt is 1–3% of the mass of the intermediate, and the mass fraction of the intermediate in the intermediate dispersion is 8–10%. The mass fraction of zirconium oxychloride in the zirconium oxychloride solution is 7-9%; the mass ratio of the intermediate dispersion to the zirconium oxychloride in the zirconium oxychloride solution is 4-6:

1.

4. The organic-inorganic hybrid coating according to claim 1 or 2, characterized in that, The average particle size of the nano-alumina is 10~20nm.

5. The organic-inorganic hybrid coating according to claim 1, characterized in that, The preparation method of the modified zirconia-coated alumina is as follows: branched polyolefin quaternary ammonium salt silane coupling agent, water, ethanol and zirconia-coated alumina are mixed and reacted at 90~95℃ for 9~12h to obtain modified zirconia-coated alumina; the mass ratio of the branched polyolefin quaternary ammonium salt silane coupling agent, water, ethanol and zirconia-coated alumina is 8~10:25~35:70~90:3~5.

6. The organic-inorganic hybrid coating according to claim 1 or 5, characterized in that, The modified diamond nanosheets are prepared as follows: branched polyolefin quaternary ammonium salt silane coupling agent, water, ethanol and diamond nanosheets are mixed and reacted at 90~95℃ for 9~12h to obtain modified diamond nanosheets; the mass ratio of the branched polyolefin quaternary ammonium salt silane coupling agent, water, ethanol and diamond nanosheets is 8~10:25~35:70~90:4~6.

7. The organic-inorganic hybrid coating according to claim 6, characterized in that, The diamond nanosheets have an average diameter of 50-80 nm.

8. The organic-inorganic hybrid coating according to claim 1, characterized in that, The photocurable monomer is composed of 2-acrylate-2-[[(butylamino)-carbonyl]oxo]ethyl ester, trimethylolpropane triacrylate and tripropylene glycol diacrylate, the photocurable resin is an aliphatic polyurethane acrylate; the epoxy resin is epoxy resin E51; the organic-inorganic hybrid coating also includes a release agent, which is isooctyl phosphate.

9. The organic-inorganic hybrid coating according to claim 1, characterized in that, The photocurable resin and photocurable monomers constitute a photocurable mixture. The mass ratio of the photocurable mixture, epoxy resin, modified diamond nanosheets, modified zirconia-coated alumina, photoinitiator, and release agent is 50~60:20~30:5~8:10~15:3~5:0.5~1. The mass ratio of aliphatic polyurethane acrylate, 2-acrylate-2-[[(butylamino)-carbonyl]oxo]ethyl acrylate, trimethylolpropane triacrylate, and tripropylene glycol diacrylate is 50~65:10~15:7~10:18~20.

10. The application of an organic-inorganic hybrid coating as described in any one of claims 1-9 in the preparation of a surface coating for building decorative materials.

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