High-adhesion nanometer silicon coating and preparation method thereof

Abstract

The invention discloses a high-adhesion nanometer silicon coating and a preparation method thereof, and the high-adhesion nanometer silicon coating comprises the following components in parts by weight: 40-50 parts of a silicone acrylic emulsion, 10-15 parts of a titanium-silicon-based reinforcing agent, 5-9 parts of a vanadium-bismuth photoactive protective agent, 2-8 parts of an adhesion promoter, 5-10 parts of a coalescing agent, 15-30 parts of a pigment filler, 0.5-3 parts of a dispersant, 0.2-1 part of a defoaming agent, 0.5-2 parts of a thickening agent and 15-20 parts of deionized water. According to the high-adhesion nano silicon coating provided by the invention, the components are scientifically proportioned, so that excellent comprehensive performance is realized. The titanium-silicon-based reinforcing agent utilizes the high specific surface area and regular structure of the MCM-41 molecular sieve, and the surface modified amino and Schiff base structure of the MCM-41 molecular sieve more obviously enhances the chemical bonding capacity with a base material; the vanadium-bismuth photoactive protective agent passes through the photocatalytic characteristic of the vanadium-bismuth composite oxide.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a high-adhesion nano-silicon coating and its preparation method. Background Technology

[0002] In numerous fields such as industrial manufacturing, building protection, and transportation, coatings serve as crucial protective and functional decorative materials for substrate surfaces. Their performance directly determines the substrate's service life, safety, and appearance quality. Adhesion is one of the most critical performance indicators of coatings, determining the strength of the bond between the coating and the substrate, and directly affecting the durability of the coating's protective function. With the ever-increasing demands for material protection in modern industry, coatings need to operate for extended periods in complex environments such as high temperature and humidity, acid and alkali corrosion, and frequent friction and vibration. Under these harsh conditions, insufficient adhesion can lead to coating failures such as blistering, peeling, and cracking, ultimately resulting in loss of protective function and causing substrate corrosion, aging, and even structural failure. Therefore, developing high-adhesion coatings has become a core development direction for the coating industry, playing a vital role in ensuring the safety of engineering structures and extending equipment lifespan.

[0003] Traditional coatings primarily use organic resins as film-forming bases. While they possess good film-forming and decorative properties, they have inherent limitations in improving adhesion, making them unsuitable for complex working conditions. Firstly, the surface polarity difference between organic resins and inorganic substrates (such as metals, glass, and ceramics) is significant. Interfacial bonding relies mainly on weak physical interactions like van der Waals forces, lacking strong chemical bonds, making them prone to interfacial delamination under stress or environmental corrosion. Secondly, traditional coatings are prone to structural defects such as micropores and cracks during film formation. These defects reduce the effective contact area between the coating and the substrate, weakening physical interlocking and chemical bonding sites, further reducing adhesion. Furthermore, the limitations of traditional coatings in high and low temperature resistance and chemical corrosion resistance accelerate performance degradation in extreme environments, indirectly leading to interfacial bond failure and making it difficult to guarantee adhesion stability. Although the industry has attempted improvements through adding coupling agents and optimizing surface treatment processes, these methods have limited effectiveness and cannot simultaneously address adhesion and other comprehensive properties, failing to fundamentally solve the performance bottlenecks of traditional coatings.

[0004] Therefore, how to break through the performance bottlenecks of traditional coatings, meet the stringent protection requirements of high-end fields such as aerospace, marine engineering, and new energy, and promote the upgrading of the coating industry towards high performance are currently key research issues. Summary of the Invention

[0005] The main objective of this invention is to propose a high-adhesion nano-silicon coating and its preparation method, aiming to solve the problems of poor adhesion and poor anti-fouling performance of existing coatings.

[0006] To achieve the above objectives, the present invention provides a high-adhesion nano-silicon coating, comprising the following components by weight: The ingredients are: 40-50 parts silicone-acrylic emulsion, 10-15 parts titanium-silicon based reinforcing agent, 5-9 parts vanadium-bismuth photoactive protective agent, 2-8 parts adhesion promoter, 5-10 parts film-forming aid, 15-30 parts pigments and fillers, 0.5-3 parts dispersant, 0.2-1 part defoamer, 0.5-2 parts thickener, and 15-20 parts deionized water.

[0007] Preferably, the preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven, then calcine and cool it to obtain activated MCM-41 molecular sieve; S2. The activated MCM-41 molecular sieve is mixed with an ethanol-water solution, ultrasonically dispersed, tetraethoxysilane and isopropyl titanate are added, refluxed, filtered, washed, and vacuum dried to obtain titanium-silicon supported material. S3. Mix the titanium-silicon supported material with an aqueous ethanol solution, add 3-aminopropyltriethoxysilane, reflux the reaction, filter after the reaction is complete, wash, and vacuum dry to obtain the aminated composite material. S4. The aminated composite material is mixed with anhydrous ethanol, p-hydroxybenzaldehyde is added and mixed, stirred and heated to react. After the reaction is completed, the mixture is centrifuged, washed, vacuum dried, ground and sieved to obtain the titanium silicon-based reinforcing agent.

[0008] Preferably, in step S1, the pore size of the MCM-41 molecular sieve is 2~4 nm, and the specific surface area of ​​the MCM-41 molecular sieve is ≥800 m². 2 / g; The drying temperature is 120~150℃, and the drying time is 4~6 hours; The roasting temperature is 300~350℃, and the roasting time is 2~3h.

[0009] Preferably, in step S2, the mass ratio of the activated MCM-41 molecular sieve, aqueous ethanol solution, tetraethoxysilane, and isopropyl titanate is (5~8):(18~25):(2~4):(0.5~1.5). The ultrasonic dispersion time is 30-40 minutes; The reflux reaction temperature is 75~85℃, and the reflux reaction time is 6~8h; The vacuum drying temperature is 100~120℃, and the vacuum drying time is 8~10h.

[0010] Preferably, in step S3, the mass ratio of the titanium-silicon supported material to 3-aminopropyltriethoxysilane is (6~9):(3~5). The reflux reaction temperature is 75~85℃, and the reflux reaction time is 4~5h; The vacuum drying temperature is 110~130℃, and the vacuum drying time is 2~4h.

[0011] Preferably, in step S4, the mass ratio of the aminated composite material to p-hydroxybenzaldehyde is (6~9):(2~4). The temperature is raised to 60-70°C, and the reaction time is 3-4 hours. The vacuum drying temperature is 90~110℃, and the vacuum drying time is 2~4h.

[0012] Preferably, the preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Ammonium metavanadate and bismuth nitrate were added to deionized water, stirred and dissolved, then urea and γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued for hydrothermal reaction. After the reaction was completed, the mixture was cooled, centrifuged, washed, vacuum dried, ground and sieved to obtain vanadium bismuth photoactive protective agent.

[0013] Preferably, the mass ratio of ammonium metavanadate, bismuth nitrate, urea and γ-glycidoxypropyltrimethoxysilane is (2~4):(3~5):(1~2):(2~3); The hydrothermal reaction temperature is 170~190℃, and the reaction time is 16~20h; The vacuum drying temperature is 90~110℃, and the vacuum drying time is 8~10h.

[0014] Preferably, the adhesion promoter is at least one of γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriethoxysilane; The pigments and fillers include at least one of kaolin, barium sulfate, quartz sand, corundum, titanium dioxide, anatase titanium dioxide, marble powder, or sericite powder. The film-forming aid is at least one of dodecyl alcohol ester and dipropylene glycol butyl ether; The dispersant is at least one of sodium polyacrylate, ammonium polyacrylate, and potassium polyacrylate; The defoamer is a polyoxyethylene-polyoxypropylene block copolymer; The thickener is at least one of hydroxyethyl cellulose, polyacrylic acid, and acrylic-methacrylate copolymer.

[0015] This invention also proposes a method for preparing a high-adhesion nano-silicon coating as described above, comprising the following steps: S10. Add titanium-silicon-based reinforcing agent and vanadium-bismuth photoactive protective agent to deionized water, add dispersant, and disperse at high speed to obtain dispersion; S20. Add pigments and fillers to the dispersion, transfer to a sand mill, and grind for 40-60 minutes at a speed of 2500-3500 r / min to make the fineness of pigments and fillers ≤30μm, and obtain a color paste. S30. While stirring, silicone-acrylic emulsion, adhesion promoter and film-forming aid are added sequentially to the color paste, and the mixture is stirred to obtain a mixture. S40. Add defoamer, thickener, and deionized water to the mixture, filter, seal and let stand for 24-48 hours to obtain a high-adhesion nano-silicon coating.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The high-adhesion nano-silicon coating provided by this invention achieves excellent comprehensive performance through the scientific formulation of its components. Silicone-acrylic emulsion, as the base resin, provides good film-forming properties and flexibility; the adhesion promoter enhances the bonding force between the coating and the substrate through silane coupling; film-forming aids, dispersants, defoamers, and thickeners synergistically ensure the coating's workability and film quality; pigments and fillers impart hiding power and mechanical strength to the coating; and the titanium-silicon-based reinforcing agent utilizes the high specific surface area (≥800m²) of MCM-41 molecular sieve. 2 The structure ( / g) and regular structure (2~4nm) not only provide a uniformly dispersed carrier for the titanium-silicon active components, but the amino and Schiff base structures modified on its surface also significantly enhance the chemical bonding ability with the substrate. The vanadium-bismuth photoactive protective agent, through the photocatalytic properties of the vanadium-bismuth composite oxide, generates active oxygen under light conditions, endowing the coating with self-cleaning and anti-fouling properties. Under the synergistic effect of the two, the coating achieves both excellent adhesion and long-term protective function. At the same time, the structural and surface silanization modification promotes the uniform distribution and stable bonding of the two functional components at the organic-inorganic interface, enabling the coating to achieve a multi-functional integration of high adhesion and anti-fouling performance.

[0017] (2) In the preparation process of the titanium-silicon-based reinforcing agent provided by the present invention, after the MCM-41 molecular sieve is activated, tetraethoxysilane and isopropyl titanate undergo hydrolysis and condensation reaction on the MCM-41 framework to form a Si-O-Ti covalent network, thus constructing a titanium-silicon composite structure with acidic sites. Subsequently, the grafting of 3-aminopropyltriethoxysilane introduces free amino groups (-NH2) on the surface. These amino groups undergo Schiff base condensation reaction with p-hydroxybenzaldehyde to generate C=N double bonds, forming multidentate chelating sites with strong coordination ability. The introduced benzene ring structure can improve the wear resistance of the coating. When the vanadium-bismuth photoactive protective agent (V2O5-Bi composite oxide surface modified with γ-glycidoxypropyltrimethoxysilane) is introduced into the system, its surface epoxy groups undergo ring-opening reaction with the amino and hydroxyl groups of the titanium-silicon-based reinforcing agent to form a stable covalent bridge structure, thereby achieving chemical anchoring of nano-components. Meanwhile, the Schiff base structure of the titanium-silicon based reinforcing agent interacts with metal ions (such as Fe) on the substrate surface through the π electrons of C=N. 3+ Al 3+ The vanadium-bismuth photoactive agent forms coordination bonds, and its multiple siloxane structure (-Si-O-) undergoes dehydration condensation with the hydroxyl groups of the substrate to generate Si-OM covalent bonds (M represents the substrate metal), achieving chemical adhesion. The vanadium-bismuth photoactive agent forms a photocatalytic active zone on the coating surface, generating free radicals and reactive oxygen species that decompose organic pollutants, improving the coating's antifouling performance. This three-dimensional synergistic mechanism of "bottom-layer chemical anchoring + mid-layer electronic synergy + surface photocatalytic protection" enables the coating to achieve both superior adhesion and antifouling properties, fundamentally extending the coating's service life. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0020] Example 1 A high-adhesion nano-silicon coating, comprising the following components by weight: The composition includes: 45 parts silicone-acrylic emulsion, 12.5 parts titanium-silicon based reinforcing agent, 7 parts vanadium-bismuth photoactive protective agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of titanium-silicon-based reinforcing agent and 7 parts of vanadium-bismuth photoactive protective agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 3 parts of tetraethoxysilane and 1 part of isopropyl titanate, reflux at 80°C for 7 h, filter, wash, and vacuum dry at 110°C for 9 h to obtain titanium silicon supported material. S3. Mix 6.5 parts of the titanium-silicon supported material with 10 parts of ethanol aqueous solution, add 4 parts of 3-aminopropyltriethoxysilane, reflux at 80°C for 4.5 h, filter after the reaction, wash, and vacuum dry at 120°C for 3 h to obtain the aminated composite material. S4. Mix 6.5 parts of the aminated composite material with 10 parts of anhydrous ethanol, add 3 parts of p-hydroxybenzaldehyde, stir, heat to 65°C and react for 3.5 h. After the reaction is completed, centrifuge, wash, vacuum dry at 100°C for 3 h, grind through a 200-mesh sieve to obtain the titanium silicon-based reinforcing agent. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Three parts of ammonium metavanadate and four parts of bismuth nitrate were added to deionized water, stirred and dissolved. Then, 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was then hydrothermally reacted at 180°C for 18 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 100°C for 9 hours. Finally, it was ground through a 200-mesh sieve to obtain the vanadium bismuth photoactive protective agent.

[0021] Example 2 A high-adhesion nano-silicon coating, comprising the following components by weight: 40 parts silicone-acrylic emulsion, 10 parts titanium-silicon-based reinforcing agent, 5 parts vanadium-bismuth photoactive protective agent, 2 parts γ-methacryloyloxypropyltrimethoxysilane, 5 parts dipropylene glycol butyl ether, 15 parts barium sulfate, 0.5 parts ammonium polyacrylate, 0.2 parts polyoxyethylene-polyoxypropylene block copolymer, 0.5 parts polyacrylic acid, and 15 parts deionized water; The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 10 parts of titanium-silicon-based reinforcing agent and 5 parts of vanadium-bismuth photoactive protective agent to deionized water, add 0.5 parts of ammonium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 15 parts of barium sulfate to the dispersion, transfer it to a sand mill, and grind it for 40 minutes at a speed of 2500 r / min to make the barium sulfate fineness ≤30μm, and obtain a color paste. S30. While stirring, add 40 parts of silicone-acrylic emulsion, 2 parts of γ-methacryloxypropyltrimethoxysilane, and 5 parts of dipropylene glycol butyl ether to the pigment paste in sequence, stir and mix to obtain a mixture. S40. Add 0.2 parts of polyoxyethylene-polyoxypropylene block copolymer, 0.5 parts of polyacrylic acid, and 15 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 120°C for 4 hours, then calcine it at 300°C for 2 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6 parts of the activated MCM-41 molecular sieve with 18 parts of ethanol aqueous solution, ultrasonically disperse for 30 min, add 2 parts of tetraethoxysilane and 0.5 parts of isopropyl titanate, reflux at 75°C for 6 h, filter, wash, and vacuum dry at 100°C for 8 h to obtain titanium silicon supported material. S3. Mix 6 parts of the titanium-silicon supported material with 8 parts of ethanol aqueous solution, add 3 parts of 3-aminopropyltriethoxysilane, reflux at 75°C for 4 hours, filter after the reaction, wash, and vacuum dry at 110°C for 2 hours to obtain the aminated composite material. S4. Mix 6 parts of the aminated composite material with 8 parts of anhydrous ethanol, add 2 parts of p-hydroxybenzaldehyde, stir, heat to 60°C and react for 3 hours. After the reaction is completed, centrifuge, wash, vacuum dry at 90°C for 2 hours, grind through a 200-mesh sieve to obtain the titanium silicon-based reinforcing agent. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Two parts of ammonium metavanadate and three parts of bismuth nitrate were added to deionized water, stirred and dissolved. One part of urea and two parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was then subjected to hydrothermal reaction at 170°C for 16 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 90°C for 8 hours. The mixture was then ground through a 200-mesh sieve to obtain the vanadium-bismuth photoactive protective agent.

[0022] Example 3 A high-adhesion nano-silicon coating, comprising the following components by weight: 50 parts of silicone-acrylic emulsion, 15 parts of titanium-silicon-based reinforcing agent, 9 parts of vanadium-bismuth photoactive protective agent, 8 parts of vinyltriethoxysilane, 10 parts of dodecyl alcohol ester, 30 parts of quartz sand, 3 parts of potassium polyacrylate, 1 part of polyoxyethylene-polyoxypropylene block copolymer, 2 parts of acrylic acid-methacrylate copolymer, and 20 parts of deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 15 parts of titanium-silicon-based reinforcing agent and 9 parts of vanadium-bismuth photoactive protective agent to deionized water, add 3 parts of potassium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 30 parts of quartz sand to the dispersion, transfer it to a sand mill, and grind it for 60 minutes at a speed of 3500 r / min to make the fineness of the quartz sand ≤30μm, and obtain the color paste. S30. While stirring, add 50 parts of silicone-acrylic emulsion, 8 parts of vinyltriethoxysilane, and 10 parts of dodecyl alcohol ester to the color paste in sequence, stir and mix to obtain a mixture. S40. Add 1 part of polyoxyethylene-polyoxypropylene block copolymer, 2 parts of acrylic acid-methacrylate copolymer, and 20 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 150°C for 6 hours, then calcine it at 350°C for 3 hours, and cool it to obtain the activated MCM-41 molecular sieve. S2. Mix 8 parts of the activated MCM-41 molecular sieve with 25 parts of ethanol aqueous solution, ultrasonically disperse for 40 min, add 4 parts of tetraethoxysilane and 1.5 parts of isopropyl titanate, reflux at 85°C for 8 h, filter, wash, and vacuum dry at 120°C for 10 h to obtain titanium silicon supported material. S3. Mix 8 parts of the titanium-silicon supported material with 12 parts of ethanol aqueous solution, add 5 parts of 3-aminopropyltriethoxysilane, reflux at 85°C for 5 hours, filter after the reaction, wash, and vacuum dry at 130°C for 4 hours to obtain the aminated composite material. S4. Mix 8 parts of the aminated composite material with 10 parts of anhydrous ethanol, add 4 parts of p-hydroxybenzaldehyde, stir, heat to 65°C and react for 3.5 h. After the reaction is completed, centrifuge, wash, vacuum dry at 100°C for 4 h, grind through a 200-mesh sieve to obtain the titanium silicon-based reinforcing agent. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Four parts of ammonium metavanadate and five parts of bismuth nitrate were added to deionized water, stirred and dissolved. Two parts of urea and three parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was hydrothermally reacted at 190°C for 20 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 110°C for 10 hours. The mixture was then ground through a 200-mesh sieve to obtain the vanadium bismuth photoactive protective agent.

[0023] Comparative Example 1 A high-adhesion nano-silicon coating, comprising the following components by weight: 45 parts silicone-acrylic emulsion, 7 parts vanadium-bismuth photoactive protective agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 7 parts of vanadium bismuth photoactive protective agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Three parts of ammonium metavanadate and four parts of bismuth nitrate were added to deionized water, stirred and dissolved. Then, 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was then hydrothermally reacted at 180°C for 18 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 100°C for 9 hours. Finally, it was ground through a 200-mesh sieve to obtain the vanadium bismuth photoactive protective agent.

[0024] Compared to Example 1, Comparative Example 1 lacks the titanium-silicon-based reinforcing agent component.

[0025] Comparative Example 2 A high-adhesion nano-silicon coating, comprising the following components by weight: The composition includes 45 parts silicone-acrylic emulsion, 12.5 parts titanium-based reinforcing agent, 7 parts vanadium-bismuth photoactive protective agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of titanium-based reinforcing agent and 7 parts of vanadium-bismuth photoactive protective agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 1 part of isopropyl titanate, reflux at 80℃ for 7 h, filter, wash, and vacuum dry at 110℃ for 9 h to obtain titanium-supported material. S3. Mix 6.5 parts of the titanium-supported material with 10 parts of ethanol aqueous solution, add 4 parts of 3-aminopropyltriethoxysilane, reflux at 80°C for 4.5 h, filter after the reaction, wash, and vacuum dry at 120°C for 3 h to obtain the aminated composite material. S4. Mix 6.5 parts of the aminated composite material with 10 parts of anhydrous ethanol, add 3 parts of p-hydroxybenzaldehyde, stir, heat to 65°C and react for 3.5 h. After the reaction is completed, centrifuge, wash, vacuum dry at 100°C for 3 h, grind through a 200-mesh sieve to obtain the titanium-based reinforcing agent. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Three parts of ammonium metavanadate and four parts of bismuth nitrate were added to deionized water, stirred and dissolved. Then, 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was then hydrothermally reacted at 180°C for 18 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 100°C for 9 hours. Finally, it was ground through a 200-mesh sieve to obtain the vanadium bismuth photoactive protective agent.

[0026] Compared to Example 1, in Comparative Example 2, the titanium-silicon-based reinforcing agent was replaced with a titanium-based reinforcing agent.

[0027] Comparative Example 3 A high-adhesion nano-silicon coating, comprising the following components by weight: The composition includes 45 parts silicone-acrylic emulsion, 12.5 parts silicone-based reinforcing agent, 7 parts vanadium-bismuth photoactive protective agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of silicon-based reinforcing agent and 7 parts of vanadium-bismuth photoactive protective agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion; S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 3 parts of tetraethoxysilane, reflux at 80°C for 7 h, filter, wash, and vacuum dry at 110°C for 9 h to obtain silicon-supported material. S3. Mix 6.5 parts of the silicon-supported material with 10 parts of ethanol aqueous solution, add 4 parts of 3-aminopropyltriethoxysilane, reflux at 80°C for 4.5 h, filter after the reaction, wash, and vacuum dry at 120°C for 3 h to obtain the aminated composite material. S4. Mix 6.5 parts of the aminated composite material with 10 parts of anhydrous ethanol, add 3 parts of p-hydroxybenzaldehyde, stir, heat to 65°C and react for 3.5 h. After the reaction is completed, centrifuge, wash, vacuum dry at 100°C for 3 h, grind through a 200-mesh sieve to obtain the silicon-based reinforcing agent. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Three parts of ammonium metavanadate and four parts of bismuth nitrate were added to deionized water, stirred and dissolved. Then, 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was then hydrothermally reacted at 180°C for 18 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 100°C for 9 hours. Finally, it was ground through a 200-mesh sieve to obtain the vanadium bismuth photoactive protective agent.

[0028] Compared to Example 1, in Comparative Example 3, the titanium-silicon-based reinforcing agent was replaced with a silicon-based reinforcing agent.

[0029] Comparative Example 4 A high-adhesion nano-silicon coating, comprising the following components by weight: 45 parts of silicone-acrylic emulsion, 12.5 parts of titanium-silicon loading material, 7 parts of vanadium-bismuth photoactive protective agent, 5 parts of γ-aminopropyltriethoxysilane, 7.5 parts of dodecyl alcohol ester, 22 parts of kaolin, 1.5 parts of sodium polyacrylate, 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water; The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of titanium-silicon supported material and 7 parts of vanadium-bismuth photoactive protective agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-silicon supported material includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 3 parts of tetraethoxysilane and 1 part of isopropyl titanate, reflux at 80°C for 7 h, filter, wash, and vacuum dry at 110°C for 9 h to obtain titanium silicon supported material. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Three parts of ammonium metavanadate and four parts of bismuth nitrate were added to deionized water, stirred and dissolved. Then, 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was then hydrothermally reacted at 180°C for 18 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 100°C for 9 hours. Finally, it was ground through a 200-mesh sieve to obtain the vanadium bismuth photoactive protective agent.

[0030] Compared to Example 1, Comparative Example 4 omits steps S3 and S4.

[0031] Comparative Example 5 A high-adhesion nano-silicon coating, comprising the following components by weight: The composition includes 45 parts silicone-acrylic emulsion, 12.5 parts aminated composite material, 7 parts vanadium-bismuth photoactive protective agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of the aminated composite material and 7 parts of vanadium bismuth photoactive protective agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the aminated composite material includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 3 parts of tetraethoxysilane and 1 part of isopropyl titanate, reflux at 80°C for 7 h, filter, wash, and vacuum dry at 110°C for 9 h to obtain titanium silicon supported material. S3. Mix 6.5 parts of the titanium-silicon supported material with 10 parts of ethanol aqueous solution, add 4 parts of 3-aminopropyltriethoxysilane, reflux at 80°C for 4.5 h, filter after the reaction, wash, and vacuum dry at 120°C for 3 h to obtain the aminated composite material. The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Three parts of ammonium metavanadate and four parts of bismuth nitrate were added to deionized water, stirred and dissolved. Then, 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued. The mixture was then hydrothermally reacted at 180°C for 18 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 100°C for 9 hours. Finally, it was ground through a 200-mesh sieve to obtain the vanadium bismuth photoactive protective agent.

[0032] Compared to Example 1, Comparative Example 5 omits step S4, which involves the reaction of the aminated composite material with p-hydroxybenzaldehyde.

[0033] Comparative Example 6 A high-adhesion nano-silicon coating, comprising the following components by weight: The composition includes 45 parts silicone-acrylic emulsion, 12.5 parts titanium-silicone reinforcing agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of titanium-silicon-based reinforcing agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion; S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 3 parts of tetraethoxysilane and 1 part of isopropyl titanate, reflux at 80°C for 7 h, filter, wash, and vacuum dry at 110°C for 9 h to obtain titanium silicon supported material. S3. Mix 6.5 parts of the titanium-silicon supported material with 10 parts of ethanol aqueous solution, add 4 parts of 3-aminopropyltriethoxysilane, reflux at 80°C for 4.5 h, filter after the reaction, wash, and vacuum dry at 120°C for 3 h to obtain the aminated composite material. S4. Mix 6.5 parts of the aminated composite material with 10 parts of anhydrous ethanol, add 3 parts of p-hydroxybenzaldehyde, stir, heat to 65°C and react for 3.5 h. After the reaction is completed, centrifuge, wash, vacuum dry at 100°C for 3 h, grind through a 200-mesh sieve to obtain the titanium silicon-based reinforcing agent.

[0034] Compared to Example 1, Comparative Example 6 lacks the vanadium-bismuth photoactive protective agent component.

[0035] Comparative Example 7 A high-adhesion nano-silicon coating, comprising the following components by weight: The composition includes 45 parts silicone-acrylic emulsion, 12.5 parts titanium-silicon based reinforcing agent, 7 parts bismuth photoactive protective agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of titanium-silicon-based reinforcing agent and 7 parts of bismuth photoactive protective agent to deionized water, add 1.5 parts of sodium polyacrylate, and disperse at high speed to obtain a dispersion. S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 3 parts of tetraethoxysilane and 1 part of isopropyl titanate, reflux at 80°C for 7 h, filter, wash, and vacuum dry at 110°C for 9 h to obtain titanium silicon supported material. S3. Mix 6.5 parts of the titanium-silicon supported material with 10 parts of ethanol aqueous solution, add 4 parts of 3-aminopropyltriethoxysilane, reflux at 80°C for 4.5 h, filter after the reaction, wash, and vacuum dry at 120°C for 3 h to obtain the aminated composite material. S4. Mix 6.5 parts of the aminated composite material with 10 parts of anhydrous ethanol, add 3 parts of p-hydroxybenzaldehyde, stir, heat to 65°C and react for 3.5 h. After the reaction is completed, centrifuge, wash, vacuum dry at 100°C for 3 h, grind through a 200-mesh sieve to obtain the titanium silicon-based reinforcing agent. The preparation method of the bismuth photoactive protective agent includes the following steps: Four parts of bismuth nitrate were added to deionized water, stirred and dissolved, and then 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane were added. The mixture was stirred and hydrothermally reacted at 180°C for 18 hours. After the reaction was completed, the mixture was cooled, centrifuged, washed, and vacuum dried at 100°C for 9 hours. The mixture was then ground through a 200-mesh sieve to obtain the bismuth photoactive protective agent.

[0036] Compared to Example 1, Comparative Example 7 replaced the vanadium-bismuth photoactive protective agent with a bismuth photoactive protective agent.

[0037] Comparative Example 8 A high-adhesion nano-silicon coating, comprising the following components by weight: The composition includes 45 parts silicone-acrylic emulsion, 12.5 parts titanium-silicon based reinforcing agent, 7 parts vanadium photoactive protective agent, 5 parts γ-aminopropyltriethoxysilane, 7.5 parts dodecyl alcohol ester, 22 parts kaolin, 1.5 parts sodium polyacrylate, 0.6 parts polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts hydroxyethyl cellulose, and 18 parts deionized water. The method for preparing the high-adhesion nano-silicon coating is characterized by comprising the following steps: S10. Add 12.5 parts of titanium-silicon-based reinforcing agent and 7 parts of vanadium photoactive protective agent to deionized water, add 1.5 parts of dispersant, and disperse at high speed to obtain a dispersion. S20. Add 22 parts of kaolin to the dispersion, transfer to a sand mill, and grind for 50 min at a speed of 3000 r / min to make the fineness of kaolin ≤30μm, and obtain a color paste. S30. While stirring, add 45 parts of silicone-acrylic emulsion, 5 parts of γ-aminopropyltriethoxysilane, and 7.5 parts of dodecyl alcohol ester to the pigment paste in sequence, stir and mix to obtain a mixture; S40. Add 0.6 parts of polyoxyethylene-polyoxypropylene block copolymer, 1.2 parts of hydroxyethyl cellulose, and 18 parts of deionized water to the mixture, filter, seal and let stand for 36 hours to obtain a high-adhesion nano-silicon coating. The preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven at 135°C for 5 hours, then calcine it at 325°C for 2.5 hours, and cool it to obtain activated MCM-41 molecular sieve. S2. Mix 6.5 parts of the activated MCM-41 molecular sieve with 20 parts of ethanol aqueous solution, ultrasonically disperse for 35 min, add 3 parts of tetraethoxysilane and 1 part of isopropyl titanate, reflux at 80°C for 7 h, filter, wash, and vacuum dry at 110°C for 9 h to obtain titanium silicon supported material. S3. Mix 6.5 parts of the titanium-silicon supported material with 10 parts of ethanol aqueous solution, add 4 parts of 3-aminopropyltriethoxysilane, reflux at 80°C for 4.5 h, filter after the reaction, wash, and vacuum dry at 120°C for 3 h to obtain the aminated composite material. S4. Mix 6.5 parts of the aminated composite material with 10 parts of anhydrous ethanol, add 3 parts of p-hydroxybenzaldehyde, stir, heat to 65°C and react for 3.5 h. After the reaction is completed, centrifuge, wash, vacuum dry at 100°C for 3 h, grind through a 200-mesh sieve to obtain the titanium silicon-based reinforcing agent. The preparation method of the vanadium photoactive protective agent includes the following steps: Add 3 parts of ammonium metavanadate to deionized water, stir and dissolve, then add 1.2 parts of urea and 2.5 parts of γ-glycidyl etheroxypropyltrimethoxysilane, continue stirring, and hydrothermally react at 180℃ for 18 hours. After the reaction is completed, cool, centrifuge, wash, vacuum dry at 100℃ for 9 hours, and grind through a 200-mesh sieve to obtain vanadium photoactive protective agent.

[0038] Compared to Example 1, Comparative Example 8 replaced the vanadium-bismuth photoactive protective agent with a vanadium photoactive protective agent.

[0039] Test methods and results The high-adhesion nano-silica coatings prepared in Examples 1-3 and Comparative Examples 1-8 were uniformly sprayed onto the surface of stainless steel plates. After drying at room temperature for 7 days, adhesion and stain resistance were tested. Adhesion testing was conducted according to ASTM D3359-09 Standard Test Method for Adhesion Measurement by Tape Method. The paint film was examined using a magnifying glass, and the grade was determined based on the relationship between the peeling areas and the grid area, as described below: 5B: The cut edges are very smooth, and not a single grid block has fallen off; 4B: At the mesh entry point, there are tiny, flaky pieces of paint film peeling off, affecting an area of ​​5%. 3B: The paint layer peels off along the cut point or partially or completely peels off at the cut point of the grid line, affecting an area of ​​5%-15%; 2B: Large sections or all of the paint layer have peeled off along the cutting point, or some or all of the grid-like areas have peeled off. The affected area is 15-35%. 1B: Large or complete paint peeling off along the cutting point, or partial or complete peeling off of grid squares, affecting an area of ​​35-65%; 0B: The area of ​​peeling is greater than 65%.

[0040] The stain resistance test was conducted according to GB / T9780-2013 "Test Method for Stain Resistance of Architectural Coatings", using blue-black ink as the stain. The test results are shown in Table 1.

[0041] Table 1 Adhesion test results of high-adhesion nano-silicon coatings

[0042] Table 1 shows that, compared with comparative examples 1-8, the high-adhesion nano-silicon coating prepared by the present invention has stronger adhesion and better stain resistance.

[0043] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A high-adhesion nano-silicon coating, characterized in that, By weight, it includes the following components: The ingredients are: 40-50 parts silicone-acrylic emulsion, 10-15 parts titanium-silicon based reinforcing agent, 5-9 parts vanadium-bismuth photoactive protective agent, 2-8 parts adhesion promoter, 5-10 parts film-forming aid, 15-30 parts pigments and fillers, 0.5-3 parts dispersant, 0.2-1 part defoamer, 0.5-2 parts thickener, and 15-20 parts deionized water.

2. The high-adhesion nano-silicon coating as described in claim 1, characterized in that, The preparation method of the titanium-silicon-based reinforcing agent includes the following steps: S1. Dry the MCM-41 molecular sieve in an oven, then calcine and cool it to obtain activated MCM-41 molecular sieve; S2. The activated MCM-41 molecular sieve is mixed with an ethanol-water solution, ultrasonically dispersed, tetraethoxysilane and isopropyl titanate are added, refluxed, filtered, washed, and vacuum dried to obtain titanium-silicon supported material. S3. Mix the titanium-silicon supported material with an aqueous ethanol solution, add 3-aminopropyltriethoxysilane, reflux the reaction, filter after the reaction is complete, wash, and vacuum dry to obtain the aminated composite material. S4. The aminated composite material is mixed with anhydrous ethanol, p-hydroxybenzaldehyde is added and mixed, stirred and heated to react. After the reaction is completed, the mixture is centrifuged, washed, vacuum dried, ground and sieved to obtain the titanium silicon-based reinforcing agent.

3. The high-adhesion nano-silicon coating as described in claim 2, characterized in that, In step S1, the pore size of the MCM-41 molecular sieve is 2~4 nm, and the specific surface area of ​​the MCM-41 molecular sieve is ≥800 m². 2 / g; The drying temperature is 120~150℃, and the drying time is 4~6 hours; The roasting temperature is 300~350℃, and the roasting time is 2~3h.

4. The high-adhesion nano-silicon coating as described in claim 2, characterized in that, In step S2, the mass ratio of the activated MCM-41 molecular sieve, aqueous ethanol solution, tetraethoxysilane, and isopropyl titanate is (5~8):(18~25):(2~4):(0.5~1.5). The ultrasonic dispersion time is 30-40 minutes; The reflux reaction temperature is 75~85℃, and the reflux reaction time is 6~8h; The vacuum drying temperature is 100~120℃, and the vacuum drying time is 8~10h.

5. The high-adhesion nano-silicon coating as described in claim 2, characterized in that, In step S3, the mass ratio of the titanium-silicon supported material to 3-aminopropyltriethoxysilane is (6~9):(3~5). The reflux reaction temperature is 75~85℃, and the reflux reaction time is 4~5h; The vacuum drying temperature is 110~130℃, and the vacuum drying time is 2~4h.

6. The high-adhesion nano-silicon coating as described in claim 2, characterized in that, In step S4, the mass ratio of the aminated composite material to p-hydroxybenzaldehyde is (6~9):(2~4). The temperature is raised to 60-70°C, and the reaction time is 3-4 hours. The vacuum drying temperature is 90~110℃, and the vacuum drying time is 2~4h.

7. The high-adhesion nano-silicon coating as described in claim 1, characterized in that, The preparation method of the vanadium-bismuth photoactive protective agent includes the following steps: Ammonium metavanadate and bismuth nitrate were added to deionized water, stirred and dissolved, then urea and γ-glycidyl etheroxypropyltrimethoxysilane were added, and stirring was continued for hydrothermal reaction. After the reaction was completed, the mixture was cooled, centrifuged, washed, vacuum dried, ground and sieved to obtain vanadium bismuth photoactive protective agent.

8. The high-adhesion nano-silicon coating as described in claim 1, characterized in that, The mass ratio of ammonium metavanadate, bismuth nitrate, urea, and γ-glycidoxypropyltrimethoxysilane is (2~4):(3~5):(1~2):(2~3); The hydrothermal reaction temperature is 170~190℃, and the reaction time is 16~20h; The vacuum drying temperature is 90~110℃, and the vacuum drying time is 8~10h.

9. The high-adhesion nano-silicon coating as described in claim 1, characterized in that, The adhesion promoter is at least one of γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriethoxysilane; The pigments and fillers include at least one of kaolin, barium sulfate, quartz sand, corundum, titanium dioxide, anatase titanium dioxide, marble powder, or sericite powder. The film-forming aid is at least one of dodecyl alcohol ester and dipropylene glycol butyl ether; The dispersant is at least one of sodium polyacrylate, ammonium polyacrylate, and potassium polyacrylate; The defoamer is a polyoxyethylene-polyoxypropylene block copolymer; The thickener is at least one of hydroxyethyl cellulose, polyacrylic acid, and acrylic-methacrylate copolymer.

10. A method for preparing a high-adhesion nano-silicon coating as described in any one of claims 1 to 9, characterized in that, Includes the following steps: S10. Add titanium-silicon-based reinforcing agent and vanadium-bismuth photoactive protective agent to deionized water, add dispersant, and disperse at high speed to obtain dispersion; S20. Add pigments and fillers to the dispersion, transfer to a sand mill, and grind for 40-60 minutes at a speed of 2500-3500 r / min to make the fineness of pigments and fillers ≤30μm, and obtain a color paste. S30. While stirring, silicone-acrylic emulsion, adhesion promoter and film-forming aid are added sequentially to the color paste, and the mixture is stirred to obtain a mixture. S40. Add defoamer, thickener, and deionized water to the mixture, filter, seal and let stand for 24-48 hours to obtain a high-adhesion nano-silicon coating.

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