A kind of anti-metal dust corrosion coating and its preparation method and application

Abstract

The present invention relates to the field of coating compositions and discloses a coating for preventing metal dust corrosion, its preparation method, and its application. The coating contains a controlled-release organic acid salt; the controlled-release organic acid salt comprises hollow silica nanospheres, an organic acid salt loaded within the hollow silica nanospheres, and polymethacrylic acid coating the hollow silica nanospheres. By adding the controlled-release organic acid salt to the coating, the present invention releases the organic acid salt when metal dust is first adsorbed onto the coating surface, generating a small amount of metallic rust. This prevents further oxidation of the metal particles to produce metallic rust and allows the metal particles to be easily carried away by water, thereby effectively preventing metal dust from contaminating and corroding the photovoltaic module glass.

Description

Technical Field

[0001] The present invention relates to the field of coating compositions, and in particular to a coating for preventing metal dust corrosion, a preparation method thereof and an application thereof. Background Art

[0002] Distributed commercial and industrial rooftops are a major installation site for photovoltaic power plants. The surfaces of these photovoltaic modules often contain numerous metallic dust particles. In humid environments, metallic dust easily oxidizes to form metal oxides (rust), which block sunlight from penetrating downward. Under normal circumstances, metallic rust does not react with the photovoltaic glass (SiO2). However, due to the potential-induced degradation (PID) effect common in photovoltaic strings during power generation, metallic rust can migrate into the interior of the glass under the influence of voltage, damaging the surface structure and affecting the refractive index. This further reduces the amount of sunlight received by the cells and significantly reduces module power. Furthermore, once metallic rust has penetrated the glass surface structure, conventional physical cleaning methods are nearly impossible to remove, severely impacting the power generation revenue of the power plant. However, due to the inevitable accumulation of charge on the surface of insulating materials, the adsorption of metallic dust on the photovoltaic glass surface is unavoidable.

[0003] Applying special coatings to photovoltaic glass surfaces can create anti-fouling and self-cleaning properties. However, existing anti-fouling or self-cleaning coatings for photovoltaic glass surfaces are designed to protect against organic and inorganic non-metallic dust particles (for example, the coating for fluoride corrosion prevention in patent CN119242123A and the self-cleaning coating for organic pollutants in patent CN114196241A). These coatings are ineffective in preventing corrosion from metal dust contamination. Currently, no coatings specifically targeting metal dust contamination corrosion on photovoltaic glass surfaces have been developed. Summary of the Invention

[0004] To address the aforementioned technical problem, namely the current lack of a coating that can be used to prevent metal dust contamination and corrosion on photovoltaic glass surfaces, the present invention provides a coating that prevents metal dust corrosion. This coating utilizes a controlled-release organic acid salt to prevent excessive rust from metal dust oxidation and to create a self-cleaning effect on the metal dust, effectively preventing metal dust contamination and corrosion of photovoltaic module glass.

[0005] The specific technical solutions of the present invention are:

[0006] In a first aspect, the present invention provides an anti-metal dust corrosion coating, which contains a controlled-release organic acid salt; the controlled-release organic acid salt includes: hollow silica nanospheres, an organic acid salt loaded in the hollow silica nanospheres, and polymethacrylic acid coated on the outside of the hollow silica nanospheres.

[0007] In the present invention, by using a controlled-release organic acid salt with a specific composition and structure in the coating, after being applied to the surface of the photovoltaic module glass to form a coating, it can play a role in preventing metal dust pollution and corrosion. The mechanism is as follows: after the metal dust is just adsorbed on the coating surface, it will first oxidize to form a small amount of metal rust. The formation of metal rust causes the local pH value in the coating to rise. When the pH value becomes alkaline, the polymethacrylic acid on the surface of the controlled-release organic acid salt changes from a closed state to an open-pore state, and the organic acid salt inside the silica nanospheres is released. Its organic acid radical ions are adsorbed on the surface of the metal particles, forming a hydrophilic protective film, which prevents the metal particles from continuing to oxidize and produce metal rust, thereby preventing the surface corrosion of the photovoltaic glass caused by metal rust. At the same time, the formation of the surface hydrophilic protective film, on the one hand, makes it easy for the coated metal particles to be carried away by precipitation, reducing the adsorption and deposition of metal dust on the surface of the module; on the other hand, it also makes it easy to clean the metal dust pollutants deposited on the surface of the module when the power station is operating and cleaning the module, reducing the difficulty of operation and maintenance cleaning of distributed photovoltaic modules.

[0008] Preferably, the content of the controlled-release organic acid salt in the coating is 0.3-5 wt %.

[0009] Preferably, the coating comprises the following components: a controlled-release organic acid salt, SiO2 sol, a film-forming aid, a curing accelerator, a hardening agent, and a dispersion medium.

[0010] Furthermore, the organic acid salt includes sodium citrate and / or sodium gluconate; the film-forming aid includes propylene glycol methyl ether; the curing accelerator includes acetylacetone; and the hardening agent includes polyethyl silicate and / or a silane coupling agent.

[0011] Furthermore, the silane coupling agent is methyltriethoxysilane and / or dimethyldiethoxysilane.

[0012] In a second aspect, the present invention provides a method for preparing the coating, comprising the following steps:

[0013] S1: adding hollow silica nanospheres to an organic acid salt solution, fully impregnating them, separating the product, and drying it;

[0014] S2: depositing a silane initiator onto the surface of the product obtained in step S1, mixing it with a monomer, a polymerization catalyst, and a polymerization reaction solvent, performing a polymerization reaction, and separating the product to obtain a controlled-release organic acid salt; the monomer is methacrylic acid and / or methacrylic acid salt;

[0015] S3: A metal dust corrosion resistant coating is formulated using controlled-release organic acid salts.

[0016] Preferably, in step S1, the organic acid salt is sodium citrate, and the drying temperature is 205-290°C.

[0017] In the case where sodium citrate is used as the organic acid salt, the present invention dries the hollow silica nanospheres after being immersed in and adsorbed with the organic acid salt solution at a temperature of not less than 205°C, thereby removing the crystallization water of the sodium citrate, thereby ensuring that the sodium citrate can be quickly released when metal dust is adsorbed onto the coating surface, effectively preventing metal dust from contaminating and corroding the photovoltaic module glass (when sodium citrate contains crystallization water, it will cause the local pH value in the coating to rise, and the release rate of sodium citrate will be too slow); at the same time, controlling the drying temperature to not higher than 290°C can prevent the sodium citrate from thermal decomposition and becoming ineffective.

[0018] Preferably, in step S1, the mass ratio of the hollow silica nanospheres to the organic acid salt is 1:0.5-2; the concentration of the organic acid salt solution is 0.01-0.05 g / mL; and the sufficient immersion is stirring for 20-24 hours.

[0019] Preferably, in step S2, the polymerization catalyst comprises CuBr, CuBr2 and 2,2'-bipyridine in a molar ratio of 1:0.08~0.15:2.0~2.5; the ratio between the monomer, the polymerization catalyst and the polymerization reaction solvent is 1 mol:0.05~0.10 mol:200~250 mL; the polymerization reaction temperature is 20~30°C, and the time is 1~1.5 h.

[0020] Preferably, in step S2, the silane initiator is [3-(2-bromoisobutyl)propyl]dimethylchlorosilane.

[0021] The structural formula of "[3-(2-bromoisobutyl)propyl]dimethylchlorosilane" described in the present invention is as follows:

[0022] .

[0023] Furthermore, the preparation steps of the [3-(2-bromoisobutyl)propyl]dimethylchlorosilane include: mixing 3-(2-bromoisobutyl)propylene, dimethylchlorosilane and an addition catalyst, performing an addition reaction in an inert atmosphere, and obtaining a silane initiator after purification.

[0024] The reaction formula for preparing [3-(2-bromoisobutyl)propyl]dimethylchlorosilane from 3-(2-bromoisobutyl)propylene and dimethylchlorosilane is as follows:

[0025] .

[0026] Preferably, step S3 includes the following process: mixing a controlled-release organic acid salt with an aqueous ammonia solution having a pH value not higher than 8, adding ethyl orthosilicate, reacting at 20-30° C. for 1-5 hours, distilling under reduced pressure to a pH value of 2-5, standing for 7-24 hours, adding a film-forming aid, a curing accelerator, a hardening agent and a dispersion medium to obtain a coating that prevents metal dust corrosion.

[0027] In the above-mentioned process of preparing the controlled-release organic acid salt into a coating, when the pH of the ammonia-containing aqueous solution is higher than 8, the polymethacrylic acid on the surface of the controlled-release organic acid salt will be in an open-pore state, and the organic acid salt loaded inside will be released and neutralized prematurely, losing the ability to coat metal dust, thereby resulting in poor anti-metal dust pollution and corrosion effect of the coating.

[0028] Furthermore, the ammonia-containing aqueous solution is a mixed solution of ammonia water and ethanol.

[0029] Preferably, in step S1, the preparation step of the hollow silica nanospheres includes: mixing ethyl orthosilicate, hexadecyltrimethylammonium bromide and a hydrolysis reaction solvent, adding ammonia water, reacting at 20-30° C. for 4-5 hours, separating the product, removing the hexadecyltrimethylammonium bromide, and obtaining hollow silica nanospheres.

[0030] Furthermore, in the process of preparing hollow silica nanospheres, the pH value of the ammonia water is 7.2~8; the ratio of the ethyl orthosilicate, hexadecyltrimethylammonium bromide, reaction solvent and ammonia water is 1mL:0.15~0.20g:50~100mL:1.0~1.5mL.

[0031] Furthermore, the process of separating the product and removing the hexadecyltrimethylammonium bromide comprises: separating the product by centrifugation, removing the hexadecyltrimethylammonium bromide by solvent extraction, centrifuging and dispersing, and then drying.

[0032] In a third aspect, the present invention provides the use of the coating in preventing metal dust pollution and corrosion on the glass surface of photovoltaic modules.

[0033] Preferably, the application comprises the following steps: applying the coating to the glass surface of the photovoltaic module in an amount of 10-30 mL / m 2 After curing, a coating that prevents metal dust pollution and corrosion is formed.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] (1) The present invention adds a controlled-release organic acid salt to the coating, which can release the organic acid salt when the metal dust is just adsorbed onto the coating surface to produce a small amount of metal rust, thereby preventing the metal particles from continuing to oxidize and produce metal rust, and making the metal particles easily carried away by water, thereby effectively preventing the metal dust from contaminating and corroding the photovoltaic module glass.

[0036] (2) In the process of preparing the coating of the present invention, when sodium citrate is used as the organic acid salt, the hollow silica nanospheres after being immersed in and adsorbed with the organic acid salt solution are dried at a temperature of 205-290°C, which can remove the crystal water of sodium citrate and avoid the thermal decomposition of sodium citrate, thereby improving the coating's anti-metal dust pollution and corrosion effect. DETAILED DESCRIPTION

[0037] The present invention will be further described below with reference to the embodiments.

[0038] First, the present invention relates to an anti-metal dust corrosion coating, which contains a controlled-release organic acid salt; the controlled-release organic acid salt includes: hollow silica nanospheres, an organic acid salt loaded in the hollow silica nanospheres, and polymethacrylic acid coated on the outside of the hollow silica nanospheres.

[0039] In some embodiments, the organic acid salt comprises sodium citrate and / or sodium gluconate.

[0040] In some specific embodiments, the content of the controlled-release organic acid salt in the coating is 0.3-5 wt %.

[0041] In some embodiments, the coating comprises the following components: a controlled-release organic acid salt, a SiO2 sol, a film-forming aid, a curing accelerator, a hardening agent, and a dispersion medium. Optionally or preferably, the film-forming aid comprises propylene glycol methyl ether; the curing accelerator comprises acetylacetone; and the hardening agent comprises polyethyl silicate and / or a silane coupling agent.

[0042] Second, the present invention relates to a method for preparing the coating, comprising the following steps:

[0043] S1: adding hollow silica nanospheres to an organic acid salt solution, fully impregnating them, separating the product, and drying it;

[0044] S2: depositing a silane initiator onto the surface of the product obtained in step S1, mixing it with a monomer, a polymerization catalyst, and a polymerization reaction solvent, performing a polymerization reaction, and separating the product to obtain a controlled-release organic acid salt; the monomer is methacrylic acid and / or methacrylic acid salt;

[0045] S3: A metal dust corrosion resistant coating is formulated using controlled-release organic acid salts.

[0046] In some specific embodiments, in step S1, the organic acid salt is sodium citrate, and the drying temperature is 205-290° C., and the drying time is 1-3 hours.

[0047] In some specific embodiments, in step S1, the mass ratio of the hollow silica nanospheres to the organic acid salt is 1:0.5-2; the concentration of the organic acid salt solution is 0.01-0.05 g / mL; and the sufficient immersion is stirring for 20-24 hours.

[0048] In some specific embodiments, in step S1, the preparation of the hollow silica nanospheres comprises: mixing tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, and a hydrolysis reaction solvent, adding ammonia water, reacting at 20-30°C for 4-5 hours, isolating the product, removing the hexadecyltrimethylammonium bromide, and obtaining the hollow silica nanospheres. Optionally or preferably, the pH value of the ammonia water is 7.2-8; the ratio of tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, reaction solvent, and ammonia water is 1 mL: 0.15-0.20 g: 50-100 mL: 1.0-1.5 mL; and the process of isolating the product and removing the hexadecyltrimethylammonium bromide comprises: after separating the product by centrifugation, removing the hexadecyltrimethylammonium bromide by solvent extraction, centrifuging and dispersing, and drying.

[0049] In some specific embodiments, in step S2, the polymerization catalyst includes CuBr, CuBr2 and 2,2'-bipyridine in a molar ratio of 1:0.08~0.15:2.0~2.5; the ratio between the monomer, the polymerization catalyst and the polymerization reaction solvent is 1 mol:0.05~0.10 mol:200~250 mL; the polymerization reaction temperature is 20~30°C, and the time is 1~1.5 h.

[0050] In some specific embodiments, in step S2, the silane initiator is [3-(2-bromoisobutyl)propyl]dimethylchlorosilane. Optionally or preferably, the preparation step of [3-(2-bromoisobutyl)propyl]dimethylchlorosilane comprises: mixing 3-(2-bromoisobutyl)propylene, dimethylchlorosilane, and an addition catalyst, performing an addition reaction in an inert atmosphere, and purifying to obtain the silane initiator.

[0051] In some specific embodiments, step S3 includes the following process: mixing a controlled-release organic acid salt with an aqueous ammonia solution having a pH value not higher than 8, adding ethyl orthosilicate, reacting at 20-30° C. for 1-5 hours, distilling under reduced pressure to a pH value of 2-5, allowing the mixture to stand for 7-24 hours, and adding a film-forming aid, a curing accelerator, a hardening agent, and a dispersion medium to obtain a coating for preventing metal dust corrosion. Optionally or preferably, the aqueous ammonia solution is a mixed solution of ammonia water and ethanol.

[0052] Thirdly, the present invention relates to the application of the coating in preventing metal dust pollution and corrosion on the glass surface of photovoltaic modules.

[0053] In some specific embodiments, the application includes the following steps: applying the coating to the glass surface of the photovoltaic module at a coating amount of 10-30 mL / m 2 After curing, a coating that prevents metal dust pollution and corrosion is formed.

[0054] The present invention is described below by way of specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit and scope of the inventive concept, any changes and advantages that can be imagined by those skilled in the art are included in the present invention, and the scope of protection of the present invention is defined by the appended claims and any equivalents thereof.

[0055] Example 1

[0056] The anti-metal dust corrosion coating is prepared by the following steps:

[0057] S1: 24 mL of ethanol, 56 mL of deionized water, 0.18 g of hexadecyltrimethylammonium bromide, and 1 mL of ethyl orthosilicate were mixed and stirred for 6 minutes. 1 mL of ammonia water with a pH of 7.2 was then added. After reacting at room temperature (23-25°C) for 4 hours, the product was separated by centrifugation. The product was subjected to solvent extraction by reflux extraction at 85°C for 12 hours to remove the hexadecyltrimethylammonium bromide (the extraction solvent was a mixed solution of concentrated hydrochloric acid and ethanol with a volume ratio of 1:35). After centrifugal dispersion, the product was vacuum-dried at 65°C for 8 hours to obtain hollow SiO2 nanospheres.

[0058] S2: Dissolve 200 mg of sodium citrate in 15 mL of water to form a sodium citrate solution. Weigh 200 mg of hollow SiO2 nanospheres and magnetically stir them at room temperature (23-25°C) for 20 hours. Then, centrifuge, rinse with water, and vacuum dry at 205°C for 120 minutes to obtain SiO2 nanospheres loaded with sodium citrate (denoted as "C6H5Na3O7 / SiO2 nanospheres").

[0059] S3: Mix 0.6 mL of 3-(2-bromoisobutyl)propylene and 4 mL of dimethylchlorosilane, add 1 g of chloroplatinic acid particles, and stir the reaction in a nitrogen, light-free, and room temperature (23-25°C) environment for 6 hours. Then, remove the excess dimethylchlorosilane by vacuum distillation to obtain [3-(2-bromoisobutyl)propyl]dimethylchlorosilane, which is then immediately deposited onto the surface of 3 g of C6H5Na3O7 / SiO2 nanospheres by vapor deposition to obtain C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface.

[0060] S4: Add 1 mmol of CuBr, 0.1 mmol of CuBr2, and 2.2 mmol of 2,2'-bipyridine to a dry Schlenk flask. Evacuate the flask and fill it with argon. Dissolve 50 mmol of sodium methacrylate in 10 mL of a 1:1 water / methanol mixture. Transfer the mixture to the Schlenk flask and stir for 10 minutes to obtain a monomer solution.

[0061] S5: The monomer solution was added to a vial containing C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface. After reacting at room temperature (23-25°C) for 1 hour, the solution was centrifuged, washed with deionized water, ultrasonically treated in an ethanol solution for 1 minute, immersed in deionized water for 12 hours, washed with ethanol and dried under nitrogen to obtain polymethacrylic acid-coated C6H5Na3O7 / SiO2 nanospheres, i.e., controlled-release organic acid salts (denoted as "C6H5Na3O7 / SiO2@PMAA nanospheres").

[0062] S6: Add 3g of C6H5Na3O7 / SiO2@PMAA nanospheres to 10mL of a mixed solution of ammonia and ethanol (pH 7.5). After stirring, add 15mL of ethyl orthosilicate dropwise. After reacting at room temperature (23-25°C) for 3 hours, slowly distill under reduced pressure in a 45°C water bath until the solution reaches a pH of 5 and allow to stand for 12 hours. Subsequently, add 15mL of water, 60mL of ethanol, 5mL of propylene glycol methyl ether, 1mL of acetylacetone, and 0.1g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0063] Example 2

[0064] The anti-metal dust corrosion coating is prepared by the following steps:

[0065] S1: 24 mL of ethanol, 56 mL of deionized water, 0.18 g of hexadecyltrimethylammonium bromide, and 1 mL of ethyl orthosilicate were mixed and stirred for 6 minutes. 1 mL of ammonia water with a pH of 8 was then added. After reacting at room temperature (23-25°C) for 4 hours, the product was separated by centrifugation. The product was subjected to solvent extraction by reflux extraction at 85°C for 12 hours to remove the hexadecyltrimethylammonium bromide (the extraction solvent was a mixed solution of concentrated hydrochloric acid and ethanol with a volume ratio of 1:35). After centrifugal dispersion, the product was vacuum-dried at 65°C for 8 hours to obtain hollow SiO2 nanospheres.

[0066] S2: Dissolve 200 mg of sodium citrate in 15 mL of water to form a sodium citrate solution. Weigh 200 mg of hollow SiO2 nanospheres and magnetically stir them at room temperature (23-25°C) for 20 hours. Then, centrifuge, rinse with water, and vacuum dry at 255°C for 120 minutes to obtain SiO2 nanospheres loaded with sodium citrate (denoted as "C6H5Na3O7 / SiO2 nanospheres").

[0067] S3: Mix 0.6 mL of 3-(2-bromoisobutyl)propylene and 4 mL of dimethylchlorosilane, add 1 g of chloroplatinic acid particles, and stir the reaction in a nitrogen, light-free, and room temperature (23-25°C) environment for 6 hours. Then, remove the excess dimethylchlorosilane by vacuum distillation to obtain [3-(2-bromoisobutyl)propyl]dimethylchlorosilane, which is then immediately deposited onto the surface of 3 g of C6H5Na3O7 / SiO2 nanospheres by vapor deposition to obtain C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface.

[0068] S4: Add 1 mmol of CuBr, 0.1 mmol of CuBr2, and 2.2 mmol of 2,2'-bipyridine to a dry Shrek flask. Evacuate the flask and fill it with argon. Dissolve 50 mmol of sodium methacrylate in 10 mL of a 1:1 water / methanol mixture. Transfer the mixture to the Shrek flask and stir for 10 minutes to obtain a monomer solution.

[0069] S5: The monomer solution was added to a vial containing C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface. After reacting at room temperature (23-25°C) for 1 hour, the solution was centrifuged, washed with deionized water, ultrasonically treated in an ethanol solution for 1 minute, immersed in deionized water for 12 hours, washed with ethanol and dried under nitrogen to obtain polymethacrylic acid-coated C6H5Na3O7 / SiO2 nanospheres, i.e., controlled-release organic acid salts (denoted as "C6H5Na3O7 / SiO2@PMAA nanospheres").

[0070] S6: Add 3g of C6H5Na3O7 / SiO2@PMAA nanospheres to 10mL of a mixed solution of ammonia and ethanol (pH 8). After stirring, add 15mL of ethyl orthosilicate dropwise. After reacting at room temperature (23-25°C) for 3 hours, slowly distill under reduced pressure in a 45°C water bath until the solution reaches a pH of 5 and allow to stand for 12 hours. Subsequently, add 15mL of water, 60mL of ethanol, 5mL of propylene glycol methyl ether, 1mL of acetylacetone, and 0.1g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0071] Example 3

[0072] The anti-metal dust corrosion coating is prepared by the following steps:

[0073] S1: 24 mL of ethanol, 56 mL of deionized water, 0.18 g of hexadecyltrimethylammonium bromide, and 1 mL of ethyl orthosilicate were mixed and stirred for 6 minutes. 1 mL of ammonia water with a pH of 7.5 was then added. After reacting at room temperature (23-25°C) for 4 hours, the product was separated by centrifugation. The product was subjected to solvent extraction by reflux extraction at 85°C for 12 hours to remove the hexadecyltrimethylammonium bromide (the extraction solvent was a mixed solution of concentrated hydrochloric acid and ethanol with a volume ratio of 1:35). After centrifugal dispersion, the product was vacuum-dried at 65°C for 8 hours to obtain hollow SiO2 nanospheres.

[0074] S2: Dissolve 200 mg of sodium citrate in 15 mL of water to form a sodium citrate solution. Weigh 200 mg of hollow SiO2 nanospheres and magnetically stir them at room temperature (23-25°C) for 20 hours. Then, centrifuge, rinse with water, and vacuum dry at 290°C for 90 minutes to obtain SiO2 nanospheres loaded with sodium citrate (denoted as "C6H5Na3O7 / SiO2 nanospheres").

[0075] S3: Mix 0.6 mL of 3-(2-bromoisobutyl)propylene and 4 mL of dimethylchlorosilane, add 1 g of chloroplatinic acid particles, and stir the reaction in a nitrogen, light-free, and room temperature (23-25°C) environment for 6 hours. Then, remove the excess dimethylchlorosilane by vacuum distillation to obtain [3-(2-bromoisobutyl)propyl]dimethylchlorosilane, which is then immediately deposited onto the surface of 3 g of C6H5Na3O7 / SiO2 nanospheres by vapor deposition to obtain C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface.

[0076] S4: Add 1 mmol of CuBr, 0.1 mmol of CuBr2, and 2.2 mmol of 2,2'-bipyridine to a dry Shrek flask. Evacuate the flask and fill it with argon. Dissolve 50 mmol of sodium methacrylate in 10 mL of a 1:1 water / methanol mixture. Transfer the mixture to the Shrek flask and stir for 10 minutes to obtain a monomer solution.

[0077] S5: The monomer solution was added to a vial containing C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface. After reacting at room temperature (23-25°C) for 1 hour, the solution was centrifuged, washed with deionized water, ultrasonically treated in an ethanol solution for 1 minute, immersed in deionized water for 12 hours, washed with ethanol and dried under nitrogen to obtain polymethacrylic acid-coated C6H5Na3O7 / SiO2 nanospheres, i.e., controlled-release organic acid salts (denoted as "C6H5Na3O7 / SiO2@PMAA nanospheres").

[0078] S6: Add 3g of C6H5Na3O7 / SiO2@PMAA nanospheres to 10mL of a mixed solution of ammonia and ethanol (pH 8). After stirring, add 15mL of ethyl orthosilicate dropwise. After reacting at room temperature (23-25°C) for 3 hours, slowly distill under reduced pressure in a 45°C water bath until the solution reaches a pH of 5 and allow to stand for 12 hours. Subsequently, add 15mL of water, 60mL of ethanol, 5mL of propylene glycol methyl ether, 1mL of acetylacetone, and 0.1g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0079] Example 4

[0080] The anti-metal dust corrosion coating is prepared by the following steps:

[0081] S1: 24 mL of ethanol, 56 mL of deionized water, 0.18 g of hexadecyltrimethylammonium bromide, and 1 mL of ethyl orthosilicate were mixed and stirred for 6 minutes. 1 mL of ammonia water with a pH of 7.2 was then added. After reacting at room temperature (23-25°C) for 4 hours, the product was separated by centrifugation. The product was subjected to solvent extraction by reflux extraction at 85°C for 12 hours to remove the hexadecyltrimethylammonium bromide (the extraction solvent was a mixed solution of concentrated hydrochloric acid and ethanol with a volume ratio of 1:35). After centrifugal dispersion, the product was vacuum-dried at 65°C for 8 hours to obtain hollow SiO2 nanospheres.

[0082] S2: Dissolve 200 mg of sodium citrate in 15 mL of water to form a sodium citrate solution. Weigh 200 mg of hollow SiO2 nanospheres and magnetically stir them at room temperature (23-25°C) for 20 hours. Then, centrifuge, rinse with water, and vacuum dry at 255°C for 120 minutes to obtain SiO2 nanospheres loaded with sodium citrate (denoted as "C6H5Na3O7 / SiO2 nanospheres").

[0083] S3: Mix 0.6 mL of 3-(2-bromoisobutyl)propylene and 4 mL of dimethylchlorosilane, add 1 g of chloroplatinic acid particles, and stir the reaction in a nitrogen, light-free, and room temperature (23-25°C) environment for 6 hours. Then, remove the excess dimethylchlorosilane by vacuum distillation to obtain [3-(2-bromoisobutyl)propyl]dimethylchlorosilane, which is then immediately deposited onto the surface of 3 g of C6H5Na3O7 / SiO2 nanospheres by vapor deposition to obtain C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface.

[0084] S4: Add 1 mmol of CuBr, 0.1 mmol of CuBr2, and 2.2 mmol of 2,2'-bipyridine to a dry Shrek flask. Evacuate the flask and fill it with argon. Dissolve 50 mmol of sodium methacrylate in 10 mL of a 1:1 water / methanol mixture. Transfer the mixture to the Shrek flask and stir for 10 minutes to obtain a monomer solution.

[0085] S5: The monomer solution was added to a vial containing C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface. After reacting at room temperature (23-25°C) for 1 hour, the solution was centrifuged, washed with deionized water, ultrasonically treated in an ethanol solution for 1 minute, immersed in deionized water for 12 hours, washed with ethanol and dried under nitrogen to obtain polymethacrylic acid-coated C6H5Na3O7 / SiO2 nanospheres, i.e., controlled-release organic acid salts (denoted as "C6H5Na3O7 / SiO2@PMAA nanospheres").

[0086] S6: Add 3g of C6H5Na3O7 / SiO2@PMAA nanospheres to 10mL of a mixed solution of ammonia and ethanol (pH 7.5). After stirring, add 15mL of ethyl orthosilicate dropwise. After reacting at room temperature (23-25°C) for 3 hours, slowly distill under reduced pressure in a 45°C water bath until the solution reaches a pH of 5 and allow to stand for 12 hours. Subsequently, add 15mL of water, 60mL of ethanol, 5mL of propylene glycol methyl ether, 1mL of acetylacetone, and 0.1g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0087] Comparative Example 1

[0088] This comparative example is a photovoltaic module with a self-cleaning coating on the commercially available glass surface.

[0089] Comparative Example 2

[0090] The only difference between this comparative example and Example 1 is that no controlled-release organic acid salt is added to the coating; the rest is the same as Example 1. Specifically, this comparative example prepares the coating by the following steps:

[0091] Add 15 mL of ethyl orthosilicate dropwise to 10 mL of a mixed solution of ammonia and ethanol (pH 8). After reacting at room temperature (23-25°C) for 3 hours, slowly distill the solution under reduced pressure in a 45°C water bath until the pH is 5 and allow to stand for 12 hours. Subsequently, add 15 mL of water, 60 mL of ethanol, 5 mL of propylene glycol methyl ether, 1 mL of acetylacetone, and 0.1 g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0092] Comparative Example 3

[0093] The only difference between this comparative example and Example 1 is that in step S2, the drying temperature is lowered; the rest is the same as Example 1. Specifically, this comparative example prepares the coating by the following steps:

[0094] S1: 24 mL of ethanol, 56 mL of deionized water, 0.18 g of hexadecyltrimethylammonium bromide, and 1 mL of ethyl orthosilicate were mixed and stirred for 6 minutes. 1 mL of ammonia water with a pH of 7.2 was then added. After reacting at room temperature (23-25°C) for 4 hours, the product was separated by centrifugation. The product was subjected to solvent extraction by reflux extraction at 85°C for 12 hours to remove the hexadecyltrimethylammonium bromide (the extraction solvent was a mixed solution of concentrated hydrochloric acid and ethanol with a volume ratio of 1:35). After centrifugal dispersion, the product was vacuum-dried at 65°C for 8 hours to obtain hollow SiO2 nanospheres.

[0095] S2: Dissolve 200 mg of sodium citrate in 15 mL of water to form a sodium citrate solution. Weigh 200 mg of hollow SiO2 nanospheres and magnetically stir them at room temperature (23-25°C) for 20 hours. Then, centrifuge, rinse with water, and vacuum dry at 190°C for 120 minutes to obtain SiO2 nanospheres loaded with sodium citrate (denoted as "C6H5Na3O7 / SiO2 nanospheres").

[0096] S3: Mix 0.6 mL of 3-(2-bromoisobutyl)propylene and 4 mL of dimethylchlorosilane, add 1 g of chloroplatinic acid particles, and stir the reaction in a nitrogen, light-free, and room temperature (23-25°C) environment for 6 hours. Then, remove the excess dimethylchlorosilane by vacuum distillation to obtain [3-(2-bromoisobutyl)propyl]dimethylchlorosilane, which is then immediately deposited onto the surface of 3 g of C6H5Na3O7 / SiO2 nanospheres by vapor deposition to obtain C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface.

[0097] S4: Add 1 mmol of CuBr, 0.1 mmol of CuBr2, and 2.2 mmol of 2,2'-bipyridine to a dry Shrek flask. Evacuate the flask and fill it with argon. Dissolve 50 mmol of sodium methacrylate in 10 mL of a 1:1 water / methanol mixture. Transfer the mixture to the Shrek flask and stir for 10 minutes to obtain a monomer solution.

[0098] S5: The monomer solution was added to a vial containing C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface. After reacting at room temperature (23-25°C) for 1 hour, the solution was centrifuged, washed with deionized water, ultrasonically treated in an ethanol solution for 1 minute, immersed in deionized water for 12 hours, washed with ethanol and dried under nitrogen to obtain polymethacrylic acid-coated C6H5Na3O7 / SiO2 nanospheres, i.e., controlled-release organic acid salts (denoted as "C6H5Na3O7 / SiO2@PMAA nanospheres").

[0099] S6: Add 3g of C6H5Na3O7 / SiO2@PMAA nanospheres to 10mL of a mixed solution of ammonia and ethanol (pH 7.5). After stirring, add 15mL of ethyl orthosilicate dropwise. After reacting at room temperature (23-25°C) for 3 hours, slowly distill under reduced pressure in a 45°C water bath until the solution reaches a pH of 5 and allow to stand for 12 hours. Subsequently, add 15mL of water, 60mL of ethanol, 5mL of propylene glycol methyl ether, 1mL of acetylacetone, and 0.1g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0100] Comparative Example 4

[0101] The only difference between this comparative example and Example 3 is that in step S2, the drying temperature is increased; the rest is the same as Example 3. Specifically, this comparative example prepares the coating by the following steps:

[0102] S1: 24 mL of ethanol, 56 mL of deionized water, 0.18 g of hexadecyltrimethylammonium bromide, and 1 mL of ethyl orthosilicate were mixed and stirred for 6 minutes. 1 mL of ammonia water with a pH of 7.5 was then added. After reacting at room temperature (23-25°C) for 4 hours, the product was separated by centrifugation. The product was subjected to solvent extraction by reflux extraction at 85°C for 12 hours to remove the hexadecyltrimethylammonium bromide (the extraction solvent was a mixed solution of concentrated hydrochloric acid and ethanol with a volume ratio of 1:35). After centrifugal dispersion, the product was vacuum-dried at 65°C for 8 hours to obtain hollow SiO2 nanospheres.

[0103] S2: Dissolve 200 mg of sodium citrate in 15 mL of water to form a sodium citrate solution. Weigh 200 mg of hollow SiO2 nanospheres and magnetically stir them at room temperature (23-25°C) for 20 hours. Then, centrifuge, rinse with water, and vacuum dry at 300°C for 90 minutes to obtain SiO2 nanospheres loaded with sodium citrate (denoted as "C6H5Na3O7 / SiO2 nanospheres").

[0104] S3: Mix 0.6 mL of 3-(2-bromoisobutyl)propylene and 4 mL of dimethylchlorosilane, add 1 g of chloroplatinic acid particles, and stir the reaction in a nitrogen, light-free, and room temperature (23-25°C) environment for 6 hours. Then, remove the excess dimethylchlorosilane by vacuum distillation to obtain [3-(2-bromoisobutyl)propyl]dimethylchlorosilane, which is then immediately deposited onto the surface of 3 g of C6H5Na3O7 / SiO2 nanospheres by vapor deposition to obtain C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface.

[0105] S4: Add 1 mmol of CuBr, 0.1 mmol of CuBr2, and 2.2 mmol of 2,2'-bipyridine to a dry Shrek flask. Evacuate the flask and fill it with argon. Dissolve 50 mmol of sodium methacrylate in 10 mL of a 1:1 water / methanol mixture. Transfer the mixture to the Shrek flask and stir for 10 minutes to obtain a monomer solution.

[0106] S5: The monomer solution was added to a vial containing C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface. After reacting at room temperature (23-25°C) for 1 hour, the solution was centrifuged, washed with deionized water, ultrasonically treated in an ethanol solution for 1 minute, immersed in deionized water for 12 hours, washed with ethanol and dried under nitrogen to obtain polymethacrylic acid-coated C6H5Na3O7 / SiO2 nanospheres, i.e., controlled-release organic acid salts (denoted as "C6H5Na3O7 / SiO2@PMAA nanospheres").

[0107] S6: Add 3g of C6H5Na3O7 / SiO2@PMAA nanospheres to 10mL of a mixed solution of ammonia and ethanol (pH 8). After stirring, add 15mL of ethyl orthosilicate dropwise. After reacting at room temperature (23-25°C) for 3 hours, slowly distill under reduced pressure in a 45°C water bath until the solution reaches a pH of 5 and allow to stand for 12 hours. Subsequently, add 15mL of water, 60mL of ethanol, 5mL of propylene glycol methyl ether, 1mL of acetylacetone, and 0.1g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0108] Comparative Example 5

[0109] The only difference between this comparative example and Example 2 is that in step S6, the pH value of the mixed solution of ammonia water and ethanol is increased; the rest is the same as Example 2. Specifically, this comparative example prepares the coating by the following steps:

[0110] S1: 24 mL of ethanol, 56 mL of deionized water, 0.18 g of hexadecyltrimethylammonium bromide, and 1 mL of ethyl orthosilicate were mixed and stirred for 6 minutes. 1 mL of ammonia water with a pH of 8 was then added. After reacting at room temperature (23-25°C) for 4 hours, the product was separated by centrifugation. The product was subjected to solvent extraction by reflux extraction at 85°C for 12 hours to remove the hexadecyltrimethylammonium bromide (the extraction solvent was a mixed solution of concentrated hydrochloric acid and ethanol with a volume ratio of 1:35). After centrifugal dispersion, the product was vacuum-dried at 65°C for 8 hours to obtain hollow SiO2 nanospheres.

[0111] S2: Dissolve 200 mg of sodium citrate in 15 mL of water to form a sodium citrate solution. Weigh 200 mg of hollow SiO2 nanospheres and magnetically stir them at room temperature (23-25°C) for 20 hours. Then, centrifuge, rinse with water, and vacuum dry at 255°C for 120 minutes to obtain SiO2 nanospheres loaded with sodium citrate (denoted as "C6H5Na3O7 / SiO2 nanospheres").

[0112] S3: Mix 0.6 mL of 3-(2-bromoisobutyl)propylene and 4 mL of dimethylchlorosilane, add 1 g of chloroplatinic acid particles, and stir the reaction in a nitrogen, light-free, and room temperature (23-25°C) environment for 6 hours. Then, remove the excess dimethylchlorosilane by vacuum distillation to obtain [3-(2-bromoisobutyl)propyl]dimethylchlorosilane, which is then immediately deposited onto the surface of 3 g of C6H5Na3O7 / SiO2 nanospheres by vapor deposition to obtain C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface.

[0113] S4: Add 1 mmol of CuBr, 0.1 mmol of CuBr2, and 2.2 mmol of 2,2'-bipyridine to a dry Shrek flask. Evacuate the flask and fill it with argon. Dissolve 50 mmol of sodium methacrylate in 10 mL of a 1:1 water / methanol mixture. Transfer the mixture to the Shrek flask and stir for 10 minutes to obtain a monomer solution.

[0114] S5: The monomer solution was added to a vial containing C6H5Na3O7 / SiO2 nanospheres with silane initiator deposited on the surface. After reacting at room temperature (23-25°C) for 1 hour, the solution was centrifuged, washed with deionized water, ultrasonically treated in an ethanol solution for 1 minute, immersed in deionized water for 12 hours, washed with ethanol and dried under nitrogen to obtain polymethacrylic acid-coated C6H5Na3O7 / SiO2 nanospheres, i.e., controlled-release organic acid salts (denoted as "C6H5Na3O7 / SiO2@PMAA nanospheres").

[0115] S6: Add 3g of C6H5Na3O7 / SiO2@PMAA nanospheres to 10mL of a mixed solution of ammonia and ethanol (pH 8.5). After stirring, add 15mL of ethyl orthosilicate dropwise. After reacting at room temperature (23-25°C) for 3 hours, slowly distill under reduced pressure in a 45°C water bath until the solution reaches a pH of 5 and allow to stand for 12 hours. Subsequently, add 15mL of water, 60mL of ethanol, 5mL of propylene glycol methyl ether, 1mL of acetylacetone, and 0.1g of methyltriethoxysilane and mix thoroughly to obtain a metal dust corrosion protection coating.

[0116] Application Examples

[0117] The coatings prepared according to the methods of Examples 1 to 4 and Comparative Examples 2 to 5 were applied to the glass surface of the new grid-connected photovoltaic modules in the same area of ​​the roof of the metal processing plant at a coating amount of 20 mL / m 2 The photovoltaic modules of comparative example 1 were placed in the same area. One year later (cleaned twice by simple rinsing with clean water), the accumulation of metal dust on the glass surface of the photovoltaic modules was observed (indicated by "×", where the more "×" there is, the more metal dust there is).

[0118] Table 1 Test results of metal dust pollution and corrosion prevention effect

[0119]

[0120] Analyzing the test results in Table 1, we can see that:

[0121] (1) Compared with Comparative Examples 1 and 2, Examples 1 to 4 have better anti-metal dust pollution corrosion effects. The reason is that: Examples 1 to 4 add the controlled-release organic acid salt of the present invention to the coating. When the metal dust is just adsorbed on the coating surface, it will first oxidize to form a small amount of metal rust. The formation of metal rust causes the local pH value in the coating to rise. When the pH value becomes alkaline, the polymethacrylic acid on the surface of the controlled-release organic acid salt changes from a closed state to an open-pore state, and the organic acid salt inside the silica nanospheres is released. Its organic acid radical ions are adsorbed on the surface of the metal particles to form a hydrophilic protective film, which can prevent the metal particles from continuing to oxidize to produce metal rust and make the metal particles easily carried away by water during precipitation or cleaning, thereby producing a better anti-metal dust pollution corrosion effect.

[0122] (2) Compared with Examples 1 to 3, the anti-metal dust pollution corrosion effects of Comparative Examples 3 and 4 are weaker. The reason is that during the drying process of the hollow SiO2 nanospheres after being immersed in and adsorbed with the sodium citrate solution, the drying temperature used in Comparative Example 3 is relatively low, which cannot effectively remove the crystallization water of ammonium citrate; while Comparative Example 4 uses a relatively high drying temperature, which causes the sodium citrate to thermally decompose, affecting its effect.

[0123] (3) Compared with Examples 2 and 4, the metal dust pollution corrosion protection effect of Comparative Example 5 is weaker. The reason for this is that in the process of preparing the controlled-release organic acid salt into the coating of Comparative Example 5, the pH of the mixed solution of ammonia water and ethanol used is relatively high, which causes the polymethacrylic acid on the surface of the controlled-release organic acid salt to be in an open-pore state. The organic acid salt loaded inside is released and neutralized prematurely, losing the ability to coat metal dust, thereby resulting in poor metal dust pollution corrosion protection effect of the coating.

[0124] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art to which this disclosure pertains. Unless otherwise specified, the raw materials and equipment used herein are conventional in the art and can be obtained from conventional commercial sources. The methods used herein are conventional in the art, unless otherwise specified.

[0125] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. Application of a coating for preventing metal dust pollution and corrosion on the surface of photovoltaic module glass, characterized in that: The coating contains a controlled-release organic acid salt; The controlled-release organic acid salt comprises: hollow SiO2 nanospheres, sodium citrate loaded in the hollow SiO2 nanospheres, and polymethacrylic acid coated on the outside of the hollow SiO2 nanospheres; the preparation steps of the controlled-release organic acid salt include: S1: Add the hollow SiO2 nanospheres into the sodium citrate solution, fully impregnate, separate the product, and dry it at 205-290℃; S2: depositing [3-(2-bromoisobutyl)propyl]dimethylchlorosilane onto the surface of the product obtained in S1, mixing it with a monomer, a polymerization catalyst, and a polymerization reaction solvent, conducting a polymerization reaction, and separating the product to obtain a controlled-release organic acid salt; the monomer is methacrylic acid and / or methacrylic acid salt.

2. The use according to claim 1, characterized in that In the coating, the content of the controlled-release organic acid salt is 0.3-5 wt %.

3. The use according to claim 1 or 2, characterized in that The coating comprises the following components: a controlled-release organic acid salt, SiO2 sol, a film-forming auxiliary agent, a curing accelerator, a hardening agent, and a dispersion medium.

4. The use according to claim 3, characterized in that The film-forming aid includes propylene glycol methyl ether; the curing accelerator includes acetylacetone; and the hardening agent includes polyethyl silicate and / or a silane coupling agent.

5. The use according to claim 1, characterized in that The preparation method of the coating comprises the following steps: using a controlled-release organic acid salt to prepare a coating for preventing metal dust corrosion.

6. The use according to claim 1, characterized in that In step S2, the polymerization catalyst comprises CuBr, CuBr2 and 2,2'-bipyridine in a molar ratio of 1:0.08-0.15:2.0-2.

5.

7. The use according to claim 1, characterized in that In step S2, the ratio of the monomer, the polymerization catalyst and the polymerization reaction solvent is 1 mol: 0.05-0.10 mol: 200-250 mL.

8. The use according to claim 1, characterized in that In step S2, the polymerization reaction temperature is 20-30° C., and the time is 1-1.5 h.

9. The use according to claim 5, characterized in that The preparation method of the coating specifically includes the following steps: mixing a controlled-release organic acid salt with an ammonia aqueous solution with a pH value not higher than 8, adding ethyl orthosilicate, reacting at 20-30° C. for 1-5 hours, distilling under reduced pressure to a pH value of 2-5, standing for 7-24 hours, and adding a film-forming aid, a curing accelerator, a hardening agent and a dispersion medium to obtain a coating that prevents metal dust corrosion.

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