Self-cleaning nano-coated glass panel and its preparation method and application

Abstract

The application relates to the field of coating, and discloses a self-cleaning nano-coating glass plate and a preparation method and application thereof, the nano-coating comprising: silicone resin, epoxy resin, modified nano-titanium dioxide, long-chain alkyl methyl silicone oil, a curing agent and a diluent; the modified nano-titanium dioxide is prepared by grafting modified silane coupling agents prepared by reacting modified phosphorus-containing antibacterial monomers with vinyl triethoxysilane with nano-titanium dioxide; the modified phosphorus-containing antibacterial monomers are prepared by reacting syzygium aromaticum and N-bromosuccinimide, then reacting with 2-amino-4-methylthiazole, and further reacting with diphenyl phosphinic chloride; the obtained phosphorus-containing antibacterial monomers are reacted with 1,1,3,3-tetramethyldisiloxane; the long-chain alkyl methyl silicone oil is prepared by using octamethylcyclotetrasiloxane, dodecyl methyl dimethoxysilane and hexamethyldisiloxane as raw materials; and the nano-coating prepared by the application has a super-hydrophobic surface, and simultaneously has excellent antibacterial property, wear resistance and flame resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coating, and particularly relates to a self-cleaning nano-coating glass plate and a preparation method and application thereof. BACKGROUND

[0002] The super-hydrophilic coating has strong hydrophilicity, can form a uniform water film on the surface, effectively prevents the adhesion of dirt and particles, and has photocatalytic properties, thereby realizing the self-cleaning effect. However, the super-hydrophilic surface requires a large amount of water to realize the self-cleaning effect. In contrast, the super-hydrophobic coating makes the surface extremely hydrophobic. When water droplets contact the coating, they will quickly roll and carry away the dirt and particles on the surface. This effect of cleaning the surface by rolling water droplets is called super-hydrophobic self-cleaning effect.

[0003] The super-hydrophobic coating has many unique properties. When it is applied to the surface of a glass plate to prepare a glass plate-based transparent super-hydrophobic nano-coating, it has wide application prospects. However, in the actual application at the present stage, there are still some problems. For example, in the prior art, expensive fluorine-containing low surface modifier is often used to prepare the super-hydrophobic coating. However, the fluorine-containing low surface modifier cannot be decomposed by nature and is harmful to the human body, which is very environmentally unfriendly. In addition, the fluorine-containing nano-coating has poor wear resistance and is easily scratched, which affects its transparency and aesthetics. In addition, the existing nano-coating has deficiencies in flame retardance and antibacterial properties. The prior art adds inorganic flame retardants or antibacterial agents to improve the flame retardance and antibacterial properties. However, simple physical mixing can easily cause the precipitation of inorganic flame retardants or antibacterial agents. Therefore, it is difficult to guarantee the persistent flame retardance or antibacterial effect of the nano-coating, which further makes it difficult to meet the high-end application requirements. SUMMARY

[0004] To solve the problems mentioned in the background, the purpose of the present application is to provide a self-cleaning nano-coating glass plate and a preparation method and application thereof. Through the synergistic effect of silicone resin and long-chain alkyl methyl silicone oil, and the strengthening effect of epoxy resin and modified nano-titanium dioxide, the glass plate-based nano-coating is given a super-hydrophobic surface, which has good anti-fouling and self-cleaning effects, and also has excellent antibacterial properties, wear resistance and flame retardance.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] A self-cleaning nano-coating glass plate, comprising a glass plate and a self-cleaning nano-coating attached to the surface of the glass plate, wherein the self-cleaning nano-coating comprises the following components by weight: 30-60 parts of silicone resin, 10-20 parts of epoxy resin, 5-10 parts of modified nano-titanium dioxide, 1-3 parts of long-chain alkyl methyl silicone oil, 2.5-5 parts of curing agent, and 40-65 parts of diluent.

[0007] The modified nano-titanium dioxide is prepared by grafting a modified silane coupling agent on the surface of nano-titanium dioxide through a silicon-hydrogen addition reaction of a modified phosphorus-containing antibacterial monomer and vinyl triethoxysilane; wherein the modified phosphorus-containing antibacterial monomer is prepared by a substitution reaction of eugenol bromide obtained by a reaction of eugenol and N-bromosuccinimide with 2-amino-4-methylthiazole, and then a silicon-hydrogen addition reaction of the antibacterial monomer obtained by the substitution reaction with diphenylphosphinic chloride and 1,1,3,3-tetramethyldisiloxane.

[0008] The long-chain alkyl methyl silicone oil is prepared by using octamethylcyclotetrasiloxane and dodecyl methyl dimethoxysilane as raw materials, tetramethylammonium hydroxide as a catalyst, and hexamethyldisiloxane as an end-capping agent.

[0009] Preferably, the curing agent is one or more of triethylenetetramine, curing agent 593, 4,4'-diaminodiphenyl methane, and m-xylylenediamine mixed; and the diluent is one or more of acetone, butanone, ethyl acetate, toluene, and xylene mixed.

[0010] Preferably, the preparation method of the modified nano-titanium dioxide comprises the following steps:

[0011] A. Eugenol and carbon tetrachloride are taken into a reactor, stirred and mixed under a nitrogen atmosphere at 55-70°C, then N-bromosuccinimide and dibenzoyl peroxide are added, and stirred for 5-6 hours. After the reaction is completed, the precipitate is filtered and washed with carbon tetrachloride. The obtained washing liquid and filtrate are mixed, washed with deionized water, and extracted. Anhydrous sodium sulfate is added to the obtained organic phase to remove water, then the obtained filtrate is rotary evaporated under reduced pressure to remove the organic solvent, and eugenol bromide is prepared.

[0012] B. Eugenol bromide, 2-amino-4-methylthiazole, and sodium carbonate are taken into a reactor, a mixed solution of N,N-dimethylformamide and tetrahydrofuran is added, and stirred and reacted at 60-70°C for 1.5-3 hours. After the reaction is completed, rotary evaporation, washing, and drying are performed to prepare the antibacterial monomer.

[0013] C. The antibacterial monomer and diphenylphosphinic chloride are taken into a reactor, tetrahydrofuran solvent is added, and stirred and reacted for 4-7 hours. During the reaction, triethylamine is added. After the reaction is completed, suction filtration, rotary evaporation, and drying are performed to prepare the phosphorus-containing antibacterial monomer.

[0014] D. The phosphorus-containing antibacterial monomer and tetrahydrofuran are taken into a reactor, stirred and mixed, then chloroplatinic acid isopropanol solution is added, stirred and heated to 55-65°C under a nitrogen atmosphere, then 1,1,3,3-tetramethyldisiloxane is added, and stirred and reacted for 5-8 hours. After the reaction is completed, the unreacted substances are removed by rotary evaporation to prepare the modified phosphorus-containing antibacterial monomer.

[0015] E, taking the modified phosphorus-containing antibacterial monomer and vinyl triethoxysilane in a reactor, adding toluene solvent, stirring and heating to 75-85℃ in a nitrogen atmosphere, then adding chloroplatinic acid catalyst, stirring for 5-6h, removing unreacted substances by rotary evaporation after the reaction is completed, to prepare a modified silane coupling agent;

[0016] F, ultrasonic dispersion of nano-titanium dioxide in a mixed solution of anhydrous ethanol and deionized water, then adding a modified silane coupling agent, stirring at 65-90℃ for 4-8h, centrifugation, washing and drying after the reaction is completed, to prepare a modified nano-titanium dioxide.

[0017] Preferably, the structure of the eugenol bromide is:

[0018]

[0019] Preferably, the structure of the modified silane coupling agent is:

[0020]

[0021] Preferably, the molar ratio of eugenol and N-bromosuccinimide in step A is 1; 1-1.3; the molar ratio of eugenol bromide and 2-amino-4-methylthiazole in step B is 1; 1-1.2.

[0022] Preferably, the molar ratio of antibacterial monomer and diphenylphosphinic chloride in step C is 1; 1-1.2.

[0023] Preferably, the molar ratio of phosphorus-containing antibacterial monomer and 1,1,3,3-tetramethyldisiloxane in step D is 1-1.1; 1.

[0024] Preferably, the molar ratio of modified phosphorus-containing antibacterial monomer and vinyl triethoxysilane in step E is 1; 1-1.2.

[0025] Preferably, the preparation method of long-chain alkyl methyl silicone oil comprises the following steps: taking octamethylcyclotetrasiloxane and dodecyl methyl dimethoxysilane in a reactor, stirring and heating to 75-85℃, then adding tetramethylammonium hydroxide, adding hexamethyldisiloxane after 0.5-1h of reaction, continuing to heat to 90-120℃ for 2-4h, removing the catalyst by distillation under reduced pressure after the reaction is completed, and heating to 135-140℃ to prepare long-chain alkyl methyl silicone oil.

[0026] A preparation method of a self-cleaning nano-coated glass plate, comprising the following steps:

[0027] S1, each component is weighed by parts by weight, the epoxy resin and diluent are stirred uniformly, then the curing agent is added and continues to be stirred and mixed, to prepare an epoxy resin dispersion;

[0028] S2, the silicone resin, long-chain alkyl methyl silicone oil, modified nano titanium dioxide and epoxy resin dispersion are stirred and mixed, to prepare a self-cleaning nano coating;

[0029] S3, the self-cleaning nano coating is uniformly coated on the surface of the washed and dried glass plate, and then is placed at 80-100 DEG C for 1-3 hours for curing, to prepare a self-cleaning nano coating glass plate.

[0030] Preferably, the self-cleaning nano coating glass plate is applied to a washing machine observation window, an electric meter shell, an automobile rearview mirror, a power distribution room observation window and a carriage window.

[0031] The beneficial effects of the present application are as follows:

[0032] The present application utilizes the substitution reaction of eugenol and N-bromosuccinimide to generate eugenol bromide, then utilizes the substitution reaction of the bromine atom in the structure of eugenol bromide and the amino group in the structure of 2-amino-4-methylthiazole to generate an antibacterial monomer, then utilizes the substitution reaction of the hydroxyl group in the structure of the antibacterial monomer and diphenyl phosphinic chloride to prepare a phosphorus-containing antibacterial monomer, and further utilizes the silicon-hydrogen addition reaction of the phosphorus-containing antibacterial monomer and 1,1,3,3-tetramethyldisiloxane to prepare a modified phosphorus-containing antibacterial monomer, then utilizes the silicon-hydrogen addition reaction of the remaining double bond group in the structure of the modified phosphorus-containing antibacterial monomer and vinyltriethoxysilane to prepare a modified silane coupling agent.

[0033] The present application utilizes chemical reaction to graft the modified silane coupling agent on the surface of nano titanium dioxide, so that the natural antibacterial material eugenol, the phosphorus element and silicon element with synergistic flame-retardant effect, the Si-O-Si bond with good wear resistance and the thiazole monomer with hydrophobic structure and antibacterial activity are introduced on the surface of nano titanium dioxide through firm chemical bonds, so as to endow the nano coating with excellent flame-retardant performance, antibacterial performance, hydrophobic performance and wear resistance. The present application chemically grafts the modified silane coupling agent on the surface of nano titanium dioxide with good ultraviolet radiation shielding capacity, so as to realize functional integration, make up for the defect of insufficient antibacterial activity of nano titanium dioxide when used alone in dark conditions, improve the problems of easy migration and short antibacterial action time of the antibacterial components in the structure of the modified silane coupling agent when used alone, and further improve the dispersion uniformity of nano titanium dioxide in the matrix, which is conducive to the full play of the performance of nano titanium dioxide.

[0034] The application uses octamethylcyclotetrasiloxane and dodecylmethyldimethoxysilane as raw materials, tetramethylammonium hydroxide as a catalyst, and hexamethyldisiloxane as a capping agent to prepare long-chain alkyl methyl silicone oil. The long-chain alkyl water-repellent group and the strong hydrophobicity of the silicone oil make the coating form a super-hydrophobic surface, thereby making the nano coating have a stain-repellent self-cleaning effect. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the application.

[0036] The organic silicone resin in the embodiments and comparative examples of the application is produced by Shanghai Xiato New Material Co., Ltd.

[0037] The preparation method of the modified nano titanium dioxide in Example 1 comprises the following steps:

[0038] A. 3.6 g of eugenol and 150 mL of carbon tetrachloride were taken in a reactor, and the mixture was stirred at 60°C under a nitrogen atmosphere, then 4.9 g of N-bromosuccinimide and 0.2 g of dibenzoyl peroxide were added, and the reaction was stirred for 6 h. After the reaction was completed, the precipitate was filtered and washed with 15 mL of carbon tetrachloride. The obtained washing liquid and filtrate were mixed, 20 mL of deionized water was added for washing, and extraction was performed. Anhydrous sodium sulfate was added to the obtained organic phase to remove water, and then the obtained filtrate was subjected to rotary evaporation under reduced pressure to remove the organic solvent, thereby obtaining eugenol bromide;

[0039] B. 2.4 g of eugenol bromide (Mr=243.1), 1.3 g of 2-amino-4-methylthiazole, and 1.6 g of sodium carbonate were taken in a reactor, 50 mL of a mixed solution of N,N-dimethylformamide and tetrahydrofuran in a volume ratio of 1:1 was added, and the mixture was stirred at 65°C for 2 h. After the reaction was completed, rotary evaporation, washing, and drying were performed, thereby obtaining an antibacterial monomer;

[0040] C. 3.4 g of the antibacterial monomer (Mr=276.4) and 3.1 g of diphenylphosphinic chloride were taken in a reactor, 50 mL of tetrahydrofuran was added, and the mixture was stirred for 6 h. During the reaction, 1.2 g of triethylamine was added in batches. After the reaction was completed, the mixture was subjected to suction filtration, rotary evaporation, and drying, thereby obtaining a phosphorus-containing antibacterial monomer;

[0041] D、Take 5.5 g of phosphorus-containing antibacterial monomer (Mr = 476.5) and 100 mL of tetrahydrofuran in a reactor, after stirring and mixing, add 1 mL of chloroplatinic acid isopropanol solution (0.02 g / mL), stir and heat to 60℃ under nitrogen atmosphere, then add 1.5 g of 1,1,3,3-tetramethyldisiloxane, stir for 8 h, after the reaction is completed, remove the unreacted substance by rotary evaporation, and prepare a modified phosphorus-containing antibacterial monomer;

[0042] E、Take 6.1 g of modified phosphorus-containing antibacterial monomer (Mr = 610.8) and 2.1 g of vinyl triethoxysilane in a reactor, add 50 mL of toluene solvent, stir and heat to 80℃ under nitrogen atmosphere, then add 0.2 g of chloroplatinic acid catalyst, stir for 6 h, after the reaction is completed, remove the unreacted substance by rotary evaporation, and prepare a modified silane coupling agent;

[0043] F、Take 5 g of nano titanium dioxide and ultrasonically disperse in a mixture of 90 mL of anhydrous ethanol and 10 mL of deionized water, then add 2.6 g of modified silane coupling agent, stir at 85℃ for 6 h, after the reaction is completed, centrifuge, wash and dry, and prepare a modified nano titanium dioxide.

[0044] Example 2 A method for preparing a long-chain alkyl methyl silicone oil includes the following steps:

[0045] Take 100 g of octamethylcyclotetrasiloxane and 8 g of dodecyl methyl dimethoxysilane in a reactor, stir and heat to 80℃, then add 0.08 g of tetramethylammonium hydroxide, after 1 h of reaction, add 1.2 g of hexamethyldisiloxane, continue to heat to 100℃ and react for 4 h, after the reaction is completed, distill under reduced pressure, then heat to 135℃ to remove the catalyst, and prepare a long-chain alkyl methyl silicone oil.

[0046] Example 3 A self-cleaning nano coating includes the following components by weight: silicone resin 40 parts, epoxy resin E44 12 parts, modified nano titanium dioxide prepared in Example 1 5 parts, long-chain alkyl methyl silicone oil prepared in Example 2 1.2 parts, curing agent 593 2.5 parts, diluent acetone 45 parts.

[0047] A method for preparing a self-cleaning nano coated glass plate includes the following steps:

[0048] S1, weigh each component by weight, stir the epoxy resin E44 and the diluent acetone uniformly, then add the curing agent 593 and continue to stir and mix, to prepare an epoxy resin dispersion;

[0049] S2, stir and mix the silicone resin, long-chain alkyl methyl silicone oil, modified nano titanium dioxide and epoxy resin dispersion, to prepare a self-cleaning nano coating;

[0050] S3, uniformly coating the self-cleaning nano coating on the surface of the washed and dried glass plate, and then curing at 100°C for 1h to obtain a self-cleaning nano coating glass plate.

[0051] Example 4 A self-cleaning nano coating comprises the following components by weight: silicone resin 51 parts, epoxy resin E4416 parts, modified nano titanium dioxide prepared in Example 1 7 parts, long-chain alkyl methyl silicone oil prepared in Example 2 2 parts, curing agent 5933.5 parts, diluent acetone 55 parts.

[0052] A method for preparing a self-cleaning nano coating glass plate is the same as that in Example 3.

[0053] Example 5 A self-cleaning nano coating comprises the following components by weight: silicone resin 58 parts, epoxy resin E4420 parts, modified nano titanium dioxide prepared in Example 1 9 parts, long-chain alkyl methyl silicone oil prepared in Example 2 2.7 parts, curing agent 5935 parts, diluent acetone 63 parts.

[0054] A method for preparing a self-cleaning nano coating glass plate is the same as that in Example 3.

[0055] Comparative Example 1 A method for preparing modified nano titanium dioxide comprises the following steps:

[0056] A, 3.6g of eugenol and 150mL of carbon tetrachloride were taken in a reactor, stirred and mixed under a nitrogen atmosphere at 60°C, then 4.9g of N-bromosuccinimide and 0.2g of dibenzoyl peroxide were added, stirred and reacted for 6h, after the reaction was completed, the precipitate was filtered and washed with 15mL of carbon tetrachloride, the obtained washing liquid and filtrate were mixed, 20mL of deionized water was added for washing, and extraction was carried out, anhydrous sodium sulfate was added to the obtained organic phase after extraction to remove water, then the obtained filtrate was filtered and the organic solvent was removed by rotary evaporation under reduced pressure to obtain eugenol bromide;

[0057] B, 2.4g of eugenol bromide (Mr=243.1), 1.3g of 2-amino-4-methylthiazole, and 1.6g of sodium carbonate were taken in a reactor, 50mL of a mixed solution of N,N-dimethylformamide and tetrahydrofuran in a volume ratio of 1:1 was added, stirred and reacted at 65°C for 2h, after the reaction was completed, rotary evaporation, washing, and drying were carried out to obtain an antibacterial monomer;

[0058] C, 3.2g of the antibacterial monomer (Mr=276.4) and 100mL of tetrahydrofuran were taken in a reactor, stirred and mixed, then 1mL of chloroplatinic acid isopropyl alcohol solution (0.02g / mL) was added, stirred and heated to 60°C under a nitrogen atmosphere, then 1.5g of 1,1,3,3-tetramethyldisiloxane was added, stirred and reacted for 8h, after the reaction was completed, the unreacted substances were removed by rotary evaporation to obtain a modified antibacterial monomer.

[0059] D, 4.1 g of modified antibacterial monomer (Mr = 410.7) and 2.1 g of vinyl triethoxysilane were taken in a reactor, 50 mL of toluene solvent was added, stirred and heated to 80°C under nitrogen atmosphere, then 0.2 g of chloroplatinic acid catalyst was added, stirred for 6 h, and after the reaction was completed, the unreacted substance was removed by rotary evaporation to prepare a modified silane coupling agent;

[0060] E, 5 g of nano titanium dioxide was ultrasonically dispersed in a mixed solution of 90 mL of anhydrous ethanol and 10 mL of deionized water, then 2.6 g of modified silane coupling agent was added, and stirred at 85°C for 6 h, and after the reaction was completed, centrifugation, washing and drying were carried out to prepare a modified nano titanium dioxide.

[0061] A self-cleaning nano coating according to Comparative Example 2 includes the following components by weight: silicone resin 58 parts, epoxy resin E4420 parts, modified nano titanium dioxide prepared in Comparative Example 1 9 parts, long-chain alkyl methyl silicone oil prepared in Example 2 2.7 parts, curing agent 5935 parts, diluent acetone 63 parts.

[0062] A method for preparing a self-cleaning nano coated glass plate is the same as in Example 3.

[0063] A self-cleaning nano coating according to Comparative Example 3 includes the following components by weight: silicone resin 58 parts, epoxy resin E4420 parts, nano titanium dioxide 9 parts, long-chain alkyl methyl silicone oil prepared in Example 2 2.7 parts, curing agent 5935 parts, diluent acetone 63 parts.

[0064] A method for preparing a self-cleaning nano coated glass plate is the same as in Example 3.

[0065] A self-cleaning nano coating according to Comparative Example 4 includes the following components by weight: silicone resin 58 parts, epoxy resin E4420 parts, modified nano titanium dioxide prepared in Example 1 9 parts, dimethyl silicone oil 2.7 parts, curing agent 5935 parts, diluent acetone 63 parts.

[0066] A method for preparing a self-cleaning nano coated glass plate is the same as in Example 3.

[0067] Performance testing

[0068] The self-cleaning nano coating prepared in Examples 3-5 and Comparative Examples 2-4 was subjected to performance testing: contact angle and roll angle testing was performed using a dynamic contact angle tester, 5 μL of water droplet was used for each measurement, and the average data was determined from at least three measurements at different positions of the same sample; antibacterial rate testing was performed in accordance with GB / T 21866-2008, and the test bacteria was Staphylococcus aureus; 45-mesh sand was used as a testing tool, the self-cleaning nano coated glass plate prepared in Examples 3-5 and Comparative Examples 2-4 was vertically inserted into the 45-mesh sand, and was reciprocated at a rate of 30 times / min and with an "insertion-pulling" action, the glass plate was removed after 150 abrasion tests, and the water static contact angle of the self-cleaning nano coating after mechanical abrasion was tested; the flame retardant properties of the nano coating were tested by limiting oxygen index; the self-cleaning performance was tested by placing the self-cleaning nano coated glass plate in 45-mesh sand and dropping water using a syringe, and the data results are shown in Table 1.

[0069] Table 1: Performance testing results of samples

[0070]

[0071] As can be seen from the data in Table 1, the nano coating prepared in Examples 3-5 has a high antibacterial rate, good wear resistance, and good flame retardant effect, the water contact angle is greater than 150°, the roll angle is less than 10°, has excellent super-hydrophobic properties, and good anti-fouling and self-cleaning effect. In Comparative Example 2, the modified nano titanium dioxide component added does not introduce phosphorus elements, and the measured flame retardant properties are poorer than those of Examples 3-5; in Comparative Example 3, the nano titanium dioxide is not modified, the measured water contact angle is less than 150°, the roll angle is greater than 10°, and the self-cleaning performance is poorer than that of Examples 3-5, the reason is that the surface of the nano titanium dioxide is rich in hydrophilic hydroxyl groups, and the surface of the nano titanium dioxide does not introduce a modified silane coupling agent, and the measured antibacterial rate, water static contact angle after mechanical abrasion, and limiting oxygen index are significantly lower than those of Examples 3-5, indicating that the grafting of the modified silane coupling agent can improve the wear resistance, antibacterial properties, and flame retardant properties of the nano coating to some extent; in Comparative Example 4, the long-chain alkyl methyl silicone oil is replaced with an equal amount of dimethyl silicone oil, the measured water contact angle is less than 150°, the roll angle is greater than 10°, and the self-cleaning performance is poorer than that of Examples 3-5, indicating that the introduction of long-chain alkyl methyl silicone oil can promote the formation of a super-hydrophobic surface of the nano coating and improve the anti-fouling and self-cleaning effect.

[0072] In the description of the specification, the description of the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0073] The basic principles, main features and advantages of the present application are shown and described above. Those skilled in the art should understand that the present application is not limited by the above embodiments, and the above embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A self-cleaning nano-coated glass plate, characterized in that, The invention includes a glass plate and a self-cleaning nano-coating attached to the surface of the glass plate. The self-cleaning nano-coating comprises the following components by weight: 30-60 parts of silicone resin, 10-20 parts of epoxy resin, 5-10 parts of modified nano-titanium dioxide, 1-3 parts of long-chain alkyl methyl silicone oil, 2.5-5 parts of curing agent, and 40-65 parts of diluent. The preparation method of the modified nano-titanium dioxide includes the following steps: A. Eugenol and carbon tetrachloride were placed in a reactor and stirred and mixed at 55-70°C under a nitrogen atmosphere. Then, N-bromosuccinimide and benzoyl peroxide were added and stirred for 5-6 hours. After the reaction was completed, the precipitate was filtered and washed with carbon tetrachloride. The washing liquid and filtrate were mixed and washed with deionized water and extracted. Anhydrous sodium sulfate was added to the organic phase obtained by extraction and shaken to remove water. The filtrate obtained by filtration was then removed by rotary evaporation under reduced pressure to prepare eugenol bromide. B. Take eugenol bromide, 2-amino-4-methylthiazole, and sodium carbonate in a reactor, add a mixed solution of N,N-dimethylformamide and tetrahydrofuran, and stir the reaction at 60~70℃ for 1.5~3h. After the reaction is completed, the antibacterial monomer is prepared by rotary evaporation under reduced pressure, washing and drying. C. Take the antibacterial monomer and diphenylphosphine chloride in a reactor, add tetrahydrofuran solvent, stir the reaction for 4-7 hours, add triethylamine during the reaction, and after the reaction is completed, filter, evaporate and dry to prepare the phosphorus-containing antibacterial monomer. D. Take the phosphorus-containing antibacterial monomer and tetrahydrofuran in a reactor, stir and mix them, then add the isopropanol solution of chloroplatinic acid, stir and heat to 55~65℃ in a nitrogen atmosphere, then add 1,1,3,3-tetramethyldisiloxane, stir and react for 5~8h, and after the reaction is completed, remove the unreacted material by rotary evaporation to prepare the modified phosphorus-containing antibacterial monomer. E. Take the modified phosphorus-containing antibacterial monomer and vinyltriethoxysilane into a reactor, add toluene solvent, stir and heat to 75~85℃ in a nitrogen atmosphere, then add chloroplatinic acid catalyst, stir and react for 5~6h, and remove unreacted substances by rotary evaporation after the reaction is completed to prepare the modified silane coupling agent. F. Take nano-titanium dioxide and ultrasonically disperse it in a mixed solution of anhydrous ethanol and deionized water. Then add a modified silane coupling agent and stir the mixture at 65~90℃ for 4~8h. After the reaction is completed, centrifuge, wash and dry to prepare modified nano-titanium dioxide. In step A, the molar ratio of eugenol to N-bromosuccinimide is 1:1 to 1.3; in step B, the molar ratio of eugenol bromide to 2-amino-4-methylthiazole is 1:1 to 1.2; in step C, the molar ratio of antibacterial monomer to diphenylphosphine chloride is 1:1 to 1.2; in step D, the molar ratio of phosphorus-containing antibacterial monomer to 1,1,3,3-tetramethyldisiloxane is 1 to 1.1:1; and in step E, the molar ratio of modified phosphorus-containing antibacterial monomer to vinyltriethoxysilane is 1:1 to 1.

2. The long-chain alkylmethyl silicone oil is made using octamethylcyclotetrasiloxane and dodecylmethyldimethoxysilane as raw materials, tetramethylammonium hydroxide as a catalyst, and hexamethyldisiloxane as a capping agent.

2. The self-cleaning nano-coated glass plate according to claim 1, characterized in that, The curing agent is one or more of triethylenetetramine, curing agent 593, 4,4'-diaminodiphenylmethane, and m-phenylenediamine; the diluent is one or more of acetone, butanone, ethyl acetate, toluene, and xylene.

3. The self-cleaning nano-coated glass plate according to claim 1, characterized in that, The preparation method of the long-chain alkylmethyl silicone oil includes the following steps: octamethylcyclotetrasiloxane and dodecylmethyldimethoxysilane are placed in a reactor, stirred and heated to 75-85°C, then tetramethylammonium hydroxide is added, and after reacting for 0.5-1 h, hexamethyldisiloxane is added, and the temperature is further raised to 90-120°C for 2-4 h. After the reaction is completed, the mixture is distilled under reduced pressure, and then heated to 135-140°C to remove the catalyst, thus preparing the long-chain alkylmethyl silicone oil.

4. A method for preparing a self-cleaning nano-coated glass plate according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Weigh each component according to the weight parts, stir the epoxy resin and diluent evenly, then add the curing agent and continue stirring to prepare an epoxy resin dispersion. S2. A self-cleaning nano-coating was prepared by stirring and mixing organosilicon resin, long-chain alkyl methyl silicone oil, modified nano titanium dioxide and epoxy resin dispersion. S3. Apply the self-cleaning nano-coating evenly to the cleaned and dried glass plate surface, and then cure it at 80~100℃ for 1~3h to obtain the self-cleaning nano-coated glass plate.

5. The application of the self-cleaning nano-coated glass plate according to claim 1, characterized in that, The self-cleaning nano-coated glass panel is used in washing machine viewing windows, electric meter housings, car rearview mirrors, power distribution room viewing windows, and vehicle windows.

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