Self-cleaning nano-coating glass plate as well as preparation method and application thereof

Abstract

The invention relates to the field of coatings, and discloses a self-cleaning nano-coating glass plate and a preparation method and application thereof.The nano-coating is prepared from organic silicon 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 a modified silane coupling agent and nano titanium dioxide, wherein the modified silane coupling agent is prepared by reacting a modified phosphorus-containing antibacterial monomer with vinyltriethoxysilane; the modified phosphorus-containing antibacterial monomer is prepared by reacting eugenol with N-bromosuccinimide, then reacting with 2-amino-4-methylthiazole, further reacting with diphenyl phosphinyl chloride, and reacting the obtained phosphorus-containing antibacterial monomer with 1, 1, 3, 3-tetramethyldisiloxane; the long-chain alkyl methyl silicone oil is prepared by using octamethylcyclotetrasiloxane, dodecyl methyl dimethoxy silane and hexamethyldisiloxane as raw materials, and the prepared nano coating has a super-hydrophobic surface and also has excellent antibacterial activity, wear resistance and flame retardance.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to a self-cleaning nano-coated glass plate and a preparation method and application thereof. Background Art

[0002] Superhydrophilic coatings have strong hydrophilicity and can form a uniform water film on the surface, effectively preventing the adhesion of dirt and particles. They also have photocatalytic properties, thereby achieving a self-cleaning effect. However, a large amount of water is required for hydrophilic surfaces to achieve self-cleaning effects. In contrast to superhydrophilic coatings, superhydrophobic coatings make the surface extremely hydrophobic. Water droplets will roll quickly after contacting this coating and carry away dirt and particles on the surface. This effect of cleaning the surface through rolling water droplets is called the superhydrophobic self-cleaning effect.

[0003] Super hydrophobic coating has many unique properties. It is applied to the surface of glass plate to prepare transparent super hydrophobic nano coating based on glass plate, which has broad application prospects. However, in the practical application at the current stage, there are still some problems, such as the prior art often uses expensive fluorine-containing low surface modifier to prepare super hydrophobic coating, but the fluorine-containing low surface modifier cannot be decomposed by nature, is harmful to the human body, is very environmentally unfriendly, and the wear resistance of fluorine-containing nano coating is poor, it is easy to be scraped off, affecting its transparency and aesthetics, and the existing nano coating is insufficient in flame retardant and antibacterial properties, the prior art improves flame retardant and antibacterial properties by adding inorganic flame retardants or antibacterial agents, but simple physical mixing is prone to precipitation of inorganic flame retardants or antibacterial agents, so it is actually difficult to ensure the lasting flame retardant or antibacterial effect of nano coating, and thus it is difficult to meet high-end application requirements. Summary of the invention

[0004] In order to solve the deficiencies mentioned in the above background technology, the purpose of the present invention is to provide a self-cleaning nano-coated glass plate and its preparation method and application. 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 with good anti-fouling and self-cleaning effects, and at the same time has excellent antibacterial properties, wear resistance and flame retardant properties.

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

[0006] A self-cleaning nano-coated 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 in parts by weight: 30 to 60 parts of an organic silicone resin, 10 to 20 parts of an epoxy resin, 5 to 10 parts of modified nano-titanium dioxide, 1 to 3 parts of a long-chain alkyl methyl silicone oil, 2.5 to 5 parts of a curing agent, and 40 to 65 parts of a diluent;

[0007] The modified nano titanium dioxide is prepared by grafting a modified silane coupling agent prepared by a hydrosilylation reaction between a modified phosphorus-containing antibacterial monomer and vinyl triethoxysilane onto the surface of the nano titanium dioxide; wherein the modified phosphorus-containing antibacterial monomer is prepared by a substitution reaction between a eugenol bromide obtained by a reaction between eugenol and N-bromosuccinimide and 2-amino-4-methylthiazole to obtain an antibacterial monomer, and then a substitution reaction between the antibacterial monomer and diphenylphosphinyl chloride to obtain a phosphorus-containing antibacterial monomer and 1,1,3,3-tetramethyldisiloxane to obtain the antibacterial monomer;

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

[0009] Preferably, the curing agent is a mixture of one or more of triethylenetetramine, curing agent 593, 4,4'-diaminodiphenylmethane, and meta-xylene diamine; and the diluent is a mixture of one or more of acetone, butanone, ethyl acetate, toluene, and xylene.

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

[0011] A. Put eugenol and carbon tetrachloride in a reactor, stir and mix at 55-70° C. in a nitrogen atmosphere, then add N-bromosuccinimide and dibenzoyl peroxide, stir and react for 5-6 hours, filter the precipitate after the reaction is completed, wash with carbon tetrachloride, mix the washing liquid and filtrate, add deionized water for washing, and extract, add anhydrous sodium sulfate to the organic phase obtained by extraction and shake to remove moisture, then remove the organic solvent from the filtrate obtained by filtration by vacuum rotary evaporation to prepare eugenol bromide;

[0012] B. Put eugenol bromide, 2-amino-4-methylthiazole and sodium carbonate in a reactor, add a mixed solution of N,N-dimethylformamide and tetrahydrofuran, stir and react at 60-70° C. for 1.5-3 hours, and after the reaction is completed, perform vacuum rotary evaporation, wash and dry to prepare an antibacterial monomer;

[0013] C. Take the antibacterial monomer and diphenylphosphine chloride in a reactor, add tetrahydrofuran solvent, stir and react for 4 to 7 hours, add triethylamine during the reaction, and after the reaction is completed, filter, rotary evaporate and dry to prepare a phosphorus-containing antibacterial monomer;

[0014] D. Put the phosphorus-containing antibacterial monomer and tetrahydrofuran in a reactor, stir and mix, then add the isopropanol solution of chloroplatinic acid, stir and heat to 55-65° C. in a nitrogen atmosphere, then add 1,1,3,3-tetramethyldisiloxane, stir and react for 5-8 hours, and after the reaction is completed, remove the unreacted product by rotary evaporation to prepare a modified phosphorus-containing antibacterial monomer;

[0015] E. Take the modified phosphorus-containing antibacterial monomer and vinyl triethoxysilane in a reactor, add toluene solvent, stir and heat to 75-85° C. in a nitrogen atmosphere, then add chloroplatinic acid catalyst, stir and react for 5-6 hours, and after the reaction is completed, remove the unreacted product by rotary evaporation 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 and reacting at 65-90° C. for 4-8 hours. After the reaction is completed, centrifugation, washing and drying are performed to prepare modified nano-titanium dioxide.

[0017] Preferably, the structural formula of the brominated eugenol is:

[0018]

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

[0020]

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

[0022] Preferably, in step C, the molar ratio of the antibacterial monomer to diphenylphosphine chloride is 1:1 to 1.2.

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

[0024] Preferably, in step E, the molar ratio of the modified phosphorus-containing antibacterial monomer to vinyltriethoxysilane is 1:1 to 1.2.

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

[0026] A method for preparing a self-cleaning nano-coated glass plate comprises the following steps:

[0027] S1. Weigh each component by weight, mix the epoxy resin and the diluent evenly, then add the curing agent and continue to stir and mix to prepare an epoxy resin dispersion;

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

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

[0030] Preferably, the self-cleaning nano-coated glass plate is applied to washing machine observation windows, electric meter cases, automobile rearview mirrors, distribution room observation windows, and carriage windows.

[0031] Beneficial effects of the present invention:

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

[0033] The present invention uses a chemical reaction to graft a modified silane coupling agent onto the surface of nano titanium dioxide, thereby introducing a natural antibacterial material eugenol, phosphorus and silicon elements with synergistic flame retardant effects, Si-O-Si bonds with good wear resistance, and a thiazole monomer with a hydrophobic structure and antibacterial activity onto the surface of the nano titanium dioxide through a strong chemical bond, thereby giving the nano coating excellent flame retardant properties, antibacterial properties, hydrophobic properties, and wear resistance. The present invention chemically grafts a modified silane coupling agent onto the surface of nano titanium dioxide with good ultraviolet radiation shielding ability, thereby achieving functional integration, making up for the defect of insufficient antibacterial activity of nano titanium dioxide when used alone under dark conditions, while improving the problems of easy migration and short antibacterial action time of the antibacterial component in the modified silane coupling agent structure when used alone, and further improving 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 invention uses octamethylcyclotetrasiloxane and dodecylmethyldimethoxysilane as raw materials, tetramethylammonium hydroxide as a catalyst, and hexamethyldisiloxane as a capping agent to prepare long-chain alkylmethyl silicone oil. The long-chain alkyl water-repellent group and the strong hydrophobicity of the silicone oil are used to form a super-hydrophobic surface of the coating, so that the nano coating produces an anti-fouling self-cleaning effect. DETAILED DESCRIPTION

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] The organic silicon resin in the examples and comparative examples of the present invention is produced by Shanghai Xiatu New Materials Co., Ltd.

[0037] Embodiment 1 A method for preparing modified nano titanium dioxide comprises the following steps:

[0038] A. Take 3.6 g of eugenol and 150 mL of carbon tetrachloride in a reactor, stir and mix at 60 ° C in a nitrogen atmosphere, then add 4.9 g of N-bromosuccinimide and 0.2 g of dibenzoyl peroxide, stir and react for 6 hours, filter the precipitate after the reaction is completed and wash with 15 mL of carbon tetrachloride, mix the washing liquid and the filtrate, add 20 mL of deionized water for washing, and extract, add anhydrous sodium sulfate to the organic phase obtained by extraction and shake to remove moisture, then remove the organic solvent from the filtrate obtained by filtration by vacuum rotary evaporation to prepare eugenol bromide;

[0039] B. Take 2.4g of eugenol bromide (Mr=243.1), 1.3g of 2-amino-4-methylthiazole, and 1.6g of sodium carbonate in a reactor, add 50mL of a mixed solution of N,N-dimethylformamide and tetrahydrofuran in a volume ratio of 1:1, place at 65°C and stir for 2h, and after the reaction is completed, evaporate under reduced pressure, wash, and dry to prepare an antibacterial monomer;

[0040] C. Take 3.4 g of antibacterial monomer (Mr=276.4) and 3.1 g of diphenylphosphinyl chloride in a reactor, add 50 mL of tetrahydrofuran solvent, stir and react for 6 h, add 1.2 g of triethylamine in batches during the reaction, and after the reaction is completed, filter, rotary evaporate and dry to prepare 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, stir and mix, add 1 mL of isopropanol solution of chloroplatinic acid (0.02 g / mL), stir and heat to 60° C. in a nitrogen atmosphere, then add 1.5 g of 1,1,3,3-tetramethyldisiloxane, stir and react for 8 h, and after the reaction is completed, remove the unreacted product by rotary evaporation to 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° C. in a nitrogen atmosphere, then add 0.2 g of chloroplatinic acid catalyst, stir and react for 6 h, and after the reaction is completed, remove the unreacted product by rotary evaporation to prepare a modified silane coupling agent;

[0043] F. Take 5g of nano-titanium dioxide and ultrasonically disperse it in a mixed solution of 90mL of anhydrous ethanol and 10mL of deionized water, then add 2.6g of modified silane coupling agent, place it at 85°C and stir to react for 6h. After the reaction is completed, centrifuge, wash and dry to prepare modified nano-titanium dioxide.

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

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

[0046] Example 3 A self-cleaning nano coating includes the following components in weight: 40 parts of silicone resin, 12 parts of epoxy resin E44, 5 parts of modified nano titanium dioxide prepared in Example 1, 1.2 parts of long-chain alkyl methyl silicone oil prepared in Example 2, 32.5 parts of curing agent, and 45 parts of diluent acetone.

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

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

[0049] S2, stirring and mixing 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. The self-cleaning nano-coating is uniformly coated on the surface of the cleaned and dried glass plate, and then cured at 100° C. for 1 hour to prepare a self-cleaning nano-coated glass plate.

[0051] Example 4 A self-cleaning nano coating comprises the following components in parts by weight: 51 parts of silicone resin, 16 parts of epoxy resin E44, 7 parts of modified nano titanium dioxide prepared in Example 1, 2 parts of long-chain alkyl methyl silicone oil prepared in Example 2, 5933.5 parts of curing agent, and 55 parts of diluent acetone.

[0052] The preparation method of a self-cleaning nano-coated glass plate is the same as that of Example 3.

[0053] Example 5 A self-cleaning nano coating includes the following components in parts by weight: 58 parts of silicone resin, 20 parts of epoxy resin E44, 9 parts of modified nano titanium dioxide prepared in Example 1, 2.7 parts of long-chain alkyl methyl silicone oil prepared in Example 2, 5935 parts of curing agent, and 63 parts of diluent acetone.

[0054] The preparation method of a self-cleaning nano-coated glass plate is the same as that of Example 3.

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

[0056] A. Take 3.6 g of eugenol and 150 mL of carbon tetrachloride in a reactor, stir and mix at 60 ° C in a nitrogen atmosphere, then add 4.9 g of N-bromosuccinimide and 0.2 g of dibenzoyl peroxide, stir and react for 6 hours, filter the precipitate after the reaction is completed and wash with 15 mL of carbon tetrachloride, mix the washing liquid and the filtrate, add 20 mL of deionized water for washing, and extract, add anhydrous sodium sulfate to the organic phase obtained by extraction and shake to remove moisture, then remove the organic solvent from the filtrate obtained by filtration by vacuum rotary evaporation to prepare eugenol bromide;

[0057] B. Take 2.4g of eugenol bromide (Mr=243.1), 1.3g of 2-amino-4-methylthiazole, and 1.6g of sodium carbonate in a reactor, add 50mL of a mixed solution of N,N-dimethylformamide and tetrahydrofuran in a volume ratio of 1:1, place at 65°C and stir for 2h, and after the reaction is completed, evaporate under reduced pressure, wash, and dry to prepare an antibacterial monomer;

[0058] C. Take 3.2 g of antibacterial monomer (Mr=276.4) and 100 mL of tetrahydrofuran in a reactor, stir and mix, then add 1 mL of isopropanol solution of chloroplatinic acid (0.02 g / mL), stir and heat to 60°C in a nitrogen atmosphere, then add 1.5 g of 1,1,3,3-tetramethyldisiloxane, stir and react for 8 hours, and after the reaction is completed, remove the unreacted product by rotary evaporation to prepare a modified antibacterial monomer;

[0059] D. Take 4.1 g of modified antibacterial monomer (Mr=410.7) and 2.1 g of vinyltriethoxysilane in a reactor, add 50 mL of toluene solvent, stir and heat to 80° C. in a nitrogen atmosphere, then add 0.2 g of chloroplatinic acid catalyst, stir and react for 6 h, and after the reaction is completed, remove the unreacted product by rotary evaporation to prepare a modified silane coupling agent;

[0060] E. Take 5g of nano-titanium dioxide and ultrasonically disperse it in a mixed solution of 90mL of anhydrous ethanol and 10mL of deionized water, then add 2.6g of modified silane coupling agent, place it at 85°C and stir to react for 6h. After the reaction is completed, centrifuge, wash and dry to prepare modified nano-titanium dioxide.

[0061] Comparative Example 2 A self-cleaning nano coating includes the following components in weight: 58 parts of silicone resin, 4420 parts of epoxy resin E4, 9 parts of modified nano titanium dioxide prepared in Comparative Example 1, 2.7 parts of long-chain alkyl methyl silicone oil prepared in Example 2, 5935 parts of curing agent, and 63 parts of diluent acetone.

[0062] The preparation method of a self-cleaning nano-coated glass plate is the same as that of Example 3.

[0063] Comparative Example 3 A self-cleaning nano coating includes the following components in parts by weight: 58 parts of silicone resin, 20 parts of epoxy resin E44, 9 parts of nano titanium dioxide, 2.7 parts of long-chain alkyl methyl silicone oil prepared in Example 2, 5935 parts of curing agent, and 63 parts of diluent acetone.

[0064] The preparation method of a self-cleaning nano-coated glass plate is the same as that of Example 3.

[0065] Comparative Example 4 A self-cleaning nano coating includes the following components in parts by weight: 58 parts of silicone resin, 4420 parts of epoxy resin E4, 9 parts of modified nano titanium dioxide prepared in Example 1, 2.7 parts of dimethyl silicone oil, 5935 parts of curing agent, and 63 parts of diluent acetone.

[0066] The preparation method of a self-cleaning nano-coated glass plate is the same as that of Example 3.

[0067] Performance Testing

[0068] The performance of the self-cleaning nano coatings prepared in Examples 3-5 and Comparative Examples 2-4 was tested: a dynamic contact angle tester was used to test the contact angle and rolling angle, 5 μL of water droplets were used for each measurement, and the average data was determined by at least three measurements at different positions in the same sample; the antibacterial rate test was performed with reference to GB / T 21866-2008, and the test bacteria was Staphylococcus aureus; 45-mesh sand was used as a test tool, and the self-cleaning nano-coated glass plates prepared in Examples 3-5 and Comparative Examples 2-4 were vertically inserted into the 45-mesh sand at a rate of 30 times / min and repeated in an "insert-pull" action. After 150 wear tests, the glass plates were taken out and the water static contact angle of the self-cleaning nano coating after mechanical wear was tested; the flame retardant performance of the nano coating was tested by the limiting oxygen index; the self-cleaning performance was tested by placing the self-cleaning nano-coated glass plate on 45-mesh sand and dripping water with a syringe, and the data results were shown in Table 1.

[0069] Table 1 Test results of sample performance

[0070]

[0071] It can be seen from the data in Table 1 that the nanocoatings prepared in Examples 3-5 of the present invention have a high antibacterial rate, good wear resistance, and good flame retardant effect. Their water contact angles are all greater than 150°, and their rolling angles are all less than 10°. They have excellent superhydrophobic properties and good antifouling and self-cleaning effects. Among them, the modified nano titanium dioxide component added in Comparative Example 2 did not introduce phosphorus element, and its flame retardant performance was measured to be worse than that of Examples 3-5. In Comparative Example 3, the nano titanium dioxide was not modified, and its measured water contact angle was less than 150°, the rolling angle was greater than 10°, and the self-cleaning performance was worse than that of Examples 3-5. The reason is that the surface of the nano titanium dioxide is rich in hydrophilic hydroxyl groups, and no modified silane coupling agent is introduced on the surface of the nano titanium dioxide. At the same time, its antibacterial rate, static water contact angle after mechanical wear, and limiting oxygen index were significantly lower than those of Examples 3-5, indicating that the grafting of modified silane coupling agents can improve the wear resistance, antibacterial and flame retardancy of the nano coating to a certain extent. In Comparative Example 4, the long-chain alkyl methyl silicone oil was replaced with dimethyl silicone oil in equal amounts, and its measured water contact angle was less than 150°, the rolling angle was greater than 10°, and the self-cleaning performance was worse than that of Examples 3-5, indicating that the introduction of long-chain alkyl methyl silicone oil can prompt the nano coating to form a super hydrophobic surface and improve the anti-fouling self-cleaning effect.

[0072] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, 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 above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A self-cleaning nano-coated glass plate, characterized in that: The invention comprises 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 in parts by weight: 30 to 60 parts of an organic silicone resin, 10 to 20 parts of an epoxy resin, 5 to 10 parts of modified nano titanium dioxide, 1 to 3 parts of a long-chain alkyl methyl silicone oil, 2.5 to 5 parts of a curing agent, and 40 to 65 parts of a diluent; The modified nano titanium dioxide is prepared by grafting a modified silane coupling agent prepared by a hydrosilylation reaction between a modified phosphorus-containing antibacterial monomer and vinyl triethoxysilane onto the surface of the nano titanium dioxide; wherein the modified phosphorus-containing antibacterial monomer is prepared by a substitution reaction between a eugenol bromide obtained by a reaction between eugenol and N-bromosuccinimide and 2-amino-4-methylthiazole to obtain an antibacterial monomer, and then a substitution reaction between the antibacterial monomer and diphenylphosphinyl chloride to obtain a phosphorus-containing antibacterial monomer and 1,1,3,3-tetramethyldisiloxane to obtain the antibacterial monomer; The long-chain alkyl methyl silicone oil is prepared by 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 a mixture of one or more of triethylenetetramine, curing agent 593, 4,4'-diaminodiphenylmethane, and meta-xylene diamine; the diluent is a mixture of 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 modified nano titanium dioxide comprises the following steps: A. Put eugenol and carbon tetrachloride in a reactor, stir and mix at 55-70° C. in a nitrogen atmosphere, then add N-bromosuccinimide and dibenzoyl peroxide, stir and react for 5-6 hours, filter the precipitate after the reaction is completed, wash with carbon tetrachloride, mix the washing liquid and filtrate, add deionized water for washing, and extract, add anhydrous sodium sulfate to the organic phase obtained by extraction and shake to remove moisture, then remove the organic solvent from the filtrate obtained by filtration by vacuum rotary evaporation to prepare eugenol bromide; B. Put eugenol bromide, 2-amino-4-methylthiazole and sodium carbonate in a reactor, add a mixed solution of N,N-dimethylformamide and tetrahydrofuran, stir and react at 60-70° C. for 1.5-3 hours, and after the reaction is completed, perform vacuum rotary evaporation, wash and dry to prepare an antibacterial monomer; C. Take the antibacterial monomer and diphenylphosphine chloride in a reactor, add tetrahydrofuran solvent, stir and react for 4 to 7 hours, add triethylamine during the reaction, and after the reaction is completed, filter, rotary evaporate and dry to prepare a phosphorus-containing antibacterial monomer; D. Put the phosphorus-containing antibacterial monomer and tetrahydrofuran in a reactor, stir and mix, then add the isopropanol solution of chloroplatinic acid, stir and heat to 55-65° C. in a nitrogen atmosphere, then add 1,1,3,3-tetramethyldisiloxane, stir and react for 5-8 hours, and after the reaction is completed, remove the unreacted product by rotary evaporation to prepare a modified phosphorus-containing antibacterial monomer; E. Take the modified phosphorus-containing antibacterial monomer and vinyl triethoxysilane in a reactor, add toluene solvent, stir and heat to 75-85° C. in a nitrogen atmosphere, then add chloroplatinic acid catalyst, stir and react for 5-6 hours, and after the reaction is completed, remove the unreacted product by rotary evaporation to prepare a modified silane coupling agent; 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 and reacting at 65-90° C. for 4-8 hours. After the reaction is completed, centrifugation, washing and drying are performed to prepare modified nano-titanium dioxide.

4. The self-cleaning nano-coated glass plate according to claim 3, characterized in that: The molar ratio of eugenol to N-bromosuccinimide in step A is 1:1-1.3; the molar ratio of eugenol bromide to 2-amino-4-methylthiazole in step B is 1:1-1.

2.

5. The self-cleaning nano-coated glass plate according to claim 3, characterized in that: In step C, the molar ratio of the antibacterial monomer to diphenylphosphine chloride is 1:1 to 1.

2.

6. The self-cleaning nano-coated glass plate according to claim 3, characterized in that: In the step D, the molar ratio of the phosphorus-containing antibacterial monomer to 1,1,3,3-tetramethyldisiloxane is 1-1.1:

1.

7. The self-cleaning nano-coated glass plate according to claim 3, characterized in that: In the step E, the molar ratio of the modified phosphorus-containing antibacterial monomer to vinyl triethoxysilane is 1:1 to 1.

2.

8. The self-cleaning nano-coated glass plate according to claim 1, characterized in that: The preparation method of the long-chain alkyl methyl silicone oil comprises the following steps: taking octamethylcyclotetrasiloxane and dodecylmethyldimethoxysilane in a reactor, stirring and heating to 75-85° C., then adding tetramethylammonium hydroxide, reacting for 0.5-1h, adding hexamethyldisiloxane, continuing to heat to 90-120° C. and reacting for 2-4h, performing reduced pressure distillation after the reaction is completed, and then heating to 135-140° C. to remove the catalyst, so as to prepare the long-chain alkyl methyl silicone oil.

9. A method for preparing a self-cleaning nano-coated glass plate according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Weigh each component by weight, mix the epoxy resin and the diluent evenly, then add the curing agent and continue to stir and mix to prepare an epoxy resin dispersion; S2, stirring and mixing the silicone resin, long-chain alkyl methyl silicone oil, modified nano titanium dioxide and epoxy resin dispersion to prepare a self-cleaning nano coating; S3. The self-cleaning nano-coating is uniformly coated on the surface of the cleaned and dried glass plate, and then cured at 80 to 100° C. for 1 to 3 hours to prepare a self-cleaning nano-coated glass plate.

10. The use of the self-cleaning nano-coated glass plate according to claim 1, characterized in that: The self-cleaning nano-coated glass plate is applied to washing machine observation windows, electric meter cases, automobile rearview mirrors, distribution room observation windows, and carriage windows.

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