Organic-inorganic hybrid multifunctional anti-fog coating and its preparation method and coating

Abstract

The present invention relates to the technical field of material surface modification, and provides an organic-inorganic hybrid multifunctional anti-fog coating, a preparation method thereof, and a coating. The present invention utilizes an amphiphilic polymer, vinyl silica sol, water, and a photoinitiator to prepare a coating, and then obtains an organic-inorganic hybrid multifunctional anti-fog coating after film coating and UV curing. The present invention uses organic components to change the wettability of the surface, providing antibacterial, antifouling, and antifogging functions, and uses inorganic components to improve the mechanical properties and wear resistance of the coating. In addition, the construction method of the anti-fog coating of the present invention is simple and convenient, overcoming the problem of poor stability and wear resistance caused by the solubility of traditional hydrophilic polymers in water; and the coating can be modified on the surface of most materials to achieve surface wear resistance, antibacterial, antifog, antifouling and other functions.

Description

Technical Field

[0001] The present invention relates to the technical field of surface modification, in particular to an organic-inorganic hybrid multifunctional anti-fog coating and a preparation method and coating thereof. Background Art

[0002] Transparent substrates such as glass and resin are widely used, but during use, their surfaces often condense and fog due to environmental changes, resulting in reduced visibility and affecting normal use. For example, fogging of car windshields affects driving vision, and fogging of agricultural greenhouse films affects plant photosynthesis. There are two common ideas to solve the fogging problem. One is to heat the substrate to make the surface temperature of the substrate higher than the dew point of fog condensation to prevent fogging. However, this method is costly and has limited applicable environments, making it difficult to promote in practical applications. The other is to change the wettability of the substrate. The excellent performance of hydrophilic coatings in anti-fog and self-cleaning has attracted widespread attention for its development and application. The hydrophilic effect can prevent water vapor from forming water droplet nuclei on the surface of the substrate, which can effectively reduce the scattering of incident light in all directions, achieving a good anti-fog effect. In addition, in fields such as medical devices (such as endoscopes) and food packaging, antibacterial and antifouling capabilities are also essential. Therefore, the preparation of multifunctional coatings with anti-fog, antibacterial and antifouling functions is of great significance.

[0003] Hydrophilic polymers offer advantages such as good flexibility and high transparency, but their application is limited by the poor swelling stability of the coatings caused by their hydrophilicity. Inorganic coatings are structurally stable but prone to cracking, and these shortcomings reduce their performance. Currently, there are few reports in the field on multifunctional anti-fog coatings that combine the advantages of both organic and inorganic coatings. Summary of the Invention

[0004] In light of this, the present invention provides an organic-inorganic hybrid multifunctional anti-fog coating, its preparation method, and coating. By utilizing an organic-inorganic hybrid interpenetrating network structure, the present invention maximizes the advantages of both organic and inorganic coating materials. The resulting organic-inorganic hybrid multifunctional anti-fog coating combines the advantages of both organic and inorganic coatings, exhibiting excellent antibacterial, antifouling, anti-fog, mechanical, and wear-resistant properties.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] A method for preparing an organic-inorganic hybrid multifunctional anti-fog coating comprises the following steps:

[0007] Mixing tetraethyl orthosilicate, a vinyl silane coupling agent, alcohol, water and acid, and sequentially performing hydrolysis and static aging to obtain vinyl silica sol;

[0008] Mixing a fluorine-containing acrylate monomer, an amino-containing acrylate monomer, a benzene solvent, and an initiator to carry out a polymerization reaction to obtain a copolymer; mixing the copolymer, a brominated alkane, and acetonitrile to carry out a protonation reaction to obtain an amphiphilic polymer;

[0009] The vinyl silica sol, amphiphilic polymer, water and photoinitiator are mixed to obtain an organic-inorganic hybrid multifunctional anti-fog coating.

[0010] Preferably, the acid comprises one or more of hydrochloric acid, nitric acid and acetic acid; the alcohol comprises ethanol and / or isopropyl alcohol; the volume ratio of the alcohol, tetraethyl orthosilicate, water and acid is 12-20:1-5:0.5-1.5:0.2;

[0011] The vinyl silane coupling agent includes one or more of methyltrivinylsilane, dimethyldivinylsilane, γ-methacryloxypropyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane; the mass ratio of the ethyl orthosilicate to the vinyl silane coupling agent is 20 to 150:1.

[0012] Preferably, the static aging time is 1 to 7 days.

[0013] Preferably, the fluorine-containing acrylate monomer includes one or more of perfluorooctylethyl methacrylate, hexafluorobutyl methacrylate and trifluoromethyl acrylate; the amino-containing acrylate monomer includes one or more of dimethylaminoethyl methacrylate, 2-aminoethyl methacrylate and 2-(diethylamino)ethyl methacrylate; the mass ratio of the fluorine-containing acrylate monomer to the amino-containing acrylate monomer is 1:1 to 5;

[0014] The benzene solvent is o-xylene; the mass ratio of the total mass of the fluorine-containing acrylate monomer and the amino-containing acrylate monomer to o-xylene is 0.5:1-2;

[0015] The initiator is an azo initiator; the mass ratio of the total mass of the fluorine-containing acrylate monomer and the amino-containing acrylate monomer to the initiator is 100 to 200:1;

[0016] The polymerization reaction temperature is 60-100° C., and the reaction time is 8-24 hours.

[0017] Preferably, the brominated alkane includes one or more of isopropyl bromide, dodecane bromide and n-butane bromide; the mass ratio of the copolymer to the brominated alkane is 0.1:1 to 1:1;

[0018] The temperature of the protonation reaction is 60-100° C., and the reaction time is 8-24 hours.

[0019] Preferably, the mass ratio of the vinyl silica sol, the amphiphilic polymer and water is 1-10:1-5:1-5; the mass ratio of the total mass of the vinyl silica sol and the amphiphilic polymer to the photoinitiator is 50-200:1.

[0020] The present invention also provides an organic-inorganic hybrid multifunctional anti-fog coating prepared by the preparation method described in the above scheme, the components of which include vinyl silica sol, amphiphilic polymer, water and photoinitiator.

[0021] The present invention also provides an organic-inorganic hybrid multifunctional anti-fog coating, which is obtained by coating the organic-inorganic hybrid multifunctional anti-fog coating described in the above scheme on the surface of a substrate and then UV curing it.

[0022] Preferably, the coating method is a dip-pull method; the pulling speed of the dip-pull method is 100 to 200 mm / min.

[0023] Preferably, the UV curing light wavelength is 320-365 nm, and the light intensity is 180-210 mW / cm 2 , the illumination time is 0.5 to 3 hours, and the temperature is room temperature.

[0024] The present invention provides a method for preparing an organic-inorganic hybrid multifunctional anti-fog coating, comprising the following steps: mixing tetraethyl orthosilicate, a vinyl silane coupling agent, an alcohol, water, and an acid, and sequentially hydrolyzing and aging the mixture to obtain a vinyl silica sol; mixing an acrylate monomer, a benzene solvent, and an initiator to undergo a polymerization reaction to obtain a copolymer; mixing the copolymer, a brominated alkane, and acetonitrile to undergo a protonation reaction to obtain an amphiphilic polymer; and mixing the vinyl silica sol, the amphiphilic polymer, water, and a photoinitiator to obtain an organic-inorganic hybrid multifunctional anti-fog coating. The organic-inorganic hybrid multifunctional anti-fog coating provided by the present invention includes an organic component (amphiphilic polymer) and an inorganic component (vinyl silica sol). The coating is endowed with antibacterial, antifogging, and antifouling functions by utilizing the hydrophilic, antibacterial, and antifogging properties of the quaternary ammonium cations in the amphiphilic polymer and the low surface properties of the fluorine segments; and the mechanical properties and wear resistance of the coating are improved by utilizing the high bonding strength and high hardness of the vinyl silica sol.

[0025] The present invention also provides an organic-inorganic hybrid multifunctional anti-fog coating. The organic-inorganic hybrid multifunctional anti-fog coating is applied to a substrate surface and then UV-cured to obtain the organic-inorganic hybrid multifunctional anti-fog coating. The organic-inorganic hybrid multifunctional anti-fog coating provided by the present invention exhibits wear resistance, antibacterial properties, anti-fog properties, and anti-fouling properties. It overcomes the problem of poor coating stability and wear resistance caused by the water solubility of conventional hydrophilic polymers. Furthermore, the coating construction method is simple and convenient, making it applicable to most materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The wettability contact angle of the coating prepared in Example 1 and the blank glass changes over time;

[0027] Figure 2 The light transmittance test results of the glass before and after the coating was prepared in Example 1;

[0028] Figure 3 Comparison of the wear resistance of the coatings prepared in Example 1 and Comparative Example 1 (left) and the anti-fog performance test results of the coating in Example 1 after 10,000 friction cycles;

[0029] Figure 4 The antibacterial test results of the coating prepared in Example 1 and blank glass;

[0030] Figure 5 The stain resistance test results of the coating prepared in Example 1 are shown. DETAILED DESCRIPTION

[0031] The present invention provides a method for preparing an organic-inorganic hybrid multifunctional anti-fog coating, comprising the following steps:

[0032] Mixing tetraethyl orthosilicate, a vinyl silane coupling agent, alcohol, water and acid, and sequentially performing hydrolysis and static aging to obtain vinyl silica sol;

[0033] Mixing a fluorine-containing acrylate monomer, an amino-containing acrylate monomer, a benzene solvent, and an initiator to carry out a polymerization reaction to obtain a copolymer; mixing the copolymer, a brominated alkane, and acetonitrile to carry out a protonation reaction to obtain an amphiphilic polymer;

[0034] The vinyl silica sol, amphiphilic polymer, water and photoinitiator are mixed to obtain an organic-inorganic hybrid multifunctional anti-fog coating.

[0035] In the present invention, unless otherwise specified, all raw materials used are commercially available products well known in the art.

[0036] The invention mixes tetraethyl orthosilicate, a vinyl silane coupling agent, alcohol, water and acid, and sequentially performs hydrolysis and static aging to obtain vinyl silica sol. In the present invention, the acid preferably includes one or more of hydrochloric acid, nitric acid and acetic acid, more preferably nitric acid; the hydrochloric acid is preferably concentrated hydrochloric acid (36wt%); the nitric acid is preferably concentrated nitric acid (68wt%); the acetic acid is preferably glacial acetic acid; the alcohol preferably includes ethanol and / or isopropanol, more preferably ethanol; the volume ratio of the alcohol, tetraethyl orthosilicate, water and acid is preferably 12-20:1-5:0.5-1.5:0.2, more preferably 12-15:2-5:1:0.2, and further preferably 12-13:2-3:1:0.2; the vinyl silane coupling agent preferably includes one or more of methyltrivinylsilane, dimethyldivinylsilane, γ-methacryloxypropyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane; the mass ratio of tetraethyl orthosilicate to vinyl silane coupling agent is preferably 20-150:1, more preferably 40-100:1, and further preferably 40-80:1.

[0037] In the present invention, the hydrolysis time is preferably 1 to 6 hours, and the temperature is preferably room temperature; the static aging time is preferably 1 to 7 days, more preferably 3 to 5 days, and the static aging temperature is preferably room temperature. During the hydrolysis process, ethyl orthosilicate is hydrolyzed under the action of acid to form silica sol, and the silica sol and the vinyl silane coupling agent undergo dehydration condensation to obtain vinyl silica sol.

[0038] The present invention mixes a fluorine-containing acrylate monomer, an amino-containing acrylate monomer, a benzene solvent and an initiator to carry out a polymerization reaction to obtain a copolymer; the copolymer, a brominated alkane and acetonitrile are mixed to carry out a protonation reaction to obtain an amphiphilic polymer. In the present invention, the fluorine-containing acrylate monomer preferably includes one or more of perfluorooctylethyl methacrylate, hexafluorobutyl methacrylate and trifluoromethylacrylate; the amino-containing acrylate monomer is preferably one or more of dimethylaminoethyl methacrylate, 2-aminoethyl methacrylate and 2-(diethylamino)ethyl methacrylate; the mass ratio of the fluorine-containing acrylate monomer to the amino-containing acrylate monomer is preferably 1:1 to 5, more preferably 1:2 to 4; the benzene solvent is preferably o-xylene; the fluorine-containing acrylate monomer and the amino-containing acrylate monomer are ... The mass ratio of the total mass of the ester monomer to o-xylene is preferably 0.5:1-2, more preferably 1:1-2:1; the initiator is preferably an azo initiator, more preferably azobisisobutyronitrile; the mass ratio of the total mass of the fluorine-containing acrylate monomer and the amino-containing acrylate monomer to the initiator is preferably 100-200:1, more preferably 100-160:1; the temperature of the polymerization reaction is preferably 60-100°C, more preferably 80-100°C, the reaction time is preferably 8-24h, more preferably 8-12h, and the polymerization reaction is specifically a free radical polymerization reaction.

[0039] In a specific embodiment of the present invention, the fluorine-containing acrylate monomer and the amino-containing acrylate monomer are preferably first added to a reaction apparatus containing o-xylene, followed by the addition of an initiator, and then the temperature is raised to allow the reaction to proceed. After the polymerization reaction is completed, the present invention preferably cools the resulting reaction solution to room temperature, separates the precipitate, and then washes and dries it to obtain the copolymer; the washing detergent is preferably n-hexane.

[0040] In the present invention, the brominated alkane preferably includes one or more of isopropyl bromide, dodecane bromide, and n-butane bromide; the mass ratio of the copolymer to the brominated alkane is preferably 0.1:1 to 1:1, more preferably 0.5:1 to 1:1; the temperature of the protonation reaction is preferably 60 to 100°C, more preferably 60 to 80°C. The reaction time is 8 to 24 hours, more preferably 10 to 20 hours. During the reaction, the nitrogen atom in the copolymer carries a lone pair of electrons and attacks the electrophilic halide to undergo a protonation reaction. In a specific embodiment of the present invention, the copolymer and the brominated alkane are preferably added to acetonitrile and heated to carry out the protonation reaction. After the reaction, the precipitate is preferably separated, washed with acetonitrile, and then dried to obtain the amphiphilic polymer.

[0041] After obtaining the vinyl silica sol and the amphiphilic polymer, the present invention mixes the vinyl silica sol, the amphiphilic polymer, water, and a photoinitiator to produce an organic-inorganic hybrid multifunctional anti-fog coating. In the present invention, the mass ratio of the vinyl silica sol, the amphiphilic polymer, and water is preferably 1-10:1-5:1-5, more preferably 5-10:1-3:1-3; the mass ratio of the total mass of the vinyl silica sol and the amphiphilic polymer to the photoinitiator is preferably 50-200:1, more preferably 50-100:1; and the photoinitiator preferably includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone (UV-184), 2-hydroxy-methylphenylpropane-1-one, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and benzophenone. In a specific embodiment of the present invention, the vinyl silica sol, the amphiphilic polymer, and water are preferably mixed first, followed by the addition of the photoinitiator.

[0042] The present invention also provides an organic-inorganic hybrid multifunctional anti-fog coating prepared by the preparation method, the components of which include vinyl silica sol, amphiphilic polymer, water and a photoinitiator.

[0043] The present invention also provides an organic-inorganic hybrid multifunctional anti-fog coating, which is obtained by coating the organic-inorganic hybrid multifunctional anti-fog coating described in the above scheme on the surface of a substrate and then UV curing it. In the present invention, the coating method is preferably a dip-pull method; the pulling speed of the dip-pull method is preferably 100 to 200 mm / min, more preferably 20 to 100 mm / min; the present invention can control the thickness of the coating by the pulling speed, and the thickness of the coating is preferably 80 to 150 nm, more preferably 80 nm, 100 nm, or 150 nm. In addition, the present invention has no special requirements for the material of the substrate. In the embodiments of the present invention, glass is selected as the substrate.

[0044] In the present invention, the UV curing light wavelength is preferably 320 to 365 nm, more preferably 365 nm, and the light intensity is preferably 180 to 210 mW / cm 2 The light exposure time is preferably 0.5 to 3 hours, more preferably 0.5 to 2 hours, and even more preferably 1 to 2 hours; the UV curing temperature is preferably room temperature. After UV curing is completed, the coating is preferably rinsed with water and then dried with nitrogen.

[0045] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0046] In the following embodiments and application examples, FOMA is perfluorooctylethyl methacrylate, DMAEMA is dimethylaminoethyl methacrylate, AIBN is azobisisobutyronitrile, DDS is dimethyldivinylsilane, KH570 is γ-methacryloyloxypropyltrimethoxysilane, A-172 is vinyltris(β-methoxyethoxy)silane, Bp is benzophenone, UV-184 is 1-hydroxycyclohexylphenyl ketone, and UV-2959 is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone. In the following embodiments and application examples, the nitric acid used is 68 wt% concentrated nitric acid.

[0047] Example 1

[0048] Prepare vinyl silica sol containing vinyl silane coupling agent: measure 12 mL of ethanol, 2 mL of ethyl orthosilicate, 1 mL of water and 0.2 mL of nitric acid respectively, add them into a flask and stir evenly, then add 0.05 mL of KH570, continue stirring for 1 hour, and let it stand for 3 days to obtain vinyl silica sol.

[0049] 2g of FOMA and 7g of DMAEMA were added to a round-bottom flask containing 10g of o-xylene. 0.1g of AIBN was then added as a thermal initiator. The polymerization reaction was carried out in an 80°C oil bath for 8 hours. The resulting copolymer solution was precipitated and washed with hexane, then dried in a vacuum oven to obtain the copolymer. 2g of the copolymer, 2g of n-butyl bromide, and 20ml of acetonitrile were added to a round-bottom flask and protonated at 80°C for 10 hours. The product was washed with acetonitrile, purified, and dried to obtain an amphiphilic polymer.

[0050] Vinyl silica sol, amphiphilic polymer and water were mixed evenly in the ratio of 8g:2g:3g, UV-184 (the mass was one percent of the total mass of vinyl silica sol and amphiphilic polymer) was added, and the cleaned glass sheet was immersed in the above solution. Then, it was pulled out with a pulling machine at a speed of 20mm / min, reacted at room temperature under 365nm UV light for 1h, rinsed with water and blown dry with nitrogen to obtain a glass sheet modified with an organic-inorganic hybrid multifunctional anti-fog coating.

[0051] Comparative Example 1

[0052] Prepare a single amphiphilic polymer coating as follows:

[0053] Ethanol, amphiphilic polymer and water were mixed in the ratio of 8g:2g:3g, 0.002g / mL UV-184 was added, and a cleaned glass slide was immersed in the above solution. Then, it was pulled out with a pulling machine at a speed of 20mm / min. The reaction was carried out at room temperature under 365nm UV light for 1h. The glass slide was rinsed with water and dried with nitrogen to obtain a glass slide modified with a single amphiphilic polymer coating.

[0054] Performance characterization:

[0055] 1. The wettability contact angle of the coating prepared in Example 1 and the blank glass changes with time as shown in the following table: Figure 1 As shown. Figure 1 It can be seen that the contact angle of the coating gradually changes from hydrophobic (~120°) to hydrophilic (~16°), while the wettability of the glass surface remains almost unchanged.

[0056] 2. Figure 2 The light transmittance test results of the glass before and after the coating is prepared in Example 1. Figure 2 It can be seen that after the coating of Example 1 is applied to the glass surface, the light transmittance of the glass surface is almost unchanged, and the light transmittance is consistent with that of the bare glass substrate.

[0057] 3. The coatings prepared in Example 1 and Comparative Example 1 were respectively placed under a load of 2N and a frequency of 1Hz and rubbed against a silicone rubber ball in water to test the friction coefficient. After the coatings were rubbed 10,000 times, they were placed on a 60°C water bath and fumigated for 12 hours. The samples were then removed and placed on top of text to visually observe the transparency of the samples to test their anti-fog effect. The test results are shown in the figure below. Figure 3 As shown, Figure 3 The left side shows the friction coefficient test results, and the right side shows the anti-fog performance test results of the coating of Example 1 after rubbing 10,000 times. Figure 3 The results in Example 1 (corresponding to Figure 3 The friction coefficient of the coating surface (organic-inorganic hybrid structure) remained around 0.01 after 10,000 cycles, demonstrating excellent water-lubricated wear resistance. In contrast, the friction coefficient of the coating surface of Comparative Example 1 rapidly increased to 0.4 after 1,000 cycles of friction and wear, indicating that the amphiphilic surface without the silica sol structure has poor wear resistance. Furthermore, the coating of Example 1 maintained anti-fog properties after 10,000 friction cycles, with continued anti-fog performance for over 12 hours.

[0058] 4. The polymer coating prepared in Example 1 and the blank glass were subjected to antibacterial sensitivity tests. Escherichia coli and Staphylococcus aureus were selected to test the antibacterial activity of the polymer coating. 100 μL of 10 8 The bacterial suspension of cfu / mL was evenly covered on the surface of the culture medium. The polymer-coated glass and the blank glass were placed in the culture medium respectively, with the coated surface in contact with the bacterial surface. Three pieces of glass were placed in each culture medium. After incubation at 37℃ for 24h, the antibacterial effect was as follows Figure 4 As shown. Figure 4 It can be seen that the blank glass has no obvious inhibition ring, indicating a lack of antibacterial effect. The polymer coating has obvious inhibition rings against Escherichia coli and Staphylococcus aureus, indicating significant antibacterial effect.

[0059] 5. The coating prepared in Example 1 was subjected to a stain resistance test. The specific steps were as follows: three oil droplets (xylene, n-hexane, butyl bromide) were dropped onto the inclined glass coating surface (inclination angle 5°). Figure 5 As shown in the figure, the three oil droplets all slid off the coating surface quickly without leaving any adhesion marks on the surface, indicating that the coating has excellent anti-fouling properties.

[0060] Example 2

[0061] Prepare vinyl silica sol containing vinyl silane coupling agent: measure 12 mL of ethanol, 3 mL of ethyl orthosilicate, 1 mL of water and 0.2 mL of nitric acid respectively, add them into a flask and stir evenly, then add 0.03 mL of KH570 and 0.03 mL of DDS, continue stirring for 1 hour, and let it stand for 5 days to obtain vinyl silica sol.

[0062] 2g of FOMA and 7g of DMAEMA were added to a round-bottom flask containing 10g of o-xylene to obtain a 49wt% solution. 0.1g of AIBN was then added as a thermal initiator. The polymerization reaction was carried out in an 80°C oil bath. The resulting copolymer was precipitated and washed with hexane, then dried in a vacuum oven to obtain the copolymer. 2g of the copolymer, 2g of hexadecane bromide, and 20mL of acetonitrile were added to the round-bottom flask and heated to react. The product was washed with acetonitrile for purification and dried to obtain the amphiphilic polymer.

[0063] Vinyl silica sol, amphiphilic polymer and water were mixed evenly in the ratio of 8g:3g:3g, and UV-184 (the mass was one percent of the total mass of vinyl silica sol and amphiphilic polymer) was added. The cleaned glass sheet was immersed in the above solution, and then pulled out with a pulling machine at a speed of 50mm / min. The glass sheet was reacted at room temperature for 2h under 365nm UV light, rinsed with water and then dried with nitrogen to obtain a glass sheet modified with an organic-inorganic hybrid multifunctional anti-fog coating.

[0064] After testing, the wettability, lubricity, wear resistance, antibacterial properties and antifog properties of the organic-inorganic hybrid multifunctional antifog coating prepared in this example are similar to those in Example 1.

[0065] Example 3

[0066] Prepare a vinyl silica sol mixed coating containing a vinyl silane coupling agent: measure 12 mL of ethanol, 2 mL of ethyl orthosilicate, 1 mL of water, and 0.2 mL of nitric acid, add them to a flask and stir evenly, then add 0.05 mL of A-172, continue stirring for 1 hour, and let it stand for 3 days to obtain a vinyl silica sol mixed coating.

[0067] 2g of hexafluorobutyl acrylate and 7g of DMAEMA were added to a round-bottom flask containing 10g of o-xylene to obtain a 47wt% solution. 0.1g of AIBN was then added as a thermal initiator. The polymerization reaction was carried out in an 80°C oil bath. The resulting copolymer was precipitated and washed with hexane, then dried in a vacuum oven to obtain the copolymer. 2g of the copolymer, 2g of n-butyl bromide, and 20ml of acetonitrile were added to the round-bottom flask and heated to react. The product was washed with acetonitrile for purification and dried to obtain an amphiphilic polymer.

[0068] Vinyl silica sol, amphiphilic polymer and water were mixed evenly in the ratio of 8g:3g:3g, and UV-2959 (the mass was one percent of the total mass of vinyl silica sol and amphiphilic polymer) was added. The cleaned glass sheet was immersed in the above solution, and then pulled out with a pulling machine at a speed of 50mm / min. The glass sheet was reacted at room temperature for 2h under 365nm UV light, rinsed with water and then dried with nitrogen to obtain a glass sheet modified with an organic-inorganic hybrid multifunctional anti-fog coating.

[0069] After testing, the wettability, lubricity, wear resistance, antibacterial properties and antifog properties of the organic-inorganic hybrid multifunctional antifog coating prepared in this example are similar to those in Example 1.

[0070] Example 4

[0071] Prepare vinyl silica sol containing vinyl silane coupling agent: measure 12 mL of ethanol, 3 mL of ethyl orthosilicate, 1 mL of water and 0.2 mL of nitric acid respectively, add them into a flask and stir evenly, then add 0.01 mL of KH570, 0.02 mL of A-172 and 0.02 mL of DDS, continue stirring for 1 hour, and let it stand for 3 days to obtain vinyl silica sol.

[0072] 3g of hexafluorobutyl acrylate and 7g of DMAEMA were added to a round-bottom flask containing 10g of o-xylene to obtain a 50wt% solution. 0.1g of AIBN was then added as a thermal initiator. Polymerization was carried out in an 80°C oil bath. The resulting copolymer was precipitated and washed with hexane, then dried in a vacuum oven to obtain the copolymer. 2g of the copolymer, 2g of isobutyl bromide, and 20ml of acetonitrile were added to the round-bottom flask and heated to react. The product was washed with acetonitrile for purification and dried to obtain an amphiphilic polymer.

[0073] Vinyl silica sol, amphiphilic polymer and water were mixed evenly in the ratio of 8g:3g:3g, and UV-2959 (the mass was one percent of the total mass of vinyl silica sol and amphiphilic polymer) was added. The cleaned glass sheet was immersed in the above solution, and then pulled out with a pulling machine at a speed of 50mm / min. The glass sheet was reacted at room temperature for 2h under 365nm UV light, rinsed with water and then dried with nitrogen to obtain a glass sheet modified with an organic-inorganic hybrid multifunctional anti-fog coating.

[0074] After testing, the wettability, lubricity, wear resistance, antibacterial properties and antifog properties of the organic-inorganic hybrid multifunctional antifog coating prepared in this example are similar to those in Example 1.

[0075] In summary, the organic-inorganic hybrid multifunctional anti-fog coating provided by the present invention uses organic components to modify surface wettability, providing antibacterial, antifouling, and anti-fog properties, while inorganic components improve the coating's mechanical and wear-resistant properties. The method for constructing the anti-fog coating provided by the present invention is simple and convenient, overcoming the poor stability and wear resistance associated with traditional hydrophilic polymers soluble in water. Furthermore, the coating can be applied to the surfaces of most materials, achieving surface wear resistance, antibacterial, antifogging, and antifouling properties.

[0076] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing an organic-inorganic hybrid multifunctional anti-fog coating, characterized in that: The following steps are involved: Mixing tetraethyl orthosilicate, a vinyl silane coupling agent, alcohol, water and acid, and sequentially performing hydrolysis and static aging to obtain vinyl silica sol; A fluorine-containing acrylate monomer, an amino-containing acrylate monomer, a benzene solvent, and an initiator are mixed for polymerization reaction to obtain a copolymer; the copolymer, a brominated alkane, and acetonitrile are mixed for protonation reaction to obtain an amphiphilic polymer; the fluorine-containing acrylate monomer comprises one or more of perfluorooctylethyl methacrylate, hexafluorobutyl methacrylate, and trifluoromethylacrylate; and the mass ratio of the fluorine-containing acrylate monomer to the amino-containing acrylate monomer is 1:1-5; mixing the vinyl silica sol, an amphiphilic polymer, water and a photoinitiator to obtain an organic-inorganic hybrid multifunctional anti-fog coating; The mass ratio of the vinyl silica sol, the amphiphilic polymer and water is 1-10:1-5:1-5.

2. The preparation method according to claim 1, characterized in that The acid includes one or more of hydrochloric acid, nitric acid and acetic acid; the alcohol includes ethanol and / or isopropyl alcohol; the volume ratio of the alcohol, tetraethyl orthosilicate, water and acid is 12-20:1-5:0.5-1.5:0.2; The vinyl silane coupling agent includes one or more of methyltrivinylsilane, dimethyldivinylsilane, γ-methacryloxypropyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane; the mass ratio of the ethyl orthosilicate to the vinyl silane coupling agent is 20~150:

1.

3. The preparation method according to claim 1, characterized in that The time of standing and aging is 1 to 7 days.

4. The preparation method according to claim 1, characterized in that The amino group-containing acrylate monomer is one or more of dimethylaminoethyl methacrylate, 2-aminoethyl methacrylate and 2-(diethylamino)ethyl methacrylate; The benzene solvent is o-xylene; the mass ratio of the total mass of the fluorine-containing acrylate monomer and the amino-containing acrylate monomer to o-xylene is 0.5:1-2; The initiator is an azo initiator; the mass ratio of the total mass of the fluorine-containing acrylate monomer and the amino-containing acrylate monomer to the initiator is 100-200:1; The polymerization reaction temperature is 60-100° C., and the reaction time is 8-24 hours.

5. The preparation method according to claim 1, characterized in that The brominated alkane includes one or more of isopropyl bromide, dodecane bromide and n-butane bromide; the mass ratio of the copolymer to the brominated alkane is 0.1:1 to 1:1; The temperature of the protonation reaction is 60-100° C., and the reaction time is 8-24 hours.

6. The preparation method according to claim 1, characterized in that The mass ratio of the total mass of the vinyl silica sol and the amphiphilic polymer to the photoinitiator is 50-200:

1.

7. An organic-inorganic hybrid multifunctional anti-fog coating prepared by the preparation method according to any one of claims 1 to 6, comprising vinyl silica sol, an amphiphilic polymer, water and a photoinitiator.

8. An organic-inorganic hybrid multifunctional anti-fog coating, characterized in that: The organic-inorganic hybrid multifunctional anti-fog coating according to claim 7 is coated on the surface of a substrate and then UV cured.

9. The organic-inorganic hybrid multifunctional anti-fog coating according to claim 8, characterized in that: The coating method is a dip-pull method; the pulling speed of the dip-pull method is 100-200 mm / min.

10. The organic-inorganic hybrid multifunctional anti-fog coating according to claim 8, characterized in that: The UV curing light wavelength is 320-365 nm, and the light intensity is 180-210 mW / cm 2 , the illumination time is 0.5~3h, and the temperature is room temperature.

Images