Anti-fog automobile glass film and preparation method thereof

Abstract

The invention discloses an anti-fog automobile glass film and a preparation method thereof, and relates to the technical field of glass films. The anti-fog automobile glass film prepared by the invention is prepared from modified polyacrylate, modified silicon dioxide and pyrrole, the modified polyacrylate is obtained by reacting polyacrylate with 4-ethynyl acetophenone, and then reacting with 1H-pyrrole-3-formaldoxime; the modified silicon dioxide is obtained by formylating amino silicon dioxide coated with sodium alginate and then polymerizing the formylated amino silicon dioxide, 4, 4 '-diformyl-2, 2'-disulfonic acid biphenyl and pyrrole-3-formaldehyde. The anti-fog automobile glass film prepared by the invention has good antibacterial, anti-aging and photocatalytic properties.

Description

Technical Field

[0001] The present invention relates to the technical field of glass films, and particularly to an anti-fog automotive glass film and a preparation method thereof. Background Art

[0002] An anti-fog automotive glass film is an automotive safety protection material that eliminates water vapor condensation by coating a special functional coating on the glass surface. Its core function is to improve the clarity of the driving vision, especially to prevent the formation of a fog layer on the glass surface due to the condensation of water vapor in a large temperature difference or humid environment. Currently, anti-fog glass mainly includes two categories: hydrophobic anti-fog and hydrophilic anti-fog.

[0003] The hydrophilic anti-fog coating is a hydrophilic coating applied on the surface of the substrate, thereby improving the wetting state of the material surface and reducing the contact angle of water on its surface. When the contact angle approaches 0, water vapor does not condense into small water droplets on the substrate surface, but spreads highly to form a uniform water film, thus achieving the anti-fog function.

[0004] However, traditional anti-fog films have multiple technical defects. For example, although the hydrophilic coating can adsorb water molecules to inhibit fog droplets, it is prone to adsorb dust and oil due to long-term exposure to the air, resulting in a rough surface and failure. Moreover, the hydrophilicity decreases at low temperature or high humidity. Therefore, antibacterial function is needed to inhibit bacterial pollutants or photocatalytic function to decompose organic pollutants. The anti-fog glass film works outdoors for a long time. Endowing the film with good anti-ultraviolet aging performance can extend the life of the film. Therefore, generally speaking, the anti-fog film needs to solve multi-dimensional problems such as antibacterial, anti-ultraviolet aging, and photocatalytic efficiency at the same time. Summary of the Invention

[0005] The purpose of the present invention is to provide an anti-fog automotive glass film and a preparation method thereof to solve the problems existing in the prior art.

[0006] To solve the above technical problems, the present invention provides the following technical solutions:

[0007] A preparation method of an anti-fog automotive glass film includes the following preparation steps:

[0008] (1) Mix n-butyl acrylate, methyl methacrylate, acrylic acid, and toluene evenly. Under nitrogen protection, heat up to 80 - 90 °C, add benzoyl peroxide which is 0.2 - 0.3 times the mass of n-butyl acrylate, and stir for 2 - 3 h. Then obtain polyacrylate through rotary evaporation under reduced pressure, washing, and drying.

[0009] (2) Mix polyacrylate, 4-ethynylacetophenone, and acetone. Under nitrogen protection, heat up to 90 - 100 °C, then add sodium methoxide, and reflux for 4 - 5 h. After rotary evaporation under reduced pressure, washing, and filtering, obtain pre-modified polyacrylate.

[0010] (3) Mix the pre-modified polyacrylate, 1H-pyrrole-3-carboxaldehyde oxime, N-chlorosuccinimide, diisopropylethylamine, and N,N-dimethylformamide, and react in a microwave reactor for 10 min at a reaction temperature of 110 - 120 °C. After the reaction, obtain the modified polyacrylate through rotary evaporation under reduced pressure, filtration, and washing.

[0011] (4) Stir the pretreated silica, pure water, and 10 wt% sodium periodate solution in the dark for 4 - 5 h, then add ethylene glycol and stir for 5 - 10 min. Obtain the aldehyde-functionalized silica through filtration, washing, and drying.

[0012] (5) Mix the aldehyde-functionalized silica, dithiourea oxamide, and N,N-dimethylformamide, heat to 150 °C and stir for 1 - 2 h. Add 4,4'-diformyl-2,2'-disulfonic acid biphenyl, continue stirring for 5 - 6 h, then add pyrrole-3-carboxaldehyde and continue stirring for 2 - 3 h. Obtain the modified silica through filtration, washing, and drying.

[0013] (6) Ultrasonically mix the modified polyacrylate, modified silica, 0.3 M ammonium persulfate solution, pyrrole, and 70 wt% ethanol-acetone solution, heat to 50 - 60 °C and react for 5 - 6 h. Uniformly coat on the glass surface by the glass rod scraping method and dry at 70 - 80 °C to obtain the anti-fog automotive glass film.

[0014] As an optimization, the mass ratio of n-butyl acrylate, methyl methacrylate, acrylic acid, toluene, and benzoyl peroxide in step (1) is 1:(2 - 3):(3 - 4):(20 - 30):(0.2 - 0.3).

[0015] As an optimization, the mass ratio of polyacrylate, 4-ethynylacetophenone, acetone, and sodium methoxide in step (2) is 1:(0.2 - 0.3):(20 - 30):(0.2 - 0.3).

[0016] As an optimization, the mass ratio of the pre-modified polyacrylate, 1H-pyrrole-3-carboxaldehyde oxime, N-chlorosuccinimide, diisopropylethylamine, and N,N-dimethylformamide in step (3) is 1:(0.2 - 0.3):(0.5 - 0.6):(0.2 - 0.3):(20 - 30).

[0017] As an optimization, the preparation method of the pretreated silica in step (4) is as follows: Mix silica, 3-aminopropyltrimethoxysilane, ethanol, and pure water in a mass ratio of 1:(1 - 2):(20 - 30):(10 - 15), heat up to 50 - 60°C and react for 5 - 6 h. After the reaction, filter, wash, and dry to obtain amino-functionalized silica. Mix the amino-functionalized silica, sodium dodecyl sulfate, and pure water in a mass ratio of 1:(2 - 3):(50 - 60), heat up to 40°C and stir for 3 - 4 h. Add an aqueous sodium alginate solution with a concentration of 0.02 g / mL and a volume 10 - 12 times the mass of the amino-functionalized silica dropwise at a rate of 0.5 mL / min. After reacting for 1 - 2 h, add glutaraldehyde with a mass 2 - 3 times that of the amino-functionalized silica, continue to react for 1 - 2 h. Use 1 M hydrochloric acid to dissolve and adjust the pH to 4, heat up to 65 - 75°C, and then react for 2 - 3 h. Filter, wash, and dry to obtain the pretreated silica.

[0018] As an optimization, the mass ratio of the pretreated silica, pure water, 10 wt% sodium periodate solution, and ethylene glycol in step (4) is 1:(50 - 60):(15 - 17):(2 - 3).

[0019] As an optimization, the mass ratio of the aldehyde-functionalized silica, dithiobiureaoxamide, and N,N-dimethylformamide in step (5) is 1:(0.5 - 0.7):(20 - 30); the molar ratio of 4,4'-diformyl-2,2'-disulfonic acid biphenyl, dithiobiureaoxamide, and pyrrole-3-carboxaldehyde is 1:(3.1 - 3.2):(2.4 - 2.5).

[0020] As an optimization, the mass ratio of the modified polyacrylate, modified silica, 0.3 M ammonium persulfate solution, pyrrole, and 70 wt% ethanol-acetone solution in step (6) is 1:(0.03 - 0.05):(0.06 - 0.07):(0.01 - 0.02):(10 - 12).

[0021] The present invention also provides an anti-fog automotive glass film prepared by the preparation method of the anti-fog automotive glass film according to the above.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0023] The anti-fog automotive glass film prepared by the present invention contains modified polyacrylate, modified silica, and pyrrole; the modified polyacrylate is obtained by reacting polyacrylate with 4-ethynylacetophenone and then reacting with 1H-pyrrole-3-carboxaldehyde oxime; the modified silica is obtained by aldehyde-functionalizing amino-silica coated with sodium alginate and then polymerizing with 4,4'-diformyl-2,2'-disulfonic acid biphenyl and pyrrole-3-carboxaldehyde.

[0024] First, acrylic monomers, monomers such as methyl methacrylate are polymerized to generate polyacrylate with good hydrophilicity. The ester group on the side chain of polyacrylate undergoes Claisen condensation with 4-ethynylacetophenone to generate a β-diketone structure. The β-diketone structure can convert the absorbed light energy into heat energy by relying on the conversion between the keto form and enol form in the molecular structure, thereby achieving the effect of anti-ultraviolet aging; the alkynyl group on 4-ethynylacetophenone and 1H-pyrrole-3-carbaldehyde oxime generate arylisoxazole with antibacterial properties through a cycloaddition reaction, endowing the material with good antibacterial properties and introducing a pyrrole group;

[0025] Secondly, sodium alginate is wrapped on silica to endow silica with good hydrophilicity. Then, sodium alginate is oxidized with sodium periodate to generate aldehyde groups, and polymerizing with 4,4'-diformyl-2,2'-disulfonic acid biphenyl and pyrrole-3-carbaldehyde can obtain a thiazolothiazole conjugate polymer with pyrrole at the end. The thiazolothiazole conjugate polymer has good photocatalytic degradation performance and can effectively decompose small molecule pollutants on the surface of the glass film, thereby achieving the self-cleaning performance;

[0026] Finally, the modified polyacrylate, modified silica and pyrrole are mixed. In the presence of ammonium persulfate, pyrrole is oxidatively polymerized to generate polypyrrole. Since both the surface of the modified polyacrylate and the modified silica contain pyrrole functional groups that can participate in polymerization, polypyrrole generates cross-linking between the modified polyacrylate and the modified silica, which can enhance the mechanical properties of the film. Polypyrrole can improve the antistatic performance of the material and reduce the electrostatic adsorption of dust. Specific implementation mode

[0027] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0028] In the following examples and comparative examples, the particle size of the silica is 200 nm; the model of the microwave reactor is Biotage Initiator+ from Sweden, and the absorbance is set to "very high".

[0029] Example 1:

[0030] A preparation method of an anti-fog automotive glass film, the preparation method of the anti-fog automotive glass film includes the following preparation steps:

[0031] (1) Mix n-butyl acrylate, methyl methacrylate, acrylic acid, and toluene in a mass ratio of 1:2:3:20. Under nitrogen protection, heat the mixture to 90 °C, add benzoyl peroxide in an amount 0.2 times the mass of n-butyl acrylate, and stir for 3 h. Then, obtain polyacrylate through rotary evaporation under reduced pressure, washing, and drying.

[0032] (2) Mix polyacrylate, 4-ethynylacetophenone, and acetone in a mass ratio of 1:0.2:20. Under nitrogen protection, heat the mixture to 100 °C, then add sodium methoxide in an amount 0.2 times the mass of polyacrylate, and reflux for 5 h. After that, obtain pre-modified polyacrylate through rotary evaporation under reduced pressure, washing, and filtration.

[0033] (3) Mix pre-modified polyacrylate, 1H-pyrrole-3-carboxaldehyde oxime, N-chlorosuccinimide, diisopropylethylamine, and N,N-dimethylformamide in a mass ratio of 1:0.2:0.5:0.2:20. React in a microwave reactor for 10 min at a reaction temperature of 120 °C. After the reaction, obtain modified polyacrylate through rotary evaporation under reduced pressure, filtration, and washing.

[0034] (4) Mix silica, 3-aminopropyltrimethoxysilane, ethanol, and pure water in a mass ratio of 1:1:20:10. Heat the mixture to 60 °C and react for 6 h. After the reaction, obtain amino-functionalized silica through filtration, washing, and drying. Mix amino-functionalized silica, sodium dodecyl sulfate, and pure water in a mass ratio of 1:2:50. Heat the mixture to 40 °C and stir for 4 h. Then, add an aqueous sodium alginate solution with a concentration of 0.02 g / mL and a volume 12 times the mass of amino-functionalized silica at a dropping rate of 0.5 mL / min. After reacting for 2 h, add glutaraldehyde in an amount 2 times the mass of amino-functionalized silica and continue to react for 2 h. Adjust the pH to 4 using 1 M hydrochloric acid, heat the mixture to 75 °C, and react for 3 h. After that, obtain pretreated silica through filtration, washing, and drying. Mix pretreated silica, pure water, and a 10 wt% sodium periodate solution in a mass ratio of 1:50:15, stir in the dark for 5 h, then add ethylene glycol in an amount 2 times the mass of pretreated silica and stir for 10 min. After that, obtain aldehyde-functionalized silica through filtration, washing, and drying.

[0035] (5) Mix aldehyde-functionalized silica, dithiocarbazone oxamide, and N,N-dimethylformamide in a mass ratio of 1:0.5:20. Heat the mixture to 150 °C and stir for 2 h. Then, add 4,4'-diformyl-2,2'-disulfonic acid biphenyl and continue to stir for 6 h. Add pyrrole-3-carboxaldehyde and continue to stir for 3 h. After that, obtain modified silica through filtration, washing, and drying. The molar ratio of 4,4'-diformyl-2,2'-disulfonic acid biphenyl, dithiocarbazone oxamide, and pyrrole-3-carboxaldehyde is 1:3.1:2.4.

[0036] (6) Mix the modified polyacrylate, modified silica, 0.3M ammonium persulfate solution, pyrrole, and 70wt% ethanol-acetone solution by ultrasonic mixing at a mass ratio of 1:0.03:0.06:0.01:10. Heat up to 60°C and react for 6h. Coat it evenly on the glass surface by the glass rod scraping method and dry it at 80°C to obtain the anti-fog automotive glass film.

[0037] Example 2:

[0038] A preparation method of an anti-fog automotive glass film, the preparation method of the anti-fog automotive glass film includes the following preparation steps:

[0039] (1) Mix n-butyl acrylate, methyl methacrylate, acrylic acid, and toluene at a mass ratio of 1:2.5:3.5:25. Under nitrogen protection, heat up to 85°C, add benzoyl peroxide which is 0.25 times the mass of n-butyl acrylate, and stir for 2.5h. Obtain polyacrylate through reduced pressure rotary evaporation, washing, and drying.

[0040] (2) Mix polyacrylate, 4-ethynylacetophenone, and acetone at a mass ratio of 1:0.25:25. Under nitrogen protection, heat up to 95°C, then add sodium methoxide which is 0.25 times the mass of polyacrylate, and reflux for 4.5h. After reduced pressure rotary evaporation, washing, and filtration, obtain pre-modified polyacrylate.

[0041] (3) Mix pre-modified polyacrylate, 1H-pyrrole-3-carboxaldoxime, N-chlorosuccinimide, diisopropylethylamine, and N,N-dimethylformamide at a mass ratio of 1:0.25:0.55:0.25:25. React in a microwave reactor for 10min, the reaction temperature is 105°C. After the reaction, obtain modified polyacrylate through reduced pressure rotary evaporation, filtration, and washing.

[0042] (4) Mix silica, 3-aminopropyltrimethoxysilane, ethanol, and pure water at a mass ratio of 1:1.5:25:13. Heat up to 55°C and react for 5.5h. After the reaction, obtain amino-functionalized silica through filtration, washing, and drying. Mix amino-functionalized silica, sodium dodecyl sulfate, and pure water at a mass ratio of 1:2.5:55. Heat up to 40°C and stir for 3.5h. Add an aqueous solution of sodium alginate with a concentration of 0.02g / mL which is 11 times the mass of amino-functionalized silica at a dropping rate of 0.5mL / min. After reacting for 1.5h, add glutaraldehyde which is 2.5 times the mass of amino-functionalized silica, and continue to react for 1.5h. Use 1M hydrochloric acid to dissolve and adjust the pH to 4. Heat up to 70°C and react for 2.5h. After filtration, washing, and drying, obtain pretreated silica. Mix pretreated silica, pure water, and 10wt% sodium periodate solution at a mass ratio of 1:55:16 and stir in the dark for 4.5h. Then add ethylene glycol which is 2.5 times the mass of pretreated silica and stir for 7min. After filtration, washing, and drying, obtain aldehyde-functionalized silica.

[0043] (5) Mix aldehyde-functionalized silica, dithiobiurea oxamide, and N,N-dimethylformamide in a mass ratio of 1:0.6:25. Heat to 150 °C and stir for 1.5 h. Add 4,4'-diformyl-2,2'-disulfonic acid biphenyl, continue stirring for 5.5 h, then add pyrrole-3-carboxaldehyde and continue stirring for 2.5 h. After filtration, washing, and drying, modified silica is obtained; the molar ratio of 4,4'-diformyl-2,2'-disulfonic acid biphenyl, dithiobiurea oxamide, and pyrrole-3-carboxaldehyde is 1:3.1:2.4;

[0044] (6) Ultrasonically mix modified polyacrylate, modified silica, 0.3 M ammonium persulfate solution, pyrrole, and 70 wt% ethanol-acetone solution in a mass ratio of 1:0.04:0.06:0.02:11. Heat to 55 °C and react for 5.5 h, then evenly coat on the glass surface by the glass rod scraping method and dry at 75 °C to obtain an anti-fog automotive glass film.

[0045] Example 3:

[0046] A method for preparing an anti-fog automotive glass film, the method for preparing the anti-fog automotive glass film comprising the following preparation steps:

[0047] (1) Mix n-butyl acrylate, methyl methacrylate, acrylic acid, and toluene in a mass ratio of 1:3:4:30. Under nitrogen protection, heat to 80 °C, add benzoyl peroxide 0.3 times the mass of n-butyl acrylate and stir for 2 h. After rotary evaporation under reduced pressure, washing, and drying, polyacrylate is obtained;

[0048] (2) Mix polyacrylate, 4-ethynylacetophenone, and acetone in a mass ratio of 1:0.3:30. Under nitrogen protection, heat to 90 °C and then add sodium methoxide 0.3 times the mass of polyacrylate. After refluxing for 4 h, perform rotary evaporation under reduced pressure, washing, and filtration to obtain pre-modified polyacrylate;

[0049] (3) Mix pre-modified polyacrylate, 1H-pyrrole-3-carboxaldehyde oxime, N-chlorosuccinimide, diisopropylethylamine, and N,N-dimethylformamide in a mass ratio of 1:0.3:0.6:0.3:30. React in a microwave reactor for 10 min at a reaction temperature of 110 °C. After the reaction, perform rotary evaporation under reduced pressure, filtration, and washing to obtain modified polyacrylate;

[0050] (4) Mix silicon dioxide, 3-aminopropyltrimethoxysilane, ethanol, and pure water in a mass ratio of 1:2:30:15, heat up to 50 °C and react for 5 h. After the reaction, filter, wash, and dry to obtain amino-functionalized silicon dioxide. Mix the amino-functionalized silicon dioxide, sodium dodecyl sulfate, and pure water in a mass ratio of 1:3:60, heat up to 40 °C and stir for 3 h. Add an aqueous sodium alginate solution with a concentration of 0.02 g / mL, which is 12 times the mass of the amino-functionalized silicon dioxide, at a dropping rate of 0.5 mL / min. After reacting for 1 h, add glutaraldehyde with a mass three times that of the amino-functionalized silicon dioxide, and continue to react for 1 h. Use 1 M hydrochloric acid to dissolve and adjust the pH to 4. After heating up to 65 °C, react for 2 h. Filter, wash, and dry to obtain pretreated silicon dioxide. Mix the pretreated silicon dioxide, pure water, and a 10 wt% sodium periodate solution in a mass ratio of 1:60:17, stir in the dark for 4 h, then add ethylene glycol with a mass three times that of the pretreated silicon dioxide and stir for 5 min. Filter, wash, and dry to obtain aldehyde-functionalized silicon dioxide;

[0051] (5) Mix the aldehyde-functionalized silicon dioxide, dithiourea oxamide, and N,N-dimethylformamide in a mass ratio of 1:0.7:30, heat up to 150 °C and stir for 1 h. Add 4,4'-diformyl-2,2'-disulfonic acid biphenyl, continue to stir for 5 h, then add pyrrole-3-carboxaldehyde and continue to stir for 2 h. Filter, wash, and dry to obtain modified silicon dioxide. The molar ratio of 4,4'-diformyl-2,2'-disulfonic acid biphenyl, dithiourea oxamide, and pyrrole-3-carboxaldehyde is 1:3.2:2.5;

[0052] (6) Ultrasonically mix the modified polyacrylate, modified silicon dioxide, 0.3 M ammonium persulfate solution, pyrrole, and a 70 wt% ethanol-acetone solution in a mass ratio of 1:0.05:0.07:0.02:12, heat up to 50 °C and react for 5 h. Use a glass rod scraping method to evenly coat it on the glass surface and dry at 70 °C to obtain an anti-fog automotive glass film.

[0053] Comparative Example 1:

[0054] The preparation method of the anti-fog automotive glass film in Comparative Example 1 is different from that in Example 2 in that the polyacrylate is not modified. Specifically, steps (2) to (3) are not included, and step (6) is modified as follows: Mix polyacrylate, modified silicon dioxide, 0.3 M ammonium persulfate solution, pyrrole, and a 70 wt% ethanol-acetone solution in a mass ratio of 1:0.04:0.13:0.02:11, ultrasonically mix, heat up to 55 °C and react for 5.5 h. Then use a glass rod scraping method to evenly coat it on the glass surface and dry at 75 °C to obtain an anti-fog automotive glass film. The remaining steps are the same as in Example 2.

[0055] Comparative Example 2:

[0056] The preparation method of the anti-fog automotive glass film of Comparative Example 2 is different from that of Example 2 in that the pre-modified polyacrylate is not modified. Specifically, step (3) is not included, and step (6) is modified as follows: The pre-modified polyacrylate, modified silica, 0.3 M ammonium persulfate solution, pyrrole, and 70 wt% ethanol-acetone solution are ultrasonically mixed at a mass ratio of 1:0.04:0.13:0.02:11, heated to 55 °C and reacted for 5.5 h, then uniformly coated on the glass surface by the glass rod scraping method, and dried at 75 °C to obtain the anti-fog automotive glass film. The remaining steps are the same as those in Example 2.

[0057] Comparative Example 3:

[0058] The preparation method of the anti-fog automotive glass film of Comparative Example 3 is different from that of Example 2 in that silica is not modified. Specifically, steps (4) to (5) are not included, and step (6) is modified as follows: The modified polyacrylate, silica, 0.3 M ammonium persulfate solution, pyrrole, and 70 wt% ethanol-acetone solution are ultrasonically mixed at a mass ratio of 1:0.04:0.13:0.02:11, heated to 55 °C and reacted for 5.5 h, then uniformly coated on the glass surface by the glass rod scraping method, and dried at 75 °C to obtain the anti-fog automotive glass film. The remaining steps are the same as those in Example 2.

[0059] Test Example 1:

[0060] Testing of antibacterial properties:

[0061] The glass films prepared in the examples and comparative examples were subjected to an antibacterial rate test on the samples according to the standard QB / T 2591-2003 under light-shielded conditions, and the results are shown in Table 1.

[0062] Table 1

[0063] Antibacterial rate (%) Antibacterial rate (%) Example 1 96.57 Comparative Example 1 47.16 Example 2 97.21 Comparative Example 2 48.34 Example 3 97.39 Comparative Example 3 92.69

[0064] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the coatings prepared by the present invention have good antibacterial properties.

[0065] In Comparative Example 1, the polyacrylate was not modified, and in Comparative Example 2, the pre-modified polyacrylate was not modified. The antibacterial properties of Examples 1 to 3 are better than those of Comparative Examples 1 to 2. This shows that first, polyacrylate with good hydrophilicity is generated by polymerizing acrylic acid monomers, methyl methacrylate and other monomers. The ester group on the side chain of polyacrylate undergoes Claisen condensation with 4-ethynylacetophenone, and the alkynyl group on 4-ethynylacetophenone undergoes cycloaddition reaction with 1H-pyrrole-3-carboxaldehyde oxime to form arylisoxazole with antibacterial properties, endowing the material with good antibacterial properties.

[0066] Test Example 2:

[0067] Testing of photocatalytic properties:

[0068] Test method: Cut the anti-fog glass films prepared in the examples and comparative examples into samples of 25 mm × 25 mm, immerse them in a methyl orange solution with a concentration of 20 mg / mL and a volume of 30 mL, irradiate them under a 500 W xenon lamp for 2 h, with the light source distance being 15 cm, test the concentration of methyl orange after photocatalysis, and calculate the photocatalytic efficiency; the results are shown in Table 2.

[0069] Table 2

[0070] Photocatalytic efficiency (%) Photocatalytic efficiency (%) Example 1 80.74 Comparative Example 1 80.22 Example 2 81.14 Comparative Example 2 80.31 Example 3 81.35 Comparative Example 3 12.31

[0071] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the coating prepared by the present invention has good photocatalytic performance.

[0072] In Comparative Example 3, silica was not modified, and the photocatalytic performance of Examples 1 to 3 was better than that of Comparative Example 3; it shows that wrapping sodium alginate on silica endows silica with good hydrophilicity, and then using sodium periodate to oxidize sodium alginate to generate aldehyde groups, and polymerizing with 4,4'-diformyl-2,2'-disulfonic acid biphenyl and pyrrole-3-carboxaldehyde can obtain a thiazolothiazole conjugate polymer with pyrrole at the end. The thiazolothiazole conjugate polymer has good photocatalytic degradation performance and can effectively decompose small molecule pollutants on the surface of the glass film, thus achieving the self-cleaning performance.

[0073] Test Example 3:

[0074] Test of mechanical properties:

[0075] Test method: According to ASTM F735-06, test the abrasion resistance of the glass films in the examples and comparative examples respectively, and measure the haze before and after abrasion; the results are shown in Table 3.

[0076] Test of anti-aging performance

[0077] Test method: Put the samples into an ultraviolet aging chamber for aging, with the aging time being 168 h and the ultraviolet lamp model being UVA-340. Test the aged samples according to the test method of mechanical properties, and calculate the abrasion resistance retention rate. The results are shown in Table 3.

[0078] Table 3

[0079] Wear resistance (%) Retention rate of wear resistance after aging (%) Example 1 2.3 Example 1 90.32 Example 2 2.1 Example 2 91.36 Example 3 2.1 Example 3 91.47 Comparative Example 1 5.7 Comparative Example 1 62.14 Comparative Example 2 5.3 Comparative Example 2 89.73 Comparative Example 3 3.4 Comparative Example 3 80.41

[0080] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 3, it can be found that the coating prepared by the present invention has good abrasion resistance and anti-aging performance;

[0081] In Comparative Example 1, polyacrylate was not modified; in Comparative Example 2, the pre-modified polyacrylate was not modified; in Comparative Example 3, silica was not modified. The wear resistance of Examples 1 to 3 was better than that of Comparative Examples 1 to 3, and the anti-aging performance of Examples 1 to 3 was better than that of Comparative Examples 1 and 3. It shows that first, acrylic acid monomers, methyl methacrylate and other monomers are polymerized to generate polyacrylate with good hydrophilicity. The ester group on the side chain of polyacrylate undergoes Claisen condensation with 4-ethynylacetophenone to generate a β-diketone structure. The β-diketone structure can convert the absorbed light energy into heat energy by relying on the conversion between the keto form and the enol form in the molecular structure, so as to achieve the effect of anti-ultraviolet aging.

[0082] The modified polyacrylate, modified silica and pyrrole were mixed. In the presence of ammonium persulfate, pyrrole was oxidatively polymerized to form polypyrrole. Since both the surfaces of the modified polyacrylate and modified silica contain pyrrole functional groups that can participate in polymerization, polypyrrole cross-links between the modified polyacrylate and modified silica, which can enhance the mechanical properties of the film. The reduction in the wear resistance retention rate of Comparative Example 3 after aging is because the conjugated porous polymer on the surface of silica also has a certain absorption performance for ultraviolet light.

[0083] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claimed claim.

Claims

1. A method for preparing an anti-fog automobile glass film, characterized in that: The method comprises the following preparation steps: (1) n-butyl acrylate, methyl methacrylate, acrylic acid and toluene are mixed, heated to 80-90° C. under nitrogen protection, benzoyl peroxide is added and stirred for 2-3 hours, and then washed and dried by vacuum rotary evaporation to obtain polyacrylate; (2) polyacrylate, 4-ethynylacetophenone and acetone are mixed, heated to 90-100° C. under nitrogen protection, and sodium methoxide is added. After reflux reaction for 4-5 hours, the mixture is washed and filtered by vacuum rotary evaporation to obtain pre-modified polyacrylate; (3) Pre-modified polyacrylate, 1H-pyrrole-3-formaldehyde oxime, N-chlorosuccinimide, diisopropylethylamine, and N,N-dimethylformamide are mixed and reacted in a microwave reactor for 10 minutes at a reaction temperature of 110-120° C. After the reaction is completed, the modified polyacrylate is filtered and washed by vacuum rotary evaporation to obtain the modified polyacrylate; (4) stirring the pretreated silica, pure water, and 10 wt% sodium periodate solution in the dark for 4-5 hours, adding ethylene glycol and stirring for 5-10 minutes, filtering, washing, and drying to obtain formaldehyde-modified silica; (5) Mixing formaldehyde-modified silica, dithiourea oxalamide, and N,N-dimethylformamide, heating to 150° C. and stirring for 1-2 hours, adding 4,4'-diformyl-2,2'-disulfonic acid biphenyl, and continuing to stir for 5-6 hours, adding pyrrole-3-carboxaldehyde and continuing to stir for 2-3 hours, filtering, washing, and drying to obtain modified silica; (6) The modified polyacrylate, modified silica, 0.3M ammonium persulfate solution, pyrrole, and 70 wt% ethanol-acetone solution were ultrasonically mixed, heated to 50-60° C. for reaction for 5-6 h, and evenly coated on the glass surface by a glass rod coating method, and dried at 70-80° C. to obtain an anti-fog automobile glass film.

2. The method for preparing an anti-fog automobile glass film according to claim 1, characterized in that: In step (1), the mass ratio of n-butyl acrylate, methyl methacrylate, acrylic acid, toluene and benzoyl peroxide is 1:(2-3):(3-4):(20-30):(0.2-0.3).

3. The method for preparing an anti-fog automobile glass film according to claim 1, characterized in that: The mass ratio of the polyacrylate, 4-ethynylacetophenone, acetone and sodium methoxide in step (2) is 1:(0.2-0.3):(20-30):(0.2-0.3).

4. The method for preparing an anti-fog automobile glass film according to claim 1, characterized in that: The mass ratio of the pre-modified polyacrylate, 1H-pyrrole-3-carboxaldehyde oxime, N-chlorosuccinimide, diisopropylethylamine and N,N-dimethylformamide in step (3) is 1:(0.2-0.3):(0.5-0.6):(0.2-0.3):(20-30).

5. The method for preparing an anti-fog automobile glass film according to claim 1, characterized in that: The preparation method of the pretreated silica in step (4) is as follows: silica, 3-aminopropyltrimethoxysilane, ethanol, and pure water are mixed in a mass ratio of 1: (1-2): (20-30): (10-15), heated to 50-60°C and reacted for 5-6 hours, and after the reaction is completed, the mixture is filtered, washed, and dried to obtain amino silica; amino silica, sodium dodecyl sulfate, and pure water are mixed in a mass ratio of 1: (2-3): (50-60), heated to 40°C and stirred for 3-4 hours, and a 0.02 g / mL sodium alginate aqueous solution with a mass of 10-12 times that of the amino silica is added at a drop rate of 0.5 mL / min. After reacting for 1-2 hours, glutaraldehyde with a mass of 2-3 times that of the amino silica is added, and the reaction is continued for 1-2 hours. 1M hydrochloric acid is used to dissolve and adjust the pH to 4, and the mixture is heated to 65-75°C and reacted for 2-3 hours. The pretreated silica is obtained by filtering, washing, and drying.

6. The method for preparing an anti-fog automobile glass film according to claim 1, characterized in that: The mass ratio of the pretreated silica, pure water, 10 wt% sodium periodate solution and ethylene glycol in step (4) is 1:(50-60):(15-17):(2-3).

7. The method for preparing an anti-fog automobile glass film according to claim 1, characterized in that: In step (5), the mass ratio of the formaldehyde-modified silica, dithiourea oxalamide, and N,N-dimethylformamide is 1:(0.5-0.7):(20-30); the molar ratio of the 4,4'-diformyl-2,2'-disulfonic acid biphenyl, dithiourea oxalamide, and pyrrole-3-carboxaldehyde is 1:(3.1-3.2):(2.4-2.5).

8. The method for preparing an anti-fog automobile glass film according to claim 1, characterized in that: In step (6), the mass ratio of the modified polyacrylate, modified silica, 0.3M ammonium persulfate solution, pyrrole, and 70wt% ethanol-acetone solution is 1:(0.03-0.05):(0.06-0.07):(0.01-0.02):(10-12).

9. An anti-fog automobile glass film prepared according to the method for preparing the anti-fog automobile glass film according to any one of claims 1 to 8.