Azobenzene-regulated amphiphilic copolymer composition as well as preparation method and application thereof

Abstract

The invention discloses an azobenzene-regulated amphiphilic copolymer composition as well as a preparation method and application thereof, and relates to the technical field of antifogging coatings. Comprising the following components in parts by weight: 5-35 parts of a fluorine-containing azobenzene amphiphilic copolymer, 5-50 parts of a cross-linking agent, 0.5-15 parts of a surfactant, 0.2-5 parts of an acid catalyst, 0.1-0.8 part of an initiator and 40-90 parts of a solvent I, the invention further provides a preparation method and application of the azobenzene-regulated amphiphilic copolymer composition, an anti-fog coating prepared from the azobenzene-regulated amphiphilic copolymer composition has good hardness, adhesive force and durability, and the anti-fog effect is good. The method is suitable for anti-fog treatment in the fields of visual optical materials such as optical devices, transparent plastics and glass, and has wide application prospects and industrialization values.

Description

Technical Field

[0001] The present invention relates to the technical field of anti - fog coatings, and specifically relates to an azobenzene - regulated amphiphilic copolymer composition, a preparation method, and an application thereof. Background Art

[0002] In many visualization application fields (such as endoscopes, optical lenses, automotive windshields, etc.), optical materials need to have excellent optical transmittance (usually > 90%) and stable environmental adaptability to ensure clear vision and durable use performance. However, when the surface of the material changes due to environmental temperature and humidity or a large temperature difference with the outside world, water vapor is easily condensed to form tiny water droplets, resulting in fogging on the surface, causing light scattering, and significantly reducing the transmittance. To solve this problem, anti - fog coating technology has been widely studied. Among them, hydrophilic coatings based on amphiphilic copolymers are considered to be a solution with great market potential due to their high light transmittance, strong adhesion, and environmental friendliness.

[0003] Traditional anti - fog coatings mostly use surfactants or soluble polymer materials to promote the spreading of water droplets into a uniform water film by reducing the surface tension. However, water - soluble small molecules (such as anionic / cationic surfactants) in such coatings are easily lost during long - term use or in high - humidity environments, resulting in a rapid decline in anti - fog performance and accompanied by defects such as flow marks and color blooming. In addition, problems such as low coating hardness, poor water resistance, and insufficient heat - aging resistance also limit their practical applications.

[0004] In the Chinese invention with the publication number CN113930121A, an anti - fog coating composition based on an amphiphilic copolymer is disclosed. By introducing the synergistic effect of sulfonic acid groups and cross - linkers, a three - dimensional network structure is formed to reduce the residue of water - soluble small molecules, and the problems of flow marks and color blooming are improved to a certain extent.

[0005] However, the anti - fog coating composition of the amphiphilic copolymer in the above patent still faces challenges: insufficient optimization of the ratio of sulfonic acid groups to alkaline compounds and cross - link density may affect the long - term stability of the coating; the degree of chemical immobilization of surfactants is limited, and they may still gradually lose under high humidity or mechanical friction, resulting in a decline in anti - fog performance. In addition, the heat - aging resistance and film - forming uniformity of the coating still need to be further improved to meet the application requirements in harsh environments. Summary of the Invention

[0006] Aiming at the deficiencies in the prior art, the purpose of the present invention is to provide an azobenzene - regulated amphiphilic copolymer composition, a preparation method, and an application thereof to solve the problem of low durability and easy attenuation of the anti - fog performance of existing anti - fog coating compositions.

[0007] To achieve the above - mentioned purpose, the present invention adopts the following technical solutions:

[0008] An azobenzene-regulated amphiphilic copolymer composition, calculated by mass fraction, comprises 5-35 parts of a fluorinated azobenzene amphiphilic copolymer, 5-50 parts of a crosslinking agent, 0.5-15 parts of a surfactant, 0.2-5 parts of an acidic catalyst, 0.1-0.8 parts of an initiator, and 40-90 parts of a solvent I.

[0009] Preferably, the fluorinated azobenzene amphiphilic copolymer comprises:

[0010] Monomer A1, which is an acrylate monomer with a hydroxyl functional group;

[0011] Monomer A2, which is a vinyl monomer with a hydrophobic functional group;

[0012] Monomer A3, which is a vinyl monomer with a hydrophilic functional group; and

[0013] Monomer A4, which is a fluorinated azobenzene acrylic monomer;

[0014] The number-average molecular weight of the fluorinated azobenzene amphiphilic copolymer is 5000-100000, and its structural schematic diagram is:

[0015]

[0016] Wherein x, y, z, and m respectively represent the degrees of polymerization of monomer A1, monomer A2, monomer A3, and monomer A4;

[0017] R1 is an alkyl group containing a hydroxyl group, and R2 is H or CH3;

[0018] R3 is an alkyl group, and R4 is H or CH3;

[0019] R5, R6, and R7 are H or CH3;

[0020] R8 is H or CH3, and R9 is one of the functional groups OCF3, OCF2CF3, OCF2CF2CF3, OCF2CF2CF2CF3.

[0021] Preferably, calculated by mass fraction, the content of monomer A1 is 10% - 20%, the content of monomer A2 is 20% - 60%, the content of monomer A3 is 20% - 60%, and the content of monomer A4 is 2% - 20%.

[0022] Preferably, monomer A1 is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate;

[0023] Monomer A2 is at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate;

[0024] The monomer A3 is at least one of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0025] Preferably, the crosslinking agent is at least one of melamine-formaldehyde resin, hexamethoxymelamine resin, and hexamethoxymethylmelamine resin;

[0026] The surfactant is at least one of perfluoroethyl ethyl alcohol, perfluoropropyl ethyl alcohol, perfluorobutyl ethyl alcohol, perfluorohexyl ethyl alcohol, perfluorooctyl ethyl alcohol, and perfluoroalkyl ethyl alcohol;

[0027] The acidic catalyst is at least one of p-toluenesulfonic acid monohydrate, hydrochloric acid, and sulfuric acid;

[0028] The solvent I is at least one of alcohol solvents, ether solvents, ester solvents, aromatic solvents, amides, and water; the initiator is azobisisobutyronitrile.

[0029] The present invention also provides a method for preparing an azobenzene-regulated amphiphilic copolymer composition, comprising the following steps:

[0030] S1. Monomer A4 is prepared by the ring-opening reaction of (meth)acrylic acid glycerol ether with N-methylaniline and using the diazo coupling reaction of its product;

[0031] S2. Monomer A1, A2, A3, A4 prepared in S1, and the initiator are weighed, and then the components are added to the solvent II and reacted at 70-100 °C for 3-24 h to obtain a fluorinated azobenzene amphiphilic copolymer;

[0032] S3. The crosslinking agent, surfactant, acidic catalyst, and solvent I are weighed and mixed uniformly with the fluorinated azobenzene amphiphilic copolymer prepared in S2 to obtain an azobenzene-regulated amphiphilic copolymer composition.

[0033] Preferably, the specific steps for preparing monomer A4 in step S1 are as follows:

[0034] S11. N,N-dimethylformamide, glycidyl methacrylate, N-methylaniline, and p-methoxyphenol are heated and reacted under stirring conditions to obtain monomer A4';

[0035] S12. The monomer A4' obtained in S11 is purified, the purified monomer A4' is dissolved in N,N-dimethylformamide and stirred evenly, then subjected to a diazo coupling reaction with a diazonium salt, and then separated and purified to obtain monomer A4.

[0036] Preferably, in step S2, the solvent II is at least one of alcohol solvents, ether solvents, ester solvents, aromatic solvents, and amide solvents.

[0037] The present invention also provides an application of an azobenzene-regulated amphiphilic copolymer composition in visual optical materials.

[0038] Preferably, the specific steps are as follows: Coating the azobenzene-regulated amphiphilic copolymer composition on the surface of a substrate by spin coating, spraying or dip coating processes, then heating and curing at 110-120 °C for 10-15 min, and finally forming an anti-fog coating on the surface of the substrate.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] 1. For the azobenzene-regulated amphiphilic copolymer composition prepared by the present invention, the monomer A4 has both structural stability and functionality. The azobenzene group in the monomer A4 endows the fluorinated azobenzene amphiphilic copolymer with good hydrophobicity. At the same time, it also has a light-responsive property. Under the action of ultraviolet light, the azobenzene group undergoes cis-trans isomerization through the rotation of the N=N bond, resulting in a decrease in the dipole moment, so that the hydrophobic group containing fluorine at the end curls from the outer layer to the inner layer, increasing the surface energy of the azobenzene-regulated amphiphilic copolymer composition and reducing the water contact angle, thereby improving the anti-fog effect. Moreover, under the influence of different ultraviolet light wavelengths, powers, and irradiation times, the energy absorbed by the azobenzene group is different, and the number and degree of cis-trans isomerized azobenzene groups are also different. Therefore, the azobenzene-regulated amphiphilic copolymer composition will show different trends of water contact angle reduction and anti-fog recovery effect.

[0041] 2. The anti-fog coating prepared from the azobenzene-regulated amphiphilic copolymer composition in the present invention has a significant effect in improving anti-fog durability. Moreover, after the anti-fog coating fails to prevent fog, it can partially or completely restore the anti-fog function under ultraviolet light irradiation with a specific wavelength, power, and time, effectively extending the service life of the anti-fog coating.

[0042] 3. The anti-fog coating prepared from the azobenzene-regulated amphiphilic copolymer composition in the present invention has good hardness, adhesion, and durability, and is suitable for anti-fog treatment in the fields of visual optical materials such as optical devices, transparent plastics, and glass, and has broad application prospects and industrialization value.

[0043] Other advantages, objectives, and features of the present invention will be partially reflected by the following description, and will also be understood by those skilled in the art through the research and practice of the present invention. Description of the Drawings

[0044] Figure 1 Results of anti-fogging of the anti-fog coating prepared in Example 5 in the initial five minutes;

[0045] Figure 2 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water once and then anti-fogging for 5 minutes;

[0046] Figure 3 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water twice and then anti-fogging for 5 minutes;

[0047] Figure 4 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water three times and then anti-fogging for 5 minutes;

[0048] Figure 5 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water four times and then anti-fogging for 5 minutes;

[0049] Figure 6 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water four times - ultraviolet irradiation for 2 minutes and then anti-fogging for 5 minutes;

[0050] Figure 7 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water four times - ultraviolet irradiation for 2 minutes - flushing with water once and then anti-fogging for 5 minutes;

[0051] Figure 8 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water four times - ultraviolet irradiation for 2 minutes - flushing with water twice and then anti-fogging for 5 minutes;

[0052] Figure 9 Results of anti-fogging of the anti-fogging coating prepared for Example 5 after 5 minutes of anti-fogging - flushing with water four times - ultraviolet irradiation for 2 minutes - flushing with water twice - ultraviolet irradiation for 2 minutes and then anti-fogging for 5 minutes. Detailed implementation manners

[0053] In order to make the technical means, creative features, achieved purposes and functions of the present invention clearer and easier to understand, the present invention will be further described below in conjunction with the accompanying drawings and specific implementation manners:

[0054] Example 1

[0055] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline and 0.01 g of p-methoxyphenol into a three-necked flask, heat it up to 100 °C under magnetic stirring, and continuously react for 6 hours to obtain monomer A4';

[0056] S2. The prepared monomer A4′ is separated and purified through a chromatography column. 8 g of the purified monomer A4′ is added to a three-necked flask, and then 200 ml of N,N-dimethylformamide is added. Stir in an ice-water bath at 0 °C for 20 min to obtain a mixed solution A;

[0057] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide and then add it to a 250-ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid, and perform an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C, then add 1.5 ml of concentrated sulfuric acid, and continue the ice-water bath for 20 min. Wait for the temperature to drop to 0 °C to obtain a mixed solution B;

[0058] S4. Add 1.7 g of sodium nitrite to a beaker, add 4 ml of deionized water and stir to dissolve. After complete dissolution, cool down for 20 min under ice-water bath conditions. Wait for the temperature to drop to 0 °C, and then drop the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After dropping, keep cooling for 20 min under ice-water bath conditions. Wait for the temperature to drop to 0 °C to obtain a mixed solution C;

[0059] S5. Slowly drop the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After dropping, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, and then vacuum dry at 38 °C for 3 d. Purify the dried solid through a chromatography column to obtain monomer A4;

[0060] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of 2-hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.84 g of N,N-dimethylacrylamide, and 0.8 g of fluorinated azobenzene to a three-necked flask. Heat and raise the temperature to 55 °C under magnetic stirring, and then add 0.36 g of azobisisobutyronitrile. Raise the temperature to 90 °C and continue to react for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer;

[0061] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, and then add 1.4 g of hexamethoxymelamine resin, 0.2 g of perfluorohexylethyl alcohol, 0.5 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. After mixing evenly, obtain an azobenzene-regulated amphiphilic copolymer composition;

[0062] S8. Spin-coat the azobenzene-regulated amphiphilic copolymer composition prepared in S7 on a substrate to make it evenly distributed on the substrate in a leveling manner. Then put it into a forced-air drying oven and cure at 110 °C for 10 min. Finally, form an anti-fog coating on the surface of the substrate.

[0063] Example 2

[0064] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline, and 0.01 g of p-methoxyphenol into a three-necked flask. Heat it up to 100 °C under magnetic stirring and continue to react for 6 hours to obtain monomer A4';

[0065] S2. Separate and purify the prepared monomer A4' through a chromatography column. Take 8 g of the purified monomer A4' and add it into a three-necked flask. Then add 200 ml of N,N-dimethylformamide and stir in an ice-water bath at 0 °C for 20 min to obtain mixed solution A;

[0066] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide and then add it into a 250-ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid and stir in an ice-water bath for 20 min. Wait until the temperature drops to 0 °C, then add 1.5 ml of concentrated sulfuric acid and continue to stir in an ice-water bath for 20 min. Wait until the temperature drops to 0 °C to obtain mixed solution B;

[0067] S4. Add 1.7 g of sodium nitrite into a beaker, add 4 ml of deionized water and stir to dissolve. After complete dissolution, cool it down for 20 min under ice-water bath conditions. Wait until the temperature drops to 0 °C, then drop the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After dropping, keep cooling in an ice-water bath for 20 min. Wait until the temperature drops to 0 °C to obtain mixed solution C;

[0068] S5. Slowly drop the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After dropping, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, then dry it in vacuo at 38 °C for 3 d. Purify the dried solid through a chromatography column to obtain monomer A4;

[0069] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of 2-hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.84 g of N,N-dimethylacrylamide, and 0.8 g of fluorinated azobenzene into a three-necked flask. Heat it up to 55 °C under magnetic stirring, then add 0.36 g of azobisisobutyronitrile, and continue to react at 90 °C for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer;

[0070] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 3.4 g of hexamethoxymelamine resin, 5 g of perfluorohexylethyl alcohol, 1.3 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. Mix them evenly to obtain an azobenzene-regulated amphiphilic copolymer composition;

[0071] S8. Spray the azobenzene-regulated amphiphilic copolymer composition prepared in S7 on the substrate so that it is evenly distributed on the substrate in a leveling manner. Subsequently, place it in a forced-air drying oven and cure it at 115 °C for 12 min. Finally, an anti-fog coating is formed on the surface of the substrate.

[0072] Example 3

[0073] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline, and 0.01 g of p-methoxyphenol to a three-necked flask. Heat it to 100 °C under magnetic stirring and react for 6 hours to obtain monomer A4'.

[0074] S2. Separate and purify the prepared monomer A4' through a chromatography column. Take 8 g of purified monomer A4' and add it to a three-necked flask. Subsequently, add 200 ml of N,N-dimethylformamide and stir in an ice-water bath at 0 °C for 20 min to obtain mixed solution A.

[0075] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide and add it to a 250 ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid and perform an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C, then add 1.5 ml of concentrated sulfuric acid and continue the ice-water bath for 20 min. Wait for the temperature to drop to 0 °C to obtain mixed solution B.

[0076] S4. Add 1.7 g of sodium nitrite to a beaker, add 4 ml of deionized water and stir to dissolve. After dissolution, cool it in an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C, then drop the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After dropping, keep cooling in an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C to obtain mixed solution C.

[0077] S5. Slowly drop the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After dropping, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, and then dry it in vacuo at 38 °C for 3 d. Purify the dried solid through a chromatography column to obtain monomer A4.

[0078] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of 2-hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.84 g of N,N-dimethylacrylamide, and 0.8 g of fluorinated azobenzene to a three-necked flask. Heat it to 55 °C under magnetic stirring, then add 0.36 g of azobisisobutyronitrile, and raise the temperature to 90 °C and continue to react for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer.

[0079] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 5.4 g of hexamethoxymelamine resin, 5 g of perfluorohexylethyl alcohol, 1.3 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. After mixing evenly, an azobenzene-regulated amphiphilic copolymer composition is obtained;

[0080] S8. Spin-coat the azobenzene-regulated amphiphilic copolymer composition prepared in S7 on the substrate, and make it evenly distributed on the substrate in a leveling manner. Subsequently, place it in a forced-air drying oven and cure it at 120 °C for 15 min. Finally, an anti-fog coating is formed on the surface of the substrate.

[0081] Example 4

[0082] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline, and 0.01 g of p-methoxyphenol to a three-necked flask. Heat it to 100 °C under magnetic stirring and react for 6 hours to obtain monomer A4';

[0083] S2. Separate and purify the prepared monomer A4' through a chromatography column. Take 8 g of the purified monomer A4' and add it to a three-necked flask. Subsequently, add 200 ml of N,N-dimethylformamide and stir in an ice-water bath at 0 °C for 20 min to obtain a mixed solution A;

[0084] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide and add it to a 250 ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid and perform an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C, then add 1.5 ml of concentrated sulfuric acid and continue the ice-water bath for 20 min. Wait for the temperature to drop to 0 °C to obtain a mixed solution B;

[0085] S4. Add 1.7 g of sodium nitrite to a beaker, add 4 ml of deionized water and stir to dissolve. After complete dissolution, cool it in an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C, then drop the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After dropping, maintain the cooling in an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C to obtain a mixed solution C;

[0086] S5. Slowly drop the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After dropping, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, then dry it in vacuo at 38 °C for 3 d. Purify the dried solid through a chromatography column to obtain monomer A4;

[0087] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of 2-hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.44 g of N,N-dimethylacrylamide, and 1.2 g of fluorinated azobenzene into a three-necked flask. Heat up to 55 °C under magnetic stirring, then add 0.36 g of azobisisobutyronitrile, and continue to react at 90 °C for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer.

[0088] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 1.4 g of hexamethoxymethyl melamine resin, 0.2 g of perfluorohexylethyl alcohol, 0.5 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. After mixing evenly, an azobenzene-regulated amphiphilic copolymer composition is obtained.

[0089] S8. Spin-coat the azobenzene-regulated amphiphilic copolymer composition prepared in S7 on a substrate to make it evenly distributed on the substrate in a leveling manner, then put it into a forced-air drying oven and cure it at 110 °C for 10 min. Finally, an anti-fog coating is formed on the surface of the substrate.

[0090] Example 5

[0091] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline, and 0.01 g of p-methoxyphenol into a three-necked flask. Heat up to 100 °C under magnetic stirring and react for 6 hours to obtain monomer A4'.

[0092] S2. Separate and purify the prepared monomer A4' through a chromatography column. Take 8 g of the purified monomer A4' and add it to a three-necked flask, then add 200 ml of N,N-dimethylformamide and stir in an ice-water bath at 0 °C for 20 min to obtain a mixed solution A.

[0093] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide, then add it to a 250 ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid, and stir in an ice-water bath for 20 min. When the temperature drops to 0 °C, add 1.5 ml of concentrated sulfuric acid and continue to stir in an ice-water bath for 20 min. When the temperature drops to 0 °C, a mixed solution B is obtained.

[0094] S4. Add 1.7 g of sodium nitrite into a beaker, add 4 ml of deionized water and stir to dissolve. After dissolution, cool down for 20 min under ice-water bath conditions. When the temperature drops to 0 °C, then drop the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After dropping, keep cooling in an ice-water bath for 20 min. When the temperature drops to 0 °C, a mixed solution C is obtained.

[0095] S5. Slowly add the mixed solution C prepared in S4 dropwise to the mixed solution A prepared in S2. After the addition is complete, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water at a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, then vacuum dry at 38 °C for 3 d, and purify the dried solid through a chromatography column to obtain monomer A4;

[0096] S6. Add 15 g of propylene glycol monomethyl ether, 15 g of n-propanol, 3 g of hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.44 g of N,N-dimethylacrylamide, and 1.2 g of fluorinated azobenzene to a three-necked flask. Heat and raise the temperature to 55 °C under magnetic stirring, then add 0.36 g of azobisisobutyronitrile, and continue to react at 90 °C for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer;

[0097] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 3.4 g of hexamethoxymelamine resin, 5 g of perfluorohexylethyl alcohol, 1.3 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. After mixing evenly, obtain an azobenzene-regulated amphiphilic copolymer composition;

[0098] S8. Spray the azobenzene-regulated amphiphilic copolymer composition prepared in S7 on the substrate, make it evenly distributed on the substrate in a leveling manner, then put it into a blast drying oven, cure at 115 °C for 13 min, and finally form an anti-fog coating on the surface of the substrate.

[0099] Example 6

[0100] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline, and 0.01 g of p-methoxyphenol to a three-necked flask. Heat and raise the temperature to 100 °C under magnetic stirring and continuously react for 6 hours to obtain monomer A4';

[0101] S2. Separate and purify the prepared monomer A4' through a chromatography column. Take 8 g of the purified monomer A4' and add it to a three-necked flask, then add 200 ml of N,N-dimethylformamide, and stir in an ice-water bath at 0 °C for 20 min to obtain mixed solution A;

[0102] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide and then add it to a 250 ml three-necked flask. Stir evenly, add 30 ml of glacial acetic acid, and perform an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C, then add 1.5 ml of concentrated sulfuric acid, and continue the ice-water bath for 20 min. Wait for the temperature to drop to 0 °C to obtain mixed solution B;

[0103] S4. Add 1.7 g of sodium nitrite into a beaker, add 4 ml of deionized water and stir to dissolve. After dissolution is completed, cool down for 20 min under an ice-water bath condition. Wait until the temperature drops to 0 °C, then drip the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After the dripping is completed, keep cooling for 20 min under an ice-water bath condition. Wait until the temperature drops to 0 °C to obtain a mixed solution C;

[0104] S5. Slowly drip the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After the dripping is completed, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, then vacuum dry at 38 °C for 3 d, and purify the dried solid through a chromatography column to obtain monomer A4;

[0105] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.44 g of N,N-dimethylacrylamide and 1.2 g of fluorinated azobenzene into a three-necked flask. Heat up to 55 °C under magnetic stirring, then add 0.36 g of azobisisobutyronitrile, and continue to react at 90 °C for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer;

[0106] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 5.4 g of hexamethoxymelamine resin, 5 g of perfluorohexylethyl alcohol, 1.3 g of p-toluenesulfonic acid monohydrate and 5 g of n-butanol. After mixing evenly, obtain an azobenzene-regulated amphiphilic copolymer composition;

[0107] S8. Pour the azobenzene-regulated amphiphilic copolymer composition prepared in S7 onto a substrate, and make it evenly distributed on the substrate in a leveling manner. Then put it into a blast drying oven and cure at 120 °C for 15 min. Finally, form an anti-fog coating on the surface of the substrate.

[0108] Example 7

[0109] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline and 0.01 g of p-methoxyphenol into a three-necked flask. Heat up to 100 °C under magnetic stirring and continuously react for 6 hours to obtain monomer A4′;

[0110] S2. Separate and purify the prepared monomer A4′ through a chromatography column. Take 8 g of the purified monomer A4′ and add it into a three-necked flask. Then add 200 ml of N,N-dimethylformamide and stir in an ice-water bath at 0 °C for 20 min to obtain a mixed solution A;

[0111] S3. Dissolve 4 g of 3-trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide, then add it to a 250-ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid, and place it in an ice-water bath for 20 min. Wait until the temperature drops to 0 °C, then add 1.5 ml of concentrated sulfuric acid, and continue the ice-water bath for 20 min. Wait until the temperature drops to 0 °C to obtain a mixed solution B;

[0112] S4. Add 1.7 g of sodium nitrite to a beaker, add 4 ml of deionized water and stir to dissolve. After dissolution, cool down for 20 min under ice-water bath conditions. Wait until the temperature drops to 0 °C, then drop the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After dropping, keep cooling for 20 min under ice-water bath conditions. Wait until the temperature drops to 0 °C to obtain a mixed solution C;

[0113] S5. Slowly drop the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After dropping, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, then vacuum dry at 38 °C for 3 d, and purify the dried solid through a chromatography column to obtain monomer A4;

[0114] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of 2-hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.04 g of N,N-dimethylacrylamide, and 1.6 g of fluorinated azobenzene to a three-necked flask. Heat up to 55 °C under magnetic stirring, then add 0.36 g of azobisisobutyronitrile, and continue to react at 90 °C for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer;

[0115] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 1.4 g of hexamethoxymelamine resin, 0.2 g of perfluorohexylethyl alcohol, 0.5 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. After mixing evenly, obtain an azobenzene-regulated amphiphilic copolymer composition;

[0116] S8. Spin-coat the azobenzene-regulated amphiphilic copolymer composition prepared in S7 on the substrate to make it evenly distributed on the substrate in a leveling manner. Then put it into a forced-air drying oven, cure at 110 °C for 10 min, and finally form an anti-fog coating on the surface of the substrate.

[0117] Example 8

[0118] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline, and 0.01 g of p-methoxyphenol to a three-necked flask. Heat up to 100 °C under magnetic stirring and continuously react for 6 hours to obtain monomer A4';

[0119] S2. Separate and purify the prepared monomer A4′ through a chromatography column. Take 8 g of the purified monomer A4′ and add it to a three-necked flask. Subsequently, add 200 ml of N,N-dimethylformamide and stir in an ice-water bath at 0 °C for 20 min to obtain a mixed solution A;

[0120] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide and then add it to a 250 ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid and perform an ice-water bath for 20 min. Wait for the temperature to drop to 0 °C, then add 1.5 ml of concentrated sulfuric acid and continue the ice-water bath for 20 min. Wait for the temperature to drop to 0 °C to obtain a mixed solution B;

[0121] S4. Add 1.7 g of sodium nitrite to a beaker, add 4 ml of deionized water and stir to dissolve. After complete dissolution, cool down for 20 min under ice-water bath conditions. Wait for the temperature to drop to 0 °C, and then drop the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After dropping, maintain the cooling for 20 min under ice-water bath conditions. Wait for the temperature to drop to 0 °C to obtain a mixed solution C;

[0122] S5. Slowly drop the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After dropping, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, and then vacuum dry at 38 °C for 3 d. Purify the dried solid through a chromatography column to obtain monomer A4;

[0123] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of 2-hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.04 g of N,N-dimethylacrylamide, and 1.6 g of fluorinated azobenzene to a three-necked flask. Heat and raise the temperature to 55 °C under magnetic stirring. Subsequently, add 0.36 g of azobisisobutyronitrile and raise the temperature to 90 °C and continue to react for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer;

[0124] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 3.4 g of hexamethoxymelamine resin, 5 g of perfluorohexylethyl alcohol, 1.3 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. After mixing evenly, obtain an azobenzene-regulated amphiphilic copolymer composition;

[0125] S8. Spray the azobenzene-regulated amphiphilic copolymer composition prepared in S7 on the substrate, make it evenly distributed on the substrate in a leveling manner, and then put it into a blast drying oven. After curing at 115 °C for 12 min, finally form an anti-fog coating on the surface of the substrate.

[0126] Example 9

[0127] S1. Add 40 g of N,N-dimethylformamide, 14 g of glycidyl methacrylate, 10 g of N-methylaniline, and 0.01 g of p-methoxyphenol into a three-necked flask. Heat it up to 100 °C under magnetic stirring and continue the reaction for 6 hours to obtain monomer A4'.

[0128] S2. Separate and purify the prepared monomer A4' through a chromatography column. Take 8 g of the purified monomer A4' and add it into a three-necked flask. Then add 200 ml of N,N-dimethylformamide and stir in an ice-water bath at 0 °C for 20 min to obtain mixed solution A.

[0129] S3. Dissolve 4 g of trifluoromethoxyaniline in 50 ml of N,N-dimethylformamide and then add it into a 250-ml three-necked flask. After stirring evenly, add 30 ml of glacial acetic acid and keep it in an ice-water bath for 20 min. Wait until the temperature drops to 0 °C, then add 1.5 ml of concentrated sulfuric acid and continue the ice-water bath for 20 min. Wait until the temperature drops to 0 °C to obtain mixed solution B.

[0130] S4. Add 1.7 g of sodium nitrite into a beaker, add 4 ml of deionized water and stir to dissolve. After complete dissolution, cool it down for 20 min under ice-water bath conditions. Wait until the temperature drops to 0 °C, then dropwise add the sodium nitrite aqueous solution into the mixed solution B prepared in S3. After the dropping is completed, keep cooling for 20 min under ice-water bath conditions. Wait until the temperature drops to 0 °C to obtain mixed solution C.

[0131] S5. Slowly drop the mixed solution C prepared in S4 into the mixed solution A prepared in S2. After the dropping is completed, continuously stir and react at 0 °C for 24 h. Dissolve the reacted solution in deionized water according to a mass ratio of 1:20. Wait for the product to precipitate, filter the product through a Buchner funnel, then dry it in vacuo at 38 °C for 3 d. Purify the dried solid through a chromatography column to obtain monomer A4.

[0132] S6. Add 15 g of propylene glycol monoether, 15 g of n-propanol, 3 g of 2-hydroxyethyl acrylate, 6 g of methyl methacrylate, 9.04 g of N,N-dimethylacrylamide, and 1.6 g of fluorinated azobenzene into a three-necked flask. Heat it up to 55 °C under magnetic stirring, then add 0.36 g of azobisisobutyronitrile, and raise the temperature to 90 °C and continue the reaction for 6 h to obtain a fluorinated azobenzene amphiphilic copolymer.

[0133] S7. Dissolve 8 g of the fluorinated azobenzene amphiphilic copolymer prepared in S6 in 6 g of n-propanol, then add 5.4 g of hexamethoxymelamine resin, 5 g of perfluorohexylethyl alcohol, 1.3 g of p-toluenesulfonic acid monohydrate, and 5 g of n-butanol. Mix them evenly to obtain an azobenzene-regulated amphiphilic copolymer composition.

[0134] S8. The azobenzene-regulated amphiphilic copolymer composition prepared in S7 is spin-coated on a substrate to be uniformly distributed on the substrate in a leveling manner, and then placed in a forced-air drying oven and cured at 120 °C for 15 min. Finally, an anti-fog coating is formed on the surface of the substrate.

[0135] The diazonium salts used in Examples 1-9 are not limited to trifluoromethoxyaniline, and may also be at least one of pentafluoroethoxyaniline, heptafluoron-propoxyaniline, and nonafluoron-butoxyaniline.

[0136] The film-forming performance, anti-fog performance, ultraviolet light-regulated anti-fog performance, hardness, and adhesion of the anti-fog coatings prepared in Examples 1-9 were respectively detected. The specific evaluation methods for each performance are as follows:

[0137] 1. Film-forming performance evaluation: Observe the leveling effect of the azobenzene-regulated amphiphilic copolymer composition on the surface of the substrate during natural surface drying and curing.

[0138] 2. Anti-fog performance evaluation: At room temperature and under laboratory atmospheric humidity conditions, place the substrate coated with the anti-fog coating 5 cm above the water surface at a temperature of 80 °C, with the side having the anti-fog coating facing down, and observe the fogging situation within 5 min.

[0139] 3. Ultraviolet light-regulated anti-fog performance evaluation: S1. Subject the substrate coated with the anti-fog coating to initial 5 min anti-fog - fixed water flow flushing for a fixed time - room temperature surface drying - second 5 min anti-fog - fixed water flow flushing for a fixed time - room temperature surface drying until the anti-fog coating fails to prevent fog; S2. Irradiate the anti-fog coating that has been flushed with water until anti-fog failure with ultraviolet light. After the irradiation is completed, test the substrate again according to S1. After the anti-fog coating on the surface of the substrate fails to prevent fog, irradiate it with ultraviolet light again. Repeat the above operations until the anti-fog coating on the surface of the substrate cannot restore the anti-fog effect after irradiation, and record the number of cycles of the repeated operations.

[0140] 4. Hardness evaluation: Test the hardness of the anti-fog coating on the surface of the substrate according to the standard of GB / T 6739-2006. If the hardness reaches 1H, it is judged that the hardness performance is excellent.

[0141] 5. Adhesion evaluation: Use a cross cutter to cut the anti-fog coating on the surface of the substrate into several pieces of 1×1 cm 2 size, then use 3M tape to press on the surface of the anti-fog coating and quickly tear it off, and observe whether the cut pieces fall off.

[0142] The results of the detection using the above evaluation methods are shown in the following table. The anti-fog performance of the anti-fog coating prepared in Example 5 and the performance of the anti-fog coating after ultraviolet light regulation are as Figures 1-9 shown.

[0143]

[0144]

[0145] Note: "√" in the table indicates excellent performance.

[0146] As shown in the above table, in the anti-fog coatings prepared in Examples 1, 4, and 7, the surfactant is only 0.2 g, resulting in a low surface energy of the azobenzene-regulated amphiphilic copolymer composition and poor anti-fog performance.

[0147] Moreover, for the anti-fog coatings prepared in Examples 1, 4, and 7, due to the simultaneous decrease of the acidic catalyst and the cross-linking agent, the amount of protons (H+) provided by the acidic catalyst becomes less and the catalytic rate becomes lower. At the same time, the condensation reaction between the hexa-methoxymelamine resin and -OH in the fluorinated azobenzene amphiphilic copolymer under acidic conditions forms fewer C-O-C cross-linking networks. Therefore, the hardness of the anti-fog coatings prepared in Examples 1, 4, and 7 is lower.

[0148] For the anti-fog coatings prepared in Examples 3, 6, and 9, the amount of the cross-linking agent and the catalyst is increased, resulting in an increase in the number of stable cross-linking networks formed by the cleavage of ether bonds, an improvement in the curing degree of the anti-fog coatings, and a decrease in the loss degree of the surfactant and hydrophilic groups, so that the maximum number of flushing times increases from 3 to 4. However, due to the too high curing degree, after ultraviolet irradiation, due to steric hindrance, the N=N bond of the azobenzene group cannot rotate. After the anti-fog coating fails to function due to flushing and is irradiated with ultraviolet light of 1000 w and 1500 w for 2 - 3 min, its anti-fog effect cannot be restored, and the maximum number of cycles is 0.

[0149] Compared with Examples 1 - 3, the anti-fog coatings prepared in Examples 4 - 5 contain 1.2 g of fluorinated azobenzene, which increases the number of azobenzene functional groups that can undergo cis / trans isomerization. And during the process of increasing the hydrophobic fluorinated azobenzene amphiphilic copolymer, the anti-fog performance of the anti-fog coating does not decrease significantly, and the hardness and adhesion do not change. Moreover, after the anti-fog coating fails to function and is irradiated with ultraviolet light of 1000 w and 1500 w for 2 - 3 min, the N=N bond absorbs energy and rotates, and the azobenzene group undergoes a transformation from trans to cis, causing the hydrophobic group with fluorine at its end to curl from the outer layer to the inner layer, increasing the surface energy and restoring the anti-fog effect of the anti-fog coating, and the maximum number of cycles reaches 1.

[0150] Compared with Examples 1 - 6, the anti-fog coatings prepared in Examples 7 - 9 contain 1.6 g of fluorinated azobenzene, and the content of azobenzene groups that can undergo cis / trans isomerization is more, making the anti-fog coating more hydrophobic.

[0151] The anti-fog coating prepared in Example 8, although it can maintain good film-forming property, anti-fog property, hardness and adhesion, has a lower content of N,N-dimethylacrylamide compared with other examples, which increases the F content in the amphiphilic copolymer composition regulated by azobenzene, increases the hydrophobicity, and increases the initial water contact angle, resulting in the loss of the anti-fog effect of the anti-fog coating after flushing three times. However, after being irradiated with ultraviolet light at a power of 1000w and 1500w for 2-3 minutes, the N=N bond absorbs energy and rotates, and the azobenzene group undergoes a trans-cis transformation. The fluorine-containing hydrophobic group at the end curls from the outer layer to the inner layer, and the anti-fog coating restores the anti-fog effect, with the maximum number of cycles reaching 1.

[0152] The anti-fog coatings prepared in Examples 1-9 have strong ultraviolet absorption peaks of the azobenzene group at 320nm-350nm, 450nm, and 500-700nm. Therefore, the transmittance of the azobenzene group in the visible light range is relatively low. The more the content of the azobenzene group, the lower the visible light transmittance of the anti-fog coating. Therefore, the visible light transmittance: Examples 1-3 > Examples 4-6 > Examples 7-9.

[0153] Compared with Examples 1-2, the anti-fog coating prepared in Example 3 increases the irradiation power and time of ultraviolet light. Since the content of the azobenzene group in the anti-fog coatings prepared in Examples 1-3 is relatively low, after increasing the excitation energy, all the azobenzene groups will undergo cis-trans isomerization, resulting in an increased surface energy that is not sufficient to restore the anti-fog performance.

[0154] Compared with the anti-fog coating prepared in Example 5, although the irradiation time and power conditions of ultraviolet light are increased in Example 6, the maximum number of cycles of the anti-fog coating prepared in Example 5 is 1 while that in Example 6 is 0. This is because the azobenzene groups in the anti-fog coating prepared in Example 6 are limited. With the increase in the number of flushing times, the loss of the surfactant increases, resulting in a weaker ability to increase the surface energy of the anti-fog coating, that is, a weaker ability to reduce the water contact angle. The inherent water contact angle of the anti-fog coating gradually increases. Therefore, the water contact angle reduced by the cis-trans isomerization of the azobenzene group under the action of ultraviolet light cannot make the anti-fog coating return to the threshold of the water contact angle for anti-fogging, so the maximum number of cycles cannot be increased.

[0155] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered by the scope of the claims of the present invention.

Claims

1. An azobenzene-regulated amphiphilic copolymer composition, characterized in that, By mass fraction, it includes 5 - 35 parts of fluorinated azobenzene amphiphilic copolymer, 5 - 50 parts of crosslinking agent, 0.5 - 15 parts of surfactant, 0.2 - 5 parts of acidic catalyst, 0.1 - 0.8 parts of initiator, and 40 - 90 parts of solvent I.

2. A kind of azobenzene - regulated amphiphilic copolymer composition according to claim 1, characterized in that The fluorinated azobenzene amphiphilic copolymer includes: Monomer A1, which is an acrylate monomer with a hydroxyl functional group; Monomer A2, which is a vinyl monomer with a hydrophobic functional group; Monomer A3, which is a vinyl monomer with a hydrophilic functional group; and Monomer A4, which is a fluorinated azobenzene acrylic monomer; The number - average molecular weight of the fluorinated azobenzene amphiphilic copolymer is 5000 - 100000, and its structural schematic diagram is: Where x, y, z, and m respectively represent the polymerization degrees of monomer A1, monomer A2, monomer A3, and monomer A4; R1 is an alkyl group containing a hydroxyl group, and R2 is H or CH3; R3 is an alkyl group, and R4 is H or CH3; R5, R6, and R7 are H or CH3; R8 is H or CH3, and R9 is one of the functional groups OCF3, OCF2CF3, OCF2CF2CF3, OCF2CF2CF2CF3.

3. An azobenzene-regulated amphiphilic copolymer composition according to claim 2, characterized in that, By mass fraction, the content of monomer A1 is 10% - 20%, the content of monomer A2 is 20% - 60%, the content of monomer A3 is 20% - 60%, and the content of monomer A4 is 2% - 20%.

4. An azobenzene-regulated amphiphilic copolymer composition according to claim 2, characterized in that, Monomer A1 is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; Monomer A2 is at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate; Monomer A3 is at least one of acrylamide, methacrylamide, N - methylmethacrylamide, N,N - dimethylacrylamide, and N,N - diethylacrylamide.

5. A kind of azobenzene - regulated amphiphilic copolymer composition according to claim 1, characterized in that The crosslinking agent is at least one of melamine - formaldehyde resin, hexamethoxymelamine resin, and hexamethoxymethylmelamine resin; The surfactant is at least one of perfluoroethyl ethyl alcohol, perfluoropropyl ethyl alcohol, perfluorobutyl ethyl alcohol, perfluorohexyl ethyl alcohol, perfluorooctyl ethyl alcohol, and perfluoroalkyl ethyl alcohol; The acidic catalyst is at least one of p - toluenesulfonic acid monohydrate, hydrochloric acid, and sulfuric acid; The solvent I is at least one of alcohol solvents, ether solvents, ester solvents, aromatic solvents, amides, and water; the initiator is azobisisobutyronitrile.

6. A method for preparing an azobenzene-regulated amphiphilic copolymer composition according to any one of claims 1-5, characterized in that, It includes the following steps: S1. Monomer A4 is prepared by the ring - opening reaction of (meth) acrylic acid glycerol ether and N - methylaniline and the diazo coupling reaction of its product; S2. Weigh monomers A1, A2, A3, A4 prepared in S1, and the initiator, then add each component into solvent II and react at 70 - 100 °C for 3 - 24 h to obtain the fluorinated azobenzene amphiphilic copolymer; S3. Weigh out the crosslinking agent, surfactant, acidic catalyst, and solvent I, mix them evenly with the fluorinated azobenzene amphiphilic copolymer prepared in S2 to obtain an azobenzene-regulated amphiphilic copolymer composition.

7. An azobenzene-regulated amphiphilic copolymer composition according to claim 6, characterized in that, The specific steps for preparing monomer A4 in step S1 are as follows: S11. React N,N-dimethylformamide, glycidyl methacrylate, N-methylaniline, and p-methoxyphenol under stirring and heating conditions to obtain monomer A4'; S12. Purify the monomer A4' obtained in S11, dissolve the purified monomer A4' in N,N-dimethylformamide and stir evenly, then carry out a diazo coupling reaction with the diazonium salt, and then obtain monomer A4 after separation and purification.

8. An azobenzene-regulated amphiphilic copolymer composition according to claim 6, characterized in that In step S2, the solvent II is at least one of an alcohol solvent, an ether solvent, an ester solvent, an aromatic solvent, and an amide solvent.

9. Application of an azobenzene-regulated amphiphilic copolymer composition according to any one of claims 1-5 in a visual optical material.

10. Use of an azobenzene-regulated amphiphilic copolymer composition according to claim 9 in a visual optical material, characterized in that, The specific steps are as follows: Coat the azobenzene-regulated amphiphilic copolymer composition on the surface of the substrate by spin coating, spraying, or dip coating processes, then heat and cure at 110-120 °C for 10-15 min, and finally form an anti-fog coating on the surface of the substrate.

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