A self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating, its preparation method and application

Abstract

The present invention provides a self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating, a preparation method thereof and an application thereof, belonging to the field of coatings. The method for preparing the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating comprises the following steps: (1) preparation of a prepolymer; (2) preparation of an organic super-hydrophilic polymer emulsion; (3) preparation of a calcium phosphate oligomer; (4) preparation of the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating. The self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating prepared by the preparation method provided by the present invention, and the super-hydrophilic organic-inorganic composite anti-fog coating obtained by coating, have excellent super-hydrophilicity, high adhesion, self-healing property and high visible light transmittance, and at the same time have excellent anti-fog performance, and can be effectively used in the fields of spectacle lenses, chemical or biological protection masks, vehicle windshields, solar panels, etc.

Description

Technical Field

[0001] The present invention belongs to the field of coatings, and particularly relates to a self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating, a preparation method thereof and an application thereof. Background Art

[0002] Super-hydrophilic coatings are widely used in transparent materials such as automotive glass, lenses, and photovoltaic modules due to their excellent self-cleaning and anti-fogging effects. Currently, various methods for preparing super-hydrophilic coatings have been developed, including template method, phase separation method, layer-by-layer self-assembly method, and chemical vapor deposition method, etc. However, the above methods are mostly involved in factors such as expensive production equipment and complex process procedures, making it difficult to realize the production and preparation of large-area coatings. In contrast, the coating method using waterborne coatings has the advantages of low equipment cost, simple and controllable reaction process, wide range of applicable substrates, and being conducive to large-scale preparation. However, the main active ingredient of currently commercially available super-hydrophilic anti-fog coating products is small molecule surfactants, which, although having a certain anti-fogging effect, are prone to losing their anti-fogging performance in humid environments or under conditions such as rain washing, and have a short lifespan. And the super-hydrophilic coatings of pure organic polymers have disadvantages such as poor water resistance and poor wear resistance, and are prone to swelling and peeling off in humid environments, and it is also difficult to achieve long-term super-hydrophilic anti-fogging effects. Therefore, the composite preparation of inorganic nanoparticles and organic polymers to form high-performance super-hydrophilic anti-fog coatings has become a research hotspot. Common inorganic components include silica sol, alumina sol, or titania sol, etc. However, agglomeration of inorganic components is prone to occur during the doping process, resulting in the coating turning white, thereby affecting the visible light transmittance and limiting its application in the field of transparent materials. Therefore, developing transparent super-hydrophilic coatings with long-term water resistance and high wear resistance has important scientific research value and commercial application value. Summary of the Invention

[0003] The purpose of the present invention is to provide a self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating, a preparation method thereof and an application thereof, which are used to solve problems such as water vapor atomization on the surface of transparent substrates, low visible light transmittance, poor wear resistance, and poor healing performance existing in the prior art.

[0004] In order to achieve the above purpose or other purposes, the present invention is realized through the following technical solutions.

[0005] A method for preparing a self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating, comprising the following steps: (1) preparation of a prepolymer; (2) preparation of an organic super-hydrophilic polymer emulsion; (3) preparation of a calcium phosphate oligomer; (4) preparation of a self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating.

[0006] Specifically, it includes the following steps:

[0007] (1) Preparation of prepolymer: Add the initiator to Solvent I for dissolution, add the emulsifier, and stir evenly to obtain a mixed solution; Mix the acrylic monomers and methacrylate monomers evenly, and then dropwise add them to the above mixed solution under stirring. After the dropping is completed, carry out the reaction under nitrogen protection. After the reaction is completed, perform a cooling treatment to obtain the prepolymer;

[0008] (2) Preparation of organic superhydrophilic polymer emulsion: Take the ionic monomer and the initiator, add Solvent II, and stir until dissolved. Then, dropwise add the prepolymer obtained in step (1) to the solution. After the dropping is completed, add the emulsifier and stir evenly. Carry out a heating reaction under nitrogen protection. After the reaction is completed, perform a cooling treatment to obtain the organic superhydrophilic polymer emulsion;

[0009] (3) Preparation of calcium phosphate oligomer: Add anhydrous calcium chloride to absolute ethanol, add triethylamine, and add the mixed solvent of phosphoric acid and ethanol under stirring, and carry out a stirring reaction. After the reaction is completed, obtain the calcium phosphate oligomer through post-treatment; Disperse the calcium phosphate oligomer in absolute ethanol to obtain a calcium phosphate oligomer dispersion;

[0010] (4) Preparation of self-healing, highly wear-resistant, superhydrophilic and antifogging coating: Take the organic superhydrophilic polymer emulsion obtained in step (2), dropwise add the diluent, and stir until evenly dispersed to obtain a diluted emulsion; Centrifuge the calcium phosphate oligomer dispersion obtained in step (3), and add the centrifuged product, calcium phosphate oligomer, to the above diluted emulsion, and ultrasonically stir evenly to obtain the self-healing, highly wear-resistant, superhydrophilic and antifogging coating.

[0011] Further, the initiator is selected from persulfate compounds. Preferably, the initiator is selected from one or more of potassium persulfate, sodium persulfate, and ammonium persulfate;

[0012] Further, the emulsifier is selected from non-ionic emulsifiers. Preferably, the emulsifier is selected from one or more of Tween-80, OP-10, and AEO-3;

[0013] Further, the Solvent I is selected from one or more of water, ethanol, propylene glycol monomethyl ether acetate, butyl acetate, and ethyl acetate.

[0014] Further, the acrylic monomers are selected from one or more of acrylic acid, hydroxyethyl acrylate, methyl acrylate, ethyl acrylate, hydroxypropyl acrylate, and tert-butyl acrylate.

[0015] Further, the methacrylate monomers are selected from one or more of methacrylic acid and methyl methacrylate.

[0016] Further, the dropping rate in step (1) is 1 - 10 mL / min.

[0017] Further, in step (1), the mass ratio of the initiator to the emulsifier is (1 to 5):(5 to 10).

[0018] Further, in step (1), the mass ratio of the initiator to the total amount of the acrylic monomer and the methacrylate monomer is (1 to 8):(35 to 200).

[0019] Further, in step (1), the mass ratio of the total amount of the acrylic monomer and the methacrylate monomer to the solvent is (1 to 5):(5 to 100).

[0020] Further, in step (1), the reaction temperature is 50 to 90 °C, and the reaction time is 0.5 to 6 h.

[0021] Further, in step (2), the ionic monomer is selected from one or more of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl dimethyl benzyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, sodium methallyl sulfonate, and sodium p-styrene sulfonate.

[0022] Further, in step (2), the solvent II is selected from one or more combinations of water, ethanol, propylene glycol methyl ether acetate, isopropanol, and glycerol.

[0023] Further, in step (2), the mass ratio of the initiator to the ionic monomer is (1 to 9):(10 to 200).

[0024] Further, in step (2), the mass ratio of the ionic monomer to the prepolymer is (1 to 7):(1 to 120).

[0025] Further, in step (2), the mass ratio of the ionic monomer to the solvent II is (1 to 5):(5 to 10).

[0026] Further, in step (2), the dropping rate of the prepolymer is 0.5 to 10 mL / min.

[0027] Further, in step (2), the reaction temperature is 50 to 90 °C, and the reaction time is 3 to 24 h.

[0028] Further, after the reactions in steps (1) and (2) are completed, the cooling treatment is carried out using an ice-water bath.

[0029] Further, in step (3), the mass concentration of anhydrous calcium chloride in absolute ethanol is 1 - 100 mg / mL;

[0030] Further, in step (3), the mass concentration of triethylamine relative to absolute ethanol is 0.2 - 10 g / mL;

[0031] Further, in step (3), the volume ratio of phosphoric acid to ethanol in the mixed solvent is (1-6):(6-50);

[0032] Further, in step (3), the concentration of the calcium phosphate oligomer dispersion is 2-500 mg / mL.

[0033] After the reaction in step (3), it is washed with absolute ethanol and centrifuged, and the number of washing and centrifugation times includes but is not limited to 3 times; after the reaction in the present invention, it can be washed and centrifuged with absolute ethanol multiple times to remove the unreacted triethylamine and obtain calcium carbonate oligomers.

[0034] Further, in step (4), the mass ratio of the organic superhydrophilic polymer emulsion to the diluent is (1-5):(1-80);

[0035] Further, in step (4), the diluent is selected from one or more of water, ethanol, propylene glycol methyl ether acetate, isopropanol, glycerol, and butyl acetate;

[0036] Further, in step (4), the stirring speed is 500-4000 rpm;

[0037] Further, in step (4), the stirring time is 0.5-2 h;

[0038] Further, in step (4), the drying temperature is 70 °C;

[0039] Further, in step (4), the amount of calcium phosphate oligomer added accounts for 0.1%-20% of the mass of the added emulsion.

[0040] The present invention also discloses a self-healing, highly wear-resistant, superhydrophilic and antifogging coating prepared by the above method.

[0041] The present invention also protects a self-healing, highly wear-resistant, superhydrophilic and antifogging coating comprising the above self-healing, highly wear-resistant, superhydrophilic and antifogging coating.

[0042] The preparation method of the super self-healing, highly wear-resistant, superhydrophilic and antifogging coating includes the following steps: uniformly coating the self-healing, highly wear-resistant, superhydrophilic and antifogging coating on the surface of a glass substrate and drying to obtain the self-healing, highly wear-resistant, superhydrophilic and antifogging coating.

[0043] Among them, the coating method can be a conventional method in the art such as spin coating or dip coating. The coating amount of the emulsion during coating is 0.1-10 g / m 2 . The drying temperature is 45-90 °C.

[0044] The present invention also protects the application of the above self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating in the fields of glasses, protective masks, windshields, and solar panels.

[0045] In the present invention, a multifunctional super-hydrophilic resin is obtained by free radical polymerization of a monomer containing an ionic group and an acrylate or methacrylate monomer. The ionic structural unit provides strong hydrophilicity, and the acrylate or methacrylate structural unit adjusts the softness, hardness and glass transition temperature of the polymer. Subsequently, a calcium phosphate oligomer is introduced as an inorganic component into the aqueous resin. Its particles have extremely small particle sizes and are not prone to agglomeration in the solution. In addition, due to the interaction (ionic crosslinking and hydrogen bonding) between Ca 2+ and PO4 3- molecules and organic molecules, a strong bond is formed between the organic polymer network and the ultrafine inorganic CPO (calcium phosphate oligomer) nanowires, thereby forming a highly continuous and dense nanostructure, which not only increases the visible light transmittance, but also helps to avoid the wear resistance of the anti-fog coating and realizes a long service life in a humid environment.

[0046] The coating in the present invention is composed of an ionic monomer, an acrylic monomer, a methacrylate monomer, and a calcium phosphate oligomer. The methacrylate structural unit is beneficial to improving the self-healing property and hardness of the coating, while the acrylic structural unit improves the adhesion of the resin and adjusts the glass transition temperature. Through ionic crosslinking and hydrogen bonding between the inorganic calcium phosphate oligomer and the organic polymer, a highly continuous and dense nanostructure is formed, improving the water resistance and friction resistance of the coating, and preventing peeling or swelling in a humid environment. This coating can form a physical hydrophilic layer on the glass surface, inhibit the formation of fog, and effectively eliminate the influence of fog formation on the surface of the transparent substrate on the use of the transparent substrate.

[0047] In summary, the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating prepared by the preparation method provided by the present invention has excellent super-hydrophilicity, high adhesion, self-healing property, and high visible light transmittance, and at the same time has excellent anti-fog performance, and can be effectively used in the fields of glasses lenses, chemical or biological protective masks, vehicle windshields, solar panels, etc. Description of the Drawings

[0048] Figure 1 Among them, Figure 1 (a) is a physical picture of the calcium phosphate oligomer dispersion; Figure 1 (b) is the particle size distribution diagram and powder schematic diagram of the calcium phosphate oligomer; Figure 1 (c) is the XRD curve of the calcium phosphate oligomer; Figure 1 (d) is the infrared spectrum of the calcium phosphate oligomer.

[0049] Figure 2 Among them, Figure 2 (a) is the physical diagram of the hot fog test and the contact angle test result of the blank glass slide; Figure 2 (b) is the physical diagram of the hot fog test and the contact angle test result of the anti-fog coating prepared in Example 1 of the present invention; Figure 2 (c)(d) are the physical diagrams of the self-healing, highly wear-resistant, and super-hydrophilic anti-fog coating of the present invention.

[0050] Figure 3 are the physical diagrams of the hot fog test and the contact angle test results of the anti-fog coatings obtained in Examples 2 to 7 of the present invention.

[0051] Figure 4 are the physical photos of the coated sheets at different stages of the self-healing, highly wear-resistant, and super-hydrophilic anti-fog coating prepared in Example 2 of the present invention: (a) before scratching; (b) after scratching; (c) during the hot fog experiment; (d) after the hot fog experiment.

[0052] Figure 5 are the hot fog test experiments and contact angle test results of the anti-fog coating prepared by the present invention and the coating prepared by the commercially available paint, where Figure 5 (a) is the physical diagram of the hot fog test result and the contact angle test result of the commercially available anti-fog coating after ultraviolet aging; Figure 5 (b) is the physical diagram of the hot fog test result and the contact angle test result of the self-healing, highly wear-resistant, and super-hydrophilic anti-fog coating prepared by the present invention. Figure 5 (c) is the ultraviolet-visible spectrum of the commercially available anti-fog coating, the blank glass slide, and the anti-fog coating prepared by the present invention.

[0053] Figure 6 are the hot fog tests of the anti-fog coating prepared by the present invention and the coating prepared by the commercially available paint after being soaked in distilled water for 2 h, where Figure 6 (a) is the physical photo of the hot fog test of the commercially available coating, Figure 6 (b) is the physical photo of the hot fog test of the anti-fog coating of Example 1.

[0054] Figure 7 is the adhesion test diagram of the anti-fog coating prepared by the present invention.

[0055] Figure 8 are the friction resistance test results of the coating without adding calcium phosphate oligomer, the anti-fog coatings of Example 1 and Example 2. Detailed implementation manners

[0056] The following describes the implementation modes of the present invention through specific specific examples. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation modes. All details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0057] It should be noted that, without conflict, the following examples and the features in the examples can be combined with each other. It should also be understood that the terms used in the embodiments of the present invention are for describing specific specific implementation schemes, rather than for limiting the protection scope of the present invention. The test methods without specific conditions noted in the following examples are usually carried out according to conventional conditions, or according to the conditions recommended by each manufacturer.

[0058] When the examples give numerical ranges, it should be understood that unless otherwise specified in the present invention, both endpoints of each numerical range and any value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention, based on the understanding of those skilled in the art of the prior art and the description of the present invention, can also use any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention to implement the present invention.

[0059] The following further illustrates the present invention through specific examples, but the present invention is not limited thereto. The specific protection scope is shown in the claims.

[0060] Example 1

[0061] Preparation of prepolymer: First, 0.7 g of ammonium persulfate initiator, 3.2 g of Tween-80 emulsifier, 300 mL of deionized water, and 180 mL of ethanol were added to a single-necked flask equipped with a magnetic stir bar, and then magnetically stirred at room temperature for 15 min; Another 20 g of tert-butyl acrylate and 50 g of methacrylic acid monomer were weighed and mixed evenly, and then added dropwise to the above mixed solution at a rate of 2.5 mL / min under stirring conditions. After the addition was completed, the reaction was stirred at 60 °C for 5 h under nitrogen protection. After the reaction was completed, it was immediately transferred to an ice-water bath for cooling to obtain the prepolymer.

[0062] Preparation of organic superhydrophilic polymer emulsion: First, 4.0 g of methacryloyloxyethyltrimethylammonium chloride, 0.06 g of ammonium persulfate, 18 mL of deionized water, and 6 mL of isopropanol were added to a single-necked flask equipped with a magnetic stir bar and stirred at room temperature until completely dissolved. 18 mL of the prepolymer obtained in step (1) was slowly added dropwise to the above solution at a dropping rate of 3 mL / min. After the addition was completed, it was stirred at room temperature until evenly dispersed. Subsequently, the temperature was raised to 80 °C and the reaction was carried out for 8 h under nitrogen protection. After the reaction was completed, it was immediately cooled with an ice-water bath to obtain the superhydrophilic polymer emulsion.

[0063] Preparation of calcium phosphate oligomers: 10.0 g of anhydrous calcium chloride was dissolved in 2 L of anhydrous ethanol, and then transferred to a flask equipped with a magnet. Subsequently, 500 mL of triethylamine was added to the above solution, and magnetic stirring was performed at room temperature for 30 min. Then, 6 mL of phosphoric acid solution was dissolved in 120 mL of anhydrous ethanol and added to the above solution. The reaction was magnetically stirred at room temperature for 12 h. After the reaction was completed, the solution was repeatedly washed with anhydrous ethanol and centrifuged to precipitate. Finally, the centrifuged product was dispersed in 1.0 L of anhydrous ethanol to obtain a calcium phosphate oligomer dispersion.

[0064] Self-healing highly wear-resistant super-hydrophilic anti-fog coating and preparation of corresponding anti-fog coating

[0065] 6.0 g of the polymer emulsion obtained in step (2) was slowly added dropwise to 80 mL of deionized water under stirring conditions, and stirred at room temperature for 2 h until uniformly dispersed. Then 10 mg of the calcium phosphate oligomer obtained in step (3) was added, and stirring was continued at room temperature for 2 h to obtain a uniform coating liquid. The coating liquid was coated on the surface of the glass substrate by spin coating, and then dried at 70° C. to obtain a coating sheet with a super hydrophilic anti-fog coating.

[0066] Example 2

[0067] Preparation of prepolymer: 0.8g ammonium persulfate initiator, 4.0g AEO-3 emulsifier, 350mL deionized water, and 190mL propylene glycol methyl ether acetate were added to a single-mouth bottle equipped with a magnetic device, and then magnetically stirred for 15 minutes at room temperature; 18g tert-butyl acrylate and 50g methacrylic acid monomer were weighed and mixed evenly, and then slowly added to the above mixed solution at a speed of 2.5mL / min under stirring conditions. After the addition was completed, the mixture was stirred at 60°C for 3h under nitrogen protection. After the reaction was completed, it was immediately moved to an ice water bath to be fully cooled to obtain a prepolymer.

[0068] Preparation of organic super-hydrophilic polymer emulsion: 4.0g methacryloyloxyethyl trimethylammonium chloride, 0.06g ammonium persulfate, 18mL deionized water and 6mL ethanol are added to a single-mouth bottle equipped with a magnet in sequence, and stirred at room temperature until completely dissolved. 20mL of the prepolymer obtained in step (1) is slowly dripped into the above solution at a dripping speed of 3mL / min. After the dripping is completed, it is stirred at room temperature until uniformly dispersed. The reaction is carried out at 90°C under nitrogen protection for 6h. After the reaction is completed, it is immediately cooled in an ice water bath to obtain a super-hydrophilic organic polymer emulsion.

[0069] Preparation of calcium phosphate oligomer: Dissolve 9.0 g of anhydrous calcium chloride in 2 L of anhydrous ethanol, then transfer it to a flask equipped with a magnetic stir bar. Subsequently, add 300 mL of triethylamine to the above solution, and stir magnetically at room temperature for 30 min. Then, dissolve 6 mL of phosphoric acid solution in 250 mL of anhydrous ethanol and add it to the above solution, and stir magnetically at room temperature for 12 h. After the reaction is completed, wash it repeatedly with anhydrous ethanol and then centrifuge the precipitate. Finally, dissolve the centrifuged product in 1.0 L of anhydrous ethanol to obtain a calcium phosphate oligomer dispersion.

[0070] Preparation of self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating and corresponding anti-fog coating

[0071] Take 8.0 g of the polymer emulsion obtained in step (2) and slowly add it dropwise to 100 mL of deionized water under stirring conditions, stir at room temperature for 2 h until evenly dispersed, then add 8 mg of calcium phosphate oligomer, and then stir at room temperature for 1.5 h. The mixed solution is uniformly coated on the surface of a glass substrate by spin coating, and then dried at 70 °C to obtain a coated glass substrate sheet with a super-hydrophilic and anti-fog functional coating.

[0072] Example 3

[0073] Preparation of prepolymer: Sequentially add 1.0 g of potassium persulfate initiator, 4.0 g of Tween-80 emulsifier, 400 mL of ethanol, and 200 mL of ethyl acetate to a single-necked flask equipped with a magnetic stir bar, and then stir magnetically at room temperature for 15 min; separately weigh 15 g of ethyl acrylate and 45 g of methacrylic acid monomer and mix them evenly, and then slowly add them dropwise to the above mixed solution at a rate of 10 mL / min under stirring conditions. After the dropping is completed, stir and react at 60 °C for 4 h under nitrogen protection. Immediately transfer it to an ice-water bath and cool it sufficiently after the reaction is completed to obtain a prepolymer.

[0074] Preparation of organic super-hydrophilic polymer emulsion: Sequentially add 4.0 g of methacryloyloxyethyltrimethylammonium chloride, 0.06 g of potassium persulfate, 20 mL of deethanol, and 8 mL of isopropanol to a single-necked flask equipped with a magnetic stir bar, and stir at room temperature until completely dissolved. Slowly add 15 mL of the prepolymer obtained in step (1) to the above solution at a dropping rate of 1 mL / min. After the dropping is completed, stir at room temperature until evenly dispersed. React at 80 °C for 8 h under nitrogen protection, and immediately cool it with an ice-water bath after the reaction is completed to obtain an emulsion of super-hydrophilic organic polymer.

[0075] Preparation of calcium phosphate oligomer: Dissolve 15.0 g of anhydrous calcium chloride in 2 L of anhydrous ethanol, then transfer it to a flask equipped with a magnetic stir bar. Then add 800 mL of triethylamine to the above solution and stir magnetically at room temperature for 30 min. Then dissolve 10 mL of phosphoric acid solution in 300 mL of anhydrous ethanol and add it to the above solution, and stir magnetically at room temperature for 12 h. After the reaction is completed, wash it repeatedly with anhydrous ethanol and then centrifuge the precipitate. Finally, dissolve the centrifuged product in 2.0 L of anhydrous ethanol to obtain a calcium phosphate oligomer dispersion.

[0076] Preparation of Self-healing, Highly Wear-resistant, Super-hydrophilic and Anti-fog Coating and Corresponding Anti-fog Coating

[0077] Take 5.0 g of the polymer emulsion obtained in step (2) and slowly add it dropwise to 80 mL of isopropanol under stirring conditions, stir at room temperature for 2 h until evenly dispersed, then add 800 mg of calcium phosphate oligomer, and then stir at room temperature for 2 h. The mixed solution is evenly coated on the surface of a glass substrate by spin coating, and then dried at 70 °C to obtain a glass substrate coated sheet with a super-hydrophilic and anti-fog functional coating.

[0078] Example 4

[0079] Preparation of prepolymer: Add 0.8 g of sodium persulfate initiator, 0.8 g of OP-10 emulsifier, 500 mL of deionized water, and 150 mL of ethyl acetate to a single-necked flask equipped with a magnetic stir bar in sequence, and then stir magnetically at room temperature for 15 min; separately weigh 15 g of acrylic acid and 35 g of methacrylic acid monomers and mix them evenly, and then slowly add them dropwise to the above mixed solution at a rate of 5.0 mL / min under stirring conditions. After the addition is completed, stir and react at 90 °C for 1 h under nitrogen protection. Immediately transfer it to an ice-water bath for sufficient cooling after the reaction is completed to obtain a prepolymer.

[0080] Preparation of organic super-hydrophilic polymer emulsion: Add 4.0 g of sodium p-styrenesulfonate, 0.06 g of sodium persulfate, 20 mL of deionized water, and 10 mL of isopropanol to a single-necked flask equipped with a magnetic stir bar in sequence, and stir at room temperature until completely dissolved. Slowly add 20 mL of the prepolymer obtained in step (1) to the above solution at a dropping rate of 5 mL / min, and stir at room temperature until evenly dispersed after the addition is completed. React at 65 °C for 24 h under nitrogen protection, and immediately cool it with an ice-water bath after the reaction is completed to obtain an emulsion of super-hydrophilic organic polymer.

[0081] Preparation of calcium phosphate oligomer: Dissolve 18.0 g of anhydrous calcium chloride in 2 L of anhydrous ethanol, then transfer it to a flask equipped with a magnetic stir bar. Then add 600 mL of triethylamine to the above solution and stir magnetically at room temperature for 30 min. Then dissolve 10 mL of phosphoric acid solution in 420 mL of anhydrous ethanol and add it to the above solution, and stir magnetically at room temperature for 12 h. After the reaction, wash repeatedly with anhydrous ethanol and then centrifuge the precipitate. Finally, dissolve the centrifuged product in 1.0 L of anhydrous ethanol to obtain a calcium phosphate oligomer dispersion.

[0082] Preparation of Self-healing, Highly Wear-resistant, Super-hydrophilic and Anti-fog Coating and Corresponding Anti-fog Coating

[0083] Take 10.0 g of the polymer emulsion obtained in step (2) and slowly add it dropwise to 180 mL of deionized water under stirring conditions, stir at room temperature for 2 h until uniformly dispersed, then add 1.2 g of calcium phosphate oligomer, and then stir at room temperature for 2 h. The mixed solution is uniformly coated on the surface of a glass substrate by spin coating, and then dried at 70 °C to obtain a glass substrate coated sheet with a super-hydrophilic anti-fog functional coating.

[0084] Example 5

[0085] Preparation of prepolymer: Sequentially add 1.0 g of sodium persulfate initiator, 1.5 g of OP-10 emulsifier, 400 mL of propylene glycol methyl ether acetate, and 100 mL of ethanol to a single-necked flask equipped with a magnetic stir bar, and then stir magnetically at room temperature for 15 min; separately weigh 35 g of butyl acrylate and 45 g of 2-hydroxyethyl acrylate monomers and mix them evenly, and then slowly add them dropwise to the above mixed solution at a rate of 10.0 mL / min under stirring conditions. After the addition is completed, stir and react at 900 °C for 0.5 h under nitrogen protection. Immediately transfer it to an ice-water bath for sufficient cooling after the reaction to obtain a prepolymer.

[0086] Preparation of organic super-hydrophilic polymer emulsion: Sequentially add 4.0 g of sodium p-styrenesulfonate, 0.08 g of sodium persulfate, 20 mL of isopropyl alcohol, and 10 mL of glycerol to a single-necked flask equipped with a magnetic stir bar, and stir at room temperature until completely dissolved. Slowly add 20 mL of the prepolymer obtained in step (1) to the above solution at a dropping rate of 5 mL / min, and stir at room temperature until uniformly dispersed after the addition is completed. React at 65 °C for 6 h under nitrogen protection, and immediately cool with an ice-water bath after the reaction to obtain an emulsion of super-hydrophilic organic polymer.

[0087] Preparation of calcium phosphate oligomer: Dissolve 12.0 g of anhydrous calcium chloride in 2 L of anhydrous ethanol, then transfer it to a flask equipped with a magnetic stir bar. Then add 700 mL of triethylamine to the above solution, and stir magnetically at room temperature for 30 min. Then dissolve 6 mL of phosphoric acid solution in 6 mL of anhydrous ethanol and add it to the above solution, and stir magnetically at room temperature for 12 h. After the reaction is completed, wash it repeatedly with anhydrous ethanol and then centrifuge to precipitate. Finally, dissolve the centrifuged product in 1.0 L of anhydrous ethanol to obtain a calcium phosphate oligomer dispersion.

[0088] Preparation of Self-healing, Highly Wear-resistant, Super-hydrophilic and Anti-fog Coating and Corresponding Anti-fog Coating

[0089] Take 12 g of the polymer emulsion obtained in step (2) and slowly add it dropwise to 180 mL of butyl acetate under stirring conditions, stir at room temperature for 2 h until evenly dispersed, then add 500 mg of calcium phosphate oligomer, and then stir at room temperature for 2 h. The mixed solution is uniformly coated on the surface of a glass substrate by spin coating, and then dried at 70 °C to obtain a glass substrate coated sheet with a super-hydrophilic and anti-fog functional coating.

[0090] Example 6

[0091] Preparation of prepolymer: Sequentially add 1.0 g of potassium persulfate initiator, 1.0 g of AEO-3 emulsifier, 400 mL of ethyl acetate, and 100 mL of ethanol to a single-necked flask equipped with a magnetic stir bar, and then stir magnetically at room temperature for 15 min; separately weigh 18 g of butyl acrylate and 35 g of methyl methacrylate monomers and mix them evenly, and then slowly add them dropwise to the above mixed solution at a rate of 3.0 mL / min under stirring conditions. After the addition is completed, stir and react at 60 °C for 6 h under nitrogen protection. Immediately transfer it to an ice-water bath for sufficient cooling after the reaction is completed to obtain a prepolymer.

[0092] Preparation of organic super-hydrophilic polymer emulsion: Sequentially add 4.0 g of sodium p-styrenesulfonate, 0.04 g of sodium persulfate, 20 mL of ethanol, and 10 mL of propylene glycol methyl ether acetate to a single-necked flask equipped with a magnetic stir bar, and stir at room temperature until completely dissolved. Slowly add 20 mL of the prepolymer obtained in step (1) to the above solution at a dropping rate of 10 mL / min, and stir at room temperature until evenly dispersed after the addition is completed. React at 50 °C for 20 h under nitrogen protection, and immediately cool it with an ice-water bath after the reaction is completed to obtain an emulsion of super-hydrophilic organic polymer.

[0093] Preparation of calcium phosphate oligomers: 18.0 g of anhydrous calcium chloride was dissolved in 2 L of anhydrous ethanol, and then transferred to a flask equipped with a magnet. 600 mL of triethylamine was added to the above solution, and magnetic stirring was performed at room temperature for 30 min. 8 mL of phosphoric acid solution was dissolved in 320 mL of anhydrous ethanol and then added to the above solution. The reaction was magnetically stirred at room temperature for 12 h. After the reaction was completed, the solution was repeatedly washed with anhydrous ethanol and centrifuged to precipitate. Finally, the centrifuged product was dissolved in 1.5 L of anhydrous ethanol to obtain a calcium phosphate oligomer dispersion.

[0094] Self-healing highly wear-resistant super-hydrophilic anti-fog coating and preparation of corresponding anti-fog coating

[0095] Take 12 g of the polymer emulsion obtained in step (2) and slowly add it dropwise to 180 mL of propylene glycol under stirring conditions, stir at room temperature for 2 h until it is evenly dispersed, then add 1.0 g of calcium phosphate oligomer, and then stir at room temperature for 2 h. The mixed solution is evenly coated on the surface of the glass substrate by spin coating, and then dried at 70°C to obtain a glass substrate coated sheet with a super hydrophilic anti-fog functional coating.

[0096] Example 7

[0097] Preparation of prepolymer: 1.0g potassium persulfate initiator, 1.3g Tween-80 emulsifier, 450mL deionized water, and 105mL propylene glycol methyl ether acetate were added to a single-mouth bottle equipped with a magnetic device, and then magnetically stirred for 20 minutes at room temperature; 18g butyl acrylate and 46g methyl methacrylate monomers were weighed and mixed evenly, and then slowly added to the above mixed solution at a speed of 2.5mL / min under stirring conditions. After the addition was completed, the mixture was stirred at 90°C for 0.5h under nitrogen protection. After the reaction was completed, it was immediately moved to an ice water bath to be fully cooled to obtain a prepolymer.

[0098] Preparation of organic super-hydrophilic polymer emulsion: 4.2g sodium p-styrene sulfonate, 0.08g potassium persulfate, 20mL deionized water and 10mL propylene glycol are added to a single-mouth bottle equipped with a magnet in sequence, and stirred at room temperature until completely dissolved. 22mL of the prepolymer obtained in step (1) is slowly dripped into the above solution at a dripping speed of 8mL / min. After the dripping is completed, it is stirred at room temperature until uniformly dispersed. The reaction is carried out at 60°C under nitrogen protection for 18h. After the reaction is completed, it is immediately cooled in an ice water bath to obtain a super-hydrophilic organic polymer emulsion.

[0099] Preparation of calcium phosphate oligomer: Dissolve 20.0 g of anhydrous calcium chloride in 2.5 L of anhydrous ethanol, then transfer it to a flask equipped with a magnetic stir bar. Next, add 650 mL of triethylamine to the above solution, and stir magnetically at room temperature for 30 min. Then, dissolve 5 mL of phosphoric acid solution in 160 mL of anhydrous ethanol and add it to the above solution, and stir magnetically at room temperature for 10 h. After the reaction, wash repeatedly with anhydrous ethanol and then centrifuge the precipitate. Finally, dissolve the centrifuged product in 4.0 L of anhydrous ethanol to obtain a calcium phosphate oligomer dispersion.

[0100] Preparation of self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating and corresponding anti-fog coating

[0101] Take 15 g of the polymer emulsion obtained in step (2) and slowly add it dropwise to 150 mL of propylene glycol methyl ether acetate under stirring conditions, stir at room temperature for 2 h until uniformly dispersed, then add 750 mg of calcium phosphate oligomer, and then stir at room temperature for 2.5 h. The mixed solution is uniformly coated on the surface of a glass substrate by spin coating, and then dried at 70 °C to obtain a glass substrate coated sheet with a super-hydrophilic and anti-fog functional coating.

[0102] Performance characterization

[0103] 1. Take the calcium phosphate oligomer dispersion (ethanol dispersion of CPO) prepared in Example 1 (concentration: 10 mg / mL). Its physical picture is as shown in Figure 1 (a). It can be seen from the figure that the calcium phosphate oligomer is uniformly dispersed in the solvent without any precipitation.

[0104] Use a Fourier transform infrared spectrometer, an X-ray powder diffractometer, and a powder particle size analyzer to perform tablet pressing tests on the infrared spectrum (FTIR), X-ray diffraction (XRD) scanning test of the calcium phosphate oligomer powder prepared in Example 1, and particle size test on the CPO dispersion dispersed in ethanol. The results are shown in Figure 1 (b), 1(c), Figure 1 (d) respectively, where Figure 1 (b) is the particle size distribution diagram and powder schematic diagram of the calcium phosphate oligomer, Figure 1 (c) is the XRD curve of the calcium phosphate oligomer, Figure 1 (d) is the infrared spectrum of the calcium phosphate oligomer. It can be seen from the figure that the calcium phosphate oligomer has an ultra-small particle size (1.1 nm) and a narrow particle size distribution; it can be seen from the XRD pattern that the calcium phosphate oligomer is amorphous; the FTIR spectrum shows that the calcium phosphate oligomer has a C-N stretching vibration peak at 1282 cm -1 . It belongs to the triethylamine molecule, verifying the successful end-capping of calcium phosphate by triethylamine and the successful preparation of the oligomer.

[0105] 2. Take a blank glass slide and the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating prepared in Example 1 of the present invention, and conduct a hot fog test according to the requirements of GB / T 31726-2015. The specific steps are as follows: Place the anti-fog coating prepared by the present invention and the blank glass slide respectively above the mouth of a beaker containing hot water (80 °C) for 20 s (the distance between the sample and the water surface is 3 cm). The physical photos of the hot fog test of the blank glass slide and the anti-fog coating of Example 1 of the present invention are respectively as Figure 2 shown in (a) and (b) below. It can be observed from the figures that the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating of the present invention has excellent anti-fog performance due to being coated with a self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating material, while obvious fogging occurs on the blank glass slide, resulting in blurred vision. Further contact angle measurement shows that the contact angle of the blank glass slide is 40°, while the contact angle of the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating of the present invention is only 7°, proving that the coating has super-hydrophilic performance.

[0106] Figure 2 (c) and (d) are respectively the physical pictures of the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating of the present invention. It can be seen from the figures that the anti-fog coating of the present invention is uniform and completely transparent and can be applied to transparent materials.

[0107] Take the anti-fog coatings obtained in Examples 2 to 7 of the present invention for hot fog test and contact angle test. The results are as Figure 3 shown. It can be seen from Figure 3 that the contact angles of the anti-fog coatings in Examples 2 to 7 are 12°, 7°, 7°, 8°, 8°, 7° respectively, showing good super-hydrophilicity, further verifying that the anti-fog coating of the present invention has excellent anti-fog performance.

[0108] 3. To verify the self-healing performance of the anti-fog coating prepared by the present invention, take the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating prepared by the present invention, and use a cutter to damage the coating and draw the word "ISM" (the physical picture is as Figure 4 (b)), then conduct a hot fog experiment for 20 s (the physical picture is as Figure 4 (c)), and finally dry the anti-fog coating after the hot fog experiment (the physical picture is as Figure 4 (d)). It can be seen from the physical photos that after drying the anti-fog coating, the scratches on the coating have completely disappeared, indicating that the super-hydrophilic anti-fog coating has excellent self-healing function. When the coating is damaged by external stress, it can be repaired through the self-healing function, thereby improving the service life of the coating.

[0109] 4. To further verify the aging resistance of the anti-fog coating of the present invention, take the self-healing, highly wear-resistant and super-hydrophilic anti-fog coating prepared in Example 1 of the present invention, and conduct ultraviolet light accelerated aging (aging time: 6 days, ultraviolet radiation intensity: 0.68 W / m 2 @460 nm, equivalent to 6 months of outdoor aging) on the coating prepared with the commercially available anti-fog coating. After aging, conduct a hot fog effect test (the hot fog test refers to the above test method). The physical pictures are respectively as Figure 5 (a) and (b) shown. It can be seen from the figures that the anti-fog coating prepared by the present invention still has obvious anti-fog property after the ultraviolet accelerated aging test, while the anti-fog effect of the coating prepared with the commercially available anti-fog coating disappears, indicating that the anti-fog coating and the prepared anti-fog coating of the present invention have excellent ultraviolet aging resistance. The contact angle test results show that the contact angle of the commercially available anti-fog coating is 57°, while the contact angle of the anti-fog coating of the present invention is 10°, showing better super-hydrophilicity.

[0110] Further conduct a visible light transmittance test on the coating after the ultraviolet aging test. The results are as Figure 5 (c) shown. It can be seen from the figure that the anti-fog coating of the present invention still maintains a high visible light transmittance, which is significantly better than the coating prepared with the commercially available anti-fog coating, indicating that the anti-fog coating obtained by the present invention has a long service life.

[0111] 5. To further prove the water resistance of the anti-fog coating of the present invention. Take the coated glass sheet of the coating prepared with the commercially available anti-fog coating (the coating method is the same as that in Example 1 of the present invention), and the anti-fog coating prepared in Example 1. Conduct a water resistance test according to GB / T 1733-1993. The specific steps are as follows: Immerse the coating in distilled water for 2 h and then conduct a hot fog test. Among them, Figure 6 (a) is the physical picture of the hot fog test of the commercially available coating, Figure 6 (b) is the physical picture of the hot fog test of the anti-fog coating of Example 1. It can be observed that the commercially available coating has completely lost its anti-fog effect after soaking, while the anti-fog coating of Example 1 still shows excellent anti-fog effect. It shows that the anti-fog coating of Example 1 can maintain the anti-fog performance for a long time in a humid environment or under rain immersion and other environments. Combining its self-healing function, the service life of the anti-fog coating can be significantly improved.

[0112] 6. Take the anti-fog coating prepared in Example 1 of the present invention, and test the adhesion of the anti-fog coating according to the cross-cut method specified in GB / T 9286-88. The results are as Figure 7 shown. It can be seen from the figure that the cutting edge is completely smooth and there is no peeling, indicating that the adhesion of the coating can reach Grade 0, which is the highest grade specified by the national standard.

[0113] 7. Further, to test the wear resistance of the anti-fog coating of the present invention, the organic superhydrophilic polymer emulsion was directly coated onto the glass slide without adding calcium phosphate oligomer to obtain a 0% CPO coating. The coating method and others were the same as those in Example 1. The anti-fog coatings obtained in Example 1 and Example 2, the 0% CPO coating, the coatings of Example 1 and Example 2 were fixed on the sponge respectively, and a 30 g weight was loaded, and a reciprocating flat push friction was carried out. After every 200 reciprocating frictions, a hot fog test was carried out until the anti-fog performance of the coating failed. The corresponding hot fog test effect diagram is as Figure 8 shown. It can be seen from the figure that the coating without adding calcium phosphate oligomer only has a friction resistance number of 2000 times, while the anti-fog coatings of Example 1 and Example 2 have the friction resistance numbers increased to 2400 and 2800 times respectively. Thus, it can be shown that the addition of calcium phosphate oligomer improves the wear resistance of the anti-fog coating.

[0114] In summary, the self-healing high wear-resistant superhydrophilic anti-fog coating prepared by the self-healing high wear-resistant superhydrophilic anti-fog coating provided by the present invention has excellent wear resistance, anti-fog performance, good superhydrophilicity, can improve the transmission effect at the same time, and also has a high self-healing function.

[0115] The above embodiments only exemplarily illustrate the principle and its efficacy of the present invention, rather than limiting the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A method for preparing a self-healing, highly wear-resistant, superhydrophilic and antifogging coating, characterized in that, It includes the following steps: (1) Preparation of prepolymer; (2) Preparation of organic superhydrophilic polymer emulsion; (3) Preparation of calcium phosphate oligomer; (4) Preparation of self-healing, highly wear-resistant and superhydrophilic anti-fog coating; Specifically, it includes the following steps: (1) Preparation of prepolymer: Add initiator to solvent I for dissolution, add emulsifier, and stir evenly to obtain a mixed solution; Take acrylic monomers and methacrylate monomers and mix them evenly, then dropwise add them to the above mixed solution under stirring. After the dropping is completed, react under nitrogen protection, and after the reaction is completed, perform cooling treatment to obtain a prepolymer; (2) Preparation of organic superhydrophilic polymer emulsion: Take ionic monomers and initiator, add solvent II, stir until dissolved, then dropwise add the prepolymer obtained in step (1) to the solution. After the dropping is completed, add emulsifier, stir evenly, and perform heating reaction under nitrogen protection. After the reaction is completed, perform cooling treatment to obtain an organic superhydrophilic polymer emulsion; (3) Preparation of calcium phosphate oligomer: Add anhydrous calcium chloride to anhydrous ethanol, add triethylamine, and add a mixed solvent of phosphoric acid and ethanol under stirring to perform stirring reaction. After the reaction is completed, perform post-treatment to obtain calcium phosphate oligomer; Disperse the calcium phosphate oligomer in anhydrous ethanol to obtain a calcium phosphate oligomer dispersion; (4) Preparation of self-healing, highly wear-resistant and superhydrophilic anti-fog coating: Take the organic superhydrophilic polymer emulsion obtained in step (2), dropwise add diluent, and stir until evenly dispersed to obtain a diluted emulsion; Centrifuge the calcium phosphate oligomer dispersion obtained in step (3), and add the centrifuged product calcium phosphate oligomer to the above diluted emulsion, and ultrasonically stir evenly to obtain a self-healing, highly wear-resistant and superhydrophilic anti-fog coating; The initiators in step (1) and step (2) are each selected from one or more of potassium persulfate, sodium persulfate, and ammonium persulfate; In step (1), the reaction temperature is 50-90 °C and the reaction time is 0.5-6 h; In step (2), the reaction temperature is 50-90 °C and the reaction time is 3-24 h; The ionic monomers in step (2) are each selected from one or more of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride, acryloyloxyethyltrimethylammonium chloride, sodium methallylsulfonate, and sodium p-styrenesulfonate.

2. The method according to claim 1, characterized in that It includes one or more of the following technical features: In step (1), the dropping rate is 1-10 mL / min; In step (1), the mass ratio of the initiator to the emulsifier is (1-5):(5-10); In step (1), the mass ratio of the initiator to the total amount of acrylic monomers and methacrylate monomers is (1-8):(35-200); In step (1), the mass ratio of the total amount of acrylic monomers and methacrylate monomers to the solvent is (1-5):(5-100).

3. The method according to claim 1, wherein It includes one or more of the following technical features: In step (2), the mass ratio of the ionic monomer to solvent II is (1-5):(5-10); In step (2), the mass ratio of the initiator to the ionic monomer is (1-9):(10-200); In step (2), the mass ratio of the ionic monomer to the prepolymer is (1-7):(1-120); The dropping rate of the prepolymer described in step (2) is 0.5 - 10 mL / min.

4. The method according to claim 1, wherein One or more of the following technical features: In step (3), the mass concentration of anhydrous calcium chloride in absolute ethanol is 1 - 100 mg / mL; In step (3), the mass concentration of triethylamine relative to absolute ethanol is 0.2 - 10 g / mL; In step (3), the volume ratio of phosphoric acid to ethanol in the mixed solvent is (1 - 6):(6 - 50); In step (3), the concentration of the calcium phosphate oligomer dispersion is 2 - 500 mg / mL.

5. The method according to claim 1, wherein One or more of the following technical features: In step (4), the mass ratio of the organic super-hydrophilic polymer emulsion to the diluent is (1 - 5):(1 - 80); In step (4), the diluent is selected from one or more of water, ethanol, propylene glycol methyl ether acetate, isopropanol, glycerol, and butyl acetate; In step (4), the stirring speed is 500 - 4000 rpm; In step (4), the stirring time is 0.5 - 2 h; In step (4), the added amount of the calcium phosphate oligomer accounts for 0.1% - 20% of the mass of the added emulsion.

6. A self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating prepared by the method according to any one of claims 1 to 5.

7. A self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating, characterized in that, Including the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating according to claim 6.

8. A method for preparing the self-healing, highly wear-resistant, super-hydrophilic and anti-fogging coating according to claim 7, characterized in that, Including the following steps: uniformly coating the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating on the surface of a glass substrate, and drying to obtain a self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating.

9. Application of the self-healing, highly wear-resistant, super-hydrophilic and anti-fog coating according to claim 7 in the fields of glasses, protective masks, windshield glass, and solar panels.

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