Light-storing self-repairing super-hydrophobic polyurethane coating and preparation method thereof
By introducing components such as 3-aminophenylboric acid, N-aminoethyl-γ-aminopropyltriethoxysilane and nanosilia into the polyurethane coating, the problem of single function of the polyurethane coating is solved, and a multifunctional polyurethane coating with efficient self-healing, superhydrophobic and excellent fluorescence properties is achieved.
Patent Information
- Application Number
- CN202510292590.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-12
- Publication Date
- 2025-05-02
AI Technical Summary
The existing polyurethane coatings have a single function and are difficult to meet the needs of versatility and high performance, especially in terms of self-healing, superhydrophobic and fluorescent properties.
By introducing 3-aminophenylboric acid into the polyurethane to generate a reversible boron-oxyhexancyclic structure, the coating is imparted with self-healing properties; N-aminoethyl-γ-aminopropyltriethoxysilane is introduced as a chain extender to improve mechanical properties and dispersion properties of nanoparticles; and by adding nanosilicon dioxide and phosphor, the superhydrophobic and fluorescent properties of the coating are improved.
The high repair efficiency, superhydrophobic performance, mechanical properties and fluorescence performance of polyurethane coatings have been improved. The hydrophobic angle of the coating is greater than 150° and the repair efficiency is greater than 95%. It has broad application prospects in the fields of information storage, building decoration, etc.
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Figure CN119912868A_ABST
Abstract
Description
[0001] The invention belongs to the technical field of self-repairing materials, and in particular relates to a light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof. Background Art
[0002] Waterborne polyurethane coating is a new type of coating with water as the dispersion medium. It is non-toxic, odorless, environmentally friendly, and has good adhesion, mechanical properties, low temperature resistance, etc. The coating is inevitably mechanically damaged during use, which will reduce the performance of the coating and shorten its service life. By introducing reversible covalent bonds (disulfide bonds, imine bonds, DA reactions, 2+2 cycloadditions, etc.) or non-covalent bonds (hydrogen bonds, metal coordination bonds, electrostatic interactions, etc.) into the molecular structure of polyurethane, the coating can be self-repaired and its service life can be extended.
[0003] With the development of science and technology, higher requirements are placed on the performance of coatings, and single-function coatings can no longer meet the needs of materials. By adding various functional fillers to the coating, the coating can be given multifunctionality, which has attracted the attention of more and more researchers. For example, introducing nanoparticles into the coating can improve the water transmission angle and water resistance of the coating; by introducing photoresponsive groups, the photoluminescence and photochromic properties of the coating can be achieved; by introducing flame-retardant fillers, the flame retardant properties of the coating can be achieved. However, the direct addition of unmodified nanoparticles can easily lead to the agglomeration of nanoparticles, affecting the performance of the coating. Therefore, it is usually necessary to modify the nanoparticles before adding them, and the operation process is cumbersome.
[0004] The polyurethane prepared by the present invention is capped by 3-aminophenylboronic acid, and a reversible boron oxygen six-ring structure is generated by boric acid dehydration condensation, which gives the polyurethane coating excellent self-repairing performance, and the repair efficiency is greater than 95%. In addition, the present invention introduces a chain extender N-aminoethyl-γ-aminopropyl triethoxysilane to extend the polyurethane chain, and the silanol generated after the terminal siloxane is hydrolyzed can be combined with the matrix or condensed by itself, thereby improving the mechanical properties and water resistance of the coating. At the same time, the generated silanol can also dehydrate and condense with the alcohol hydroxyl groups on the surface of nano-silicon dioxide and phosphor, significantly improving the dispersion performance of nanoparticles, and giving the coating excellent fluorescence performance and hydrophobic performance (water delivery angle greater than 150°). In short, the multifunctional polyurethane coating prepared by the present invention has high repair efficiency, high water delivery angle, high mechanical properties and fluorescence performance, and has broad application prospects in the fields of super-hydrophobic coatings, anti-corrosion coatings, anti-counterfeiting labels, architectural decoration, information storage, etc. in the future. Summary of the invention
[0005] The present invention aims at the shortcoming that the existing polyurethane coating has a single function, and provides a multifunctional polyurethane coating with high self-repairing efficiency, high water delivery angle, high mechanical properties and fluorescence properties.
[0006] In order to achieve the above object, the present invention adopts the following technical solutions: The light-storage self-repairing super-hydrophobic polyurethane coating provided by the present invention is obtained by spraying water-based polyurethane emulsion, nano-silicon dioxide and fluorescent powder in a mass ratio of 1:0.01-0.06:0.05-0.15, and drying the solvent.
[0007] The polyurethane emulsion is obtained by reacting diisocyanate, long-chain diol, 2,2-dimethylol propionic acid, 1,4-butanediol, N-aminoethyl-γ-aminopropyltriethoxysilane, aminophenylboronic acid and triethylamine in a molar ratio of 20:5-10:1-4:4-8:0.5-3:3-10:1-4.
[0008] The diisocyanate is one or more of 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate and toluene 2,4-diisocyanate.
[0009] The long-chain diol is one or more of polysiloxane diol, polytetramethylene glycol, polypropylene glycol and polyethylene glycol with a molecular weight of 200-3000.
[0010] The method for preparing the light-storage self-repairing super-hydrophobic polyurethane coating comprises the following steps: S1. Preparation of polyurethane emulsion: under nitrogen protection, add diisocyanate, long-chain diol, 2,2-dihydroxymethyl propionic acid and dibutyltin dilaurate to a three-necked flask equipped with a stirrer and a spherical condenser, heat to 60°C, stir and react for 2-3h, then add butanediol for chain extension, continue to react for 1h, during which acetone is added to reduce viscosity; then cool to 0°C, add N-aminoethyl-γ-aminopropyltriethoxysilane acetone solution dropwise with a dropping funnel, continue to add aminophenylboronic acid acetone solution dropwise after 1h of reaction, and continue to react for 1h. Finally, heat to 40°C, add triethylamine, stir for 30min, add deionized water, and disperse at 2000rpm for 40min to obtain polyurethane emulsion. Diisocyanate, long-chain diol, 2,2-dimethylol propionic acid, 1,4-butanediol, N-aminoethyl-γ-aminopropyltriethoxysilane, aminophenylboronic acid, triethylamine in a molar ratio of 20:5~10:1~4:4~8:0.5~3:3~10:1~4; S2. Preparation of a photosensitive self-repairing super-hydrophobic polyurethane coating: polyurethane emulsion, fluorescent powder and nano-silicon dioxide are mixed in a mass ratio of 1:0.01-0.06:0.05-0.15, the mixture is sprayed on a substrate using a spray gun, and dried at room temperature and 60°C to obtain a photosensitive self-repairing super-hydrophobic polyurethane coating.
[0011] Compared with the prior art, the present invention is beneficial in that: First, the present invention introduces N-aminoethyl-γ-aminopropyltriethoxysilane as a chain extender into polyurethane for chain extension. The siloxane on the chain extender is hydrolyzed to generate silanol, which can undergo dehydration condensation with the alcoholic hydroxyl groups on the surface of nano-silicon dioxide and phosphor, thereby significantly improving the dispersion performance of the nanoparticles. In addition, the silanol generated by the hydrolysis of the siloxane on the chain extender can be combined with the matrix or condensed by itself, thereby improving the mechanical properties and water resistance of the coating.
[0012] Secondly, the present invention introduces fluorescent powder into polyurethane to give the coating excellent fluorescent properties. It has broad application prospects in the fields of information storage, building decoration, and anti-counterfeiting labels in the future.
[0013] Thirdly, the multifunctional polyurethane coating prepared by the present invention has high repair efficiency, high water transmission angle, high mechanical properties and fluorescence properties, which solves the disadvantage of the single function of the existing polyurethane coating. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 .Infrared spectrum of polyurethane film; Figure 2 .Test diagram of tensile properties and self-healing properties of polyurethane film; Figure 3 .Scanning electron microscope images of phosphor and ground modified phosphor; Figure 4 .Water contact angle diagram of light-storage self-healing superhydrophobic polyurethane coating; Figure 5 . Fluorescence emission spectrum test diagram of light-storage self-healing super-hydrophobic polyurethane coating; Figure 6 .Afterglow decay curve of light-storage self-healing superhydrophobic polyurethane coating. DETAILED DESCRIPTION
[0015] The preferred implementation cases of the present invention are described below in conjunction with the accompanying drawings. It should be understood that the preferred implementation cases described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.
[0016] Implementation Case 1: A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof, comprising the following steps: (1) Preparation of polyurethane emulsion Under nitrogen protection, the temperature was raised to 45°C, 0.54g 2,2-dihydroxymethylpropionic acid, 5.06g polytetrahydrofuran, and 1.38g polysiloxane diol were added to a three-necked flask equipped with a stirrer and a spherical condenser and mixed thoroughly, 4.5g isophorone diisocyanate and 15mL dibutyltin dilaurate were added, and the mixture was heated to 80°C and reacted for 2 hours; the temperature was lowered to 60°C, 0.502mL 1-4-butanediol was added, and the reaction was continued for 2 hours; the temperature was quickly lowered to 0°C, 0.225g KH-792 and 0.691 A mixed solution of 6g p-aminophenylborane and 0.6916g acetone was reacted for 1 hour; the temperature was lowered to 40°C, 0.59mL triethylamine was added to the mixed solution, and the reaction was continued for 30 minutes, during which acetone was added to reduce the viscosity; the temperature was lowered to room temperature, 31.7g deionized water was added, and the mixture was stirred at 1000rpm for 20 minutes; the mixture was dispersed at 2000rpm using a high-speed disperser for 30 minutes to obtain a polyurethane emulsion; the mixture was allowed to stand at room temperature for 72 hours in a polytetrafluoroethylene mold, and finally a polyurethane film was obtained after drying in a 55°C blower for 48 hours. The reaction equation is as follows: ; (2) Preparation of light-storage self-healing super-hydrophobic polyurethane coating The polyurethane emulsion, phosphor and nano-silicon dioxide were mixed in a mass ratio of 1:0.03:0.1, the mixture was sprayed on the substrate using a spray gun, and dried at room temperature and 60° C. to obtain a light-storage self-repairing super-hydrophobic polyurethane coating; Figure 1 . Infrared spectrum of the polyurethane film of Example 1 (KBr, cm -1 ), it can be seen from the figure that the wave number is about 3319cm -1 and 1094cm -1 The peaks formed are attributed to the characteristic absorption peaks of NH bonds on carbamate groups (-NH(CO)O-) and urea groups (-NHCONH-), with a wave number of 2944 cm -1 and 2855cm -1 The peaks at 1692 cm correspond to the antisymmetric absorption peaks and symmetric absorption peaks of methyl and methylene, respectively. -1 The peak corresponding to the position belongs to the stretching vibration peak of C=O on the carbamate group, with a wave number of about 709cm -1 The characteristic absorption peak corresponding to the position is the stretching vibration peak of the B3O3 group; Figure 2.The tensile properties and self-healing properties test diagram of the polyurethane film of implementation case 1. The self-healing property test method is to cut the complete polymer sample into two halves, soak the fracture surface in a mixture of water and ethanol in a ratio of 5:1 for 1 minute, and then use external force to make the fracture surfaces contact. After being placed at 70°C for 3 hours, a 500N universal testing machine is used to perform a tensile test on the repaired sample at a tensile rate of 50mm / min. The self-healing efficiency is defined as the ratio of the tensile strength of the repaired sample to the tensile strength of the original sample. The test results show that after adding 25% 3-aminophenylboronic acid, the tensile strength of the polyurethane is 5.8MPa after the action of hexacyclic borane. After being placed at 70°C for 6 hours, the same method is used again to test. At this time, the tensile strength of the polyurethane is 6.2MPa, which is close to the tensile strength of the initial sample. Figure 3 . This is a scanning electron microscope image of the phosphor of Example 1 and the phosphor after grinding. It is observed from the figure that SrAl2O4:Eu purchased directly on the market 2+ ,Dy 3+ The phosphor particles have no agglomeration phenomenon and are uniform in particle size, but the average particle size is relatively large, with most of them being between 50 and 100 mm. After grinding and modification, most of the particles become finer, which is conducive to dispersion in polymer materials; Figure 4 . This is a contact angle diagram of the photosensitive self-repairing super-hydrophobic polyurethane coating of Example 1. It can be seen from the figure that when a water drop is dropped onto the photosensitive self-repairing super-hydrophobic polyurethane coating, the contact angle is greater than 150°, proving that the coating has excellent super-hydrophobic properties; Figure 5 .This is a fluorescence emission spectrum test diagram of the light-storage self-healing super-hydrophobic polyurethane coating of implementation case 1. The solid content of the polyurethane emulsion is adjusted to 0.5%, and a fluorescence spectrometer is used for measurement, with a slit of 2.5nm and an excitation wavelength of 280nm. It can be observed in the figure that the emission spectrum shows broadband emission, and the position of the main emission peak is between 385-470nm and between 480-660nm, which belongs to the long afterglow luminescence range; Figure 6 .This is the afterglow attenuation curve of the light-storing self-healing super-hydrophobic polyurethane coating of implementation case 1. It can be clearly seen from the figure that the intensity of the afterglow of the polyurethane coating began to tend to be stable after more than 200 seconds. Before more than 200 seconds, the afterglow intensity was at a very high intensity. It can also be seen from the small picture in the upper right corner of the figure that the intensity of the afterglow reaches the highest when the wavelength reaches more than 500 nm.
[0017] Implementation Case 2: A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof, comprising the following steps: (1) Preparation of polyurethane emulsion Under nitrogen protection, the temperature was raised to 45°C, 0.54g 2,2-dihydroxymethylpropionic acid, 5.06g polytetrahydrofuran, and 1.38g polysiloxane diol were added to a three-necked flask equipped with a stirrer and a spherical condenser and mixed thoroughly, 3.4g hexamethylene diisocyanate and 15mL dibutyltin dilaurate were added, and the mixture was heated to 80°C and reacted for 2 hours; the temperature was lowered to 60°C, 0.502mL 1-4-butanediol was added, and the reaction was continued for 2 hours; the temperature was quickly lowered to 0°C, 0.225g KH-792, 0.691 A mixed solution of 6g p-aminophenylborane and 0.6916g acetone was reacted for 1 hour; the temperature was lowered to 40°C, 0.59mL triethylamine was added to the mixed solution, and the reaction was continued for 30 minutes, during which acetone was added to reduce the viscosity; the temperature was lowered to room temperature, 31.7g deionized water was added, and the mixture was stirred at 1000rpm for 20 minutes; the mixture was dispersed at 2000rpm using a high-speed disperser for 30 minutes to obtain a polyurethane emulsion; the mixture was allowed to stand at room temperature for 72 hours in a polytetrafluoroethylene mold, and finally a polyurethane film was obtained after drying in a blower at 55°C for 48 hours; (2) Preparation of light-storage self-healing super-hydrophobic polyurethane coating The polyurethane emulsion, phosphor and nano-silicon dioxide were mixed in a mass ratio of 1:0.04:0.08, and the mixture was sprayed on the substrate using a spray gun. The mixture was dried at room temperature and 60°C to obtain a light-storage self-repairing super-hydrophobic polyurethane coating.
[0018] Implementation Case 3: A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof, comprising the following steps: (1) Preparation of polyurethane emulsion Under nitrogen protection, the temperature was raised to 45°C, 0.54g 2,2-dihydroxymethylpropionic acid, 5.06g polytetrahydrofuran, and 1.38g polysiloxane diol were added to a three-necked flask equipped with a stirrer and a spherical condenser and mixed thoroughly, 5.06g 4,4′-diphenylmethane diisocyanate and 15mL dibutyltin dilaurate were added, and the mixture was heated to 80°C for reaction for 2 hours; the temperature was lowered to 60°C, 0.502mL 1-4-butanediol was added, and the reaction was continued for 2 hours; the temperature was quickly lowered to 0°C, 0.225g KH-792, 0. A mixed solution of 6916g of p-aminophenylborane and 0.6916g of acetone was reacted for 1 hour; the temperature was lowered to 40°C, 0.59mL of triethylamine was added to the mixed solution, and the reaction was continued for 30 minutes, during which acetone was added to reduce the viscosity; the temperature was lowered to room temperature, 31.7g of deionized water was added, and the mixture was stirred at 1000rpm for 20 minutes; the mixture was dispersed at 2000rpm using a high-speed disperser for 30 minutes to obtain a polyurethane emulsion; the mixture was allowed to stand at room temperature for 72 hours in a polytetrafluoroethylene mold, and finally a polyurethane film was obtained after drying in a blower at 55°C for 48 hours; (2) Preparation of light-storage self-healing super-hydrophobic polyurethane coating The polyurethane emulsion, phosphor and nano-silicon dioxide were mixed in a mass ratio of 1:0.04:0.08, and the mixture was sprayed on the substrate using a spray gun. The mixture was dried at room temperature and 60°C to obtain a light-storage self-repairing super-hydrophobic polyurethane coating.
[0019] Implementation Case 4: A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof, comprising the following steps: (1) Preparation of polyurethane emulsion Under nitrogen protection, the temperature was raised to 45°C, 0.54g 2,2-dihydroxymethylpropionic acid, 5.06g polytetrahydrofuran, and 1.38g polypropylene glycol were added to a three-necked flask equipped with a stirrer and a spherical condenser and mixed thoroughly, 3.5g toluene-2,4-diisocyanate and 15mL dibutyltin dilaurate were added, and the mixture was heated to 80°C and reacted for 2 hours; the temperature was lowered to 60°C, 0.502mL 1-4-butanediol was added, and the reaction was continued for 2 hours; the temperature was quickly lowered to 0°C, 0.225g KH-792, 0.69 A mixed solution of 16g p-aminophenylborane and 0.6916g acetone was reacted for 1 hour; the temperature was lowered to 40°C, 0.59mL triethylamine was added to the mixed solution, and the reaction was continued for 30 minutes, during which acetone was added to reduce the viscosity; the temperature was lowered to room temperature, 31.7g deionized water was added, and the mixture was stirred at 1000rpm for 20 minutes; the mixture was dispersed at 2000rpm using a high-speed disperser for 30 minutes to obtain a polyurethane emulsion; the mixture was allowed to stand at room temperature for 72 hours in a polytetrafluoroethylene mold, and finally a polyurethane film was obtained after drying in a blower at 55°C for 48 hours; (2) Preparation of light-storage self-healing super-hydrophobic polyurethane coating The polyurethane emulsion, phosphor and nano-silicon dioxide were mixed in a mass ratio of 1:0.05:0.06, and the mixture was sprayed on the substrate using a spray gun. The mixture was dried at room temperature and 60°C to obtain a light-storage self-repairing super-hydrophobic polyurethane coating.
[0020] Implementation Case 5: A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof, comprising the following steps: (1) Preparation of polyurethane emulsion Under nitrogen protection, the temperature was raised to 45°C, 0.54g 2,2-dihydroxymethylpropionic acid, 5.06g polytetrahydrofuran, and 1.38g polyethylene glycol were added to a three-necked flask equipped with a stirrer and a spherical condenser and mixed thoroughly, 5.24g 4,4′-dicyclohexylmethane diisocyanate and 15mL dibutyltin dilaurate were added, and the mixture was heated to 80°C for reaction for 2 hours; the temperature was lowered to 60°C, 0.502mL 1-4-butanediol was added, and the reaction was continued for 2 hours; the temperature was quickly lowered to 0°C, 0.225g KH-792, 0. A mixed solution of 6916g of p-aminophenylborane and 0.6916g of acetone was reacted for 1 hour; the temperature was lowered to 40°C, 0.59mL of triethylamine was added to the mixed solution, and the reaction was continued for 30 minutes, during which acetone was added to reduce the viscosity; the temperature was lowered to room temperature, 31.7g of deionized water was added, and the mixture was stirred at 1000rpm for 20 minutes; the mixture was dispersed at 2000rpm using a high-speed disperser for 30 minutes to obtain a polyurethane emulsion; the mixture was allowed to stand at room temperature for 72 hours in a polytetrafluoroethylene mold, and finally a polyurethane film was obtained after drying in a blower at 55°C for 48 hours; (2) Preparation of light-storage self-healing super-hydrophobic polyurethane coating The polyurethane emulsion, phosphor and nano-silicon dioxide were mixed in a mass ratio of 1:0.02:0.12, and the mixture was sprayed on the substrate using a spray gun. The mixture was dried at room temperature and 60°C to obtain a light-storage self-repairing super-hydrophobic polyurethane coating.
[0021] In summary, the aqueous polyurethane prepared by the present invention is end-capped by 3-aminophenylboronic acid, and a reversible boron oxygen six-ring structure is generated by boric acid dehydration condensation, which gives the polyurethane coating excellent self-repairing performance, and the repair efficiency is greater than 95%; by introducing nano-silica and phosphor, the coating is given excellent super-hydrophobic and fluorescent properties, and its hydrophobic angle is greater than 150°, and the afterglow time is greater than 200s; and N-aminoethyl-γ-aminopropyl triethoxysilane is added to improve the mechanical properties of the coating and the dispersion properties of nanoparticles. This material is suitable for various fields such as super-hydrophobic anti-corrosion coatings, architectural decoration, and information storage.
[0022] The above is only a preferred implementation case of the present invention, and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred implementation case as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent implementation cases with equivalent changes by using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above implementation cases based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.
Claims
1. A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof, characterized in that: The polyurethane coating is obtained by spraying water-based polyurethane emulsion, nano-silicon dioxide and fluorescent powder in a mass ratio of 1:0.01-0.06:0.05-0.15, and drying the solvent; the polyurethane emulsion is obtained by reacting diisocyanate, long-chain diol, 2,2-dimethylol propionic acid, 1,4-butanediol, N-aminoethyl-γ-aminopropyl triethoxysilane, 3-aminophenylboronic acid and triethylamine in a molar ratio of 20:5-10:1-4:4-8:0.5-3:3-10:1-4. Its general structural formula is: ； In the formula, R is one or more of the following structural formulas: ； In the formula, R2 is one or more of the following structural formulas: 。 2. A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof as claimed in claim 1, characterized in that: The diisocyanate is one or more of 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate and toluene 2,4-diisocyanate.
3. A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof as claimed in claim 1, characterized in that: The long-chain diol is one or more of polysiloxane diol, polytetramethylene glycol, polypropylene glycol and polyethylene glycol with a molecular weight of 200-3000.
4. A light-storage self-repairing super-hydrophobic polyurethane coating and a preparation method thereof as described in claims 1-3, characterized in that: The steps include: S1. Preparation of polyurethane emulsion: under nitrogen protection, add diisocyanate, long-chain diol, 2,2-dihydroxymethyl propionic acid and dibutyltin dilaurate to a three-necked flask equipped with a stirrer and a spherical condenser, heat to 60°C, stir and react for 2-3h, add butanediol for chain extension, continue to react for 1h, during which acetone is added to reduce viscosity; then cool to 0°C, add N-aminoethyl-γ-aminopropyltriethoxysilane acetone solution dropwise with a dropping funnel, react for 1h, continue to add 3-aminophenylboronic acid acetone solution dropwise, and continue to react for 1h. Finally, heat to 40°C, add triethylamine, stir for 30min, add deionized water, and disperse at 2000rpm for 40min to obtain polyurethane emulsion. Diisocyanate, long-chain diol, 2,2-dimethylol propionic acid, 1,4-butanediol, N-aminoethyl-γ-aminopropyltriethoxysilane, aminophenylboronic acid, triethylamine in a molar ratio of 20:5~10:1~4:4~8:0.5~3:3~10:1~4; S2. Preparation of light-storage self-healing super-hydrophobic polyurethane coating: Mix polyurethane emulsion, fluorescent powder and silica in a mass ratio of 1:0.01~0.06:0.05~0.15, spray the mixture on the substrate with a spray gun, and dry it at room temperature and 60°C to obtain a light-storage self-healing super-hydrophobic polyurethane coating.