Preparation method of rapidly-cured photo-thermal super-hydrophobic coating

Abstract

The invention provides a preparation method of a rapidly-cured photo-thermal super-hydrophobic coating, and belongs to the technical field of functional composite materials. The preparation method of the rapidly-cured photo-thermal super-hydrophobic coating comprises the following steps: S1, preparing a polypyrrole / silicon dioxide hybrid nano material; s2, preparing a super-hydrophobic modified polypyrrole / silicon dioxide hybrid nano material; s3, preparing the light-cured photo-thermal super-hydrophobic coating; and coating a substrate with the obtained solution, and carrying out irradiation curing by using an ultraviolet lamp to form the required photo-thermal super-hydrophobic coating. The photo-thermal super-hydrophobic coating is prepared in an ultraviolet curing mode, the curing method is rapid and convenient to operate, and the defects that the emission of volatile organic compounds (VOCs) is large, the environment friendliness is poor, the curing time is long, the preparation efficiency is high, the mechanical performance of the coating is poor, and the anti-icing and deicing performance is unstable when the photo-thermal super-hydrophobic coating is prepared through a conventional spraying curing method are overcome.

Description

Technical Field

[0001] This application relates to the field of functional composite materials, and more specifically, to a method for preparing a rapidly curing photothermal superhydrophobic coating. Background Technology

[0002] Currently, superhydrophobic coatings have seen significant applications in de-icing and anti-icing applications in fields such as shipbuilding, transportation, and aviation due to their excellent surface protection properties, including liquid repellency and self-cleaning. Ordinary superhydrophobic coatings can achieve delayed icing of surface droplets and low adhesion to ice through low surface energy and micro / nano structures.

[0003] At present, the preparation and application of superhydrophobic coatings still have the following problems: (1) Ordinary superhydrophobic coatings do not have active de-icing properties, and the ice layer on their surface is difficult to remove when used in a cold and humid environment for a long time; (2) The raw materials and technologies used to prepare superhydrophobic coatings are expensive and the preparation process is complicated; (3) The micro-nano structure on the surface of superhydrophobic coatings is easily damaged, and its mechanical durability is poor.

[0004] For example, Chinese patent CN119614064B uses a spraying method to prepare a photothermal superhydrophobic coating, which combines photothermal materials with superhydrophobic properties. By using photothermal properties to achieve surface heating, it can effectively achieve the dual functions of anti-icing and de-icing, thus overcoming the limitations of ordinary superhydrophobic coatings.

[0005] The existing technical solutions mentioned above have the following drawbacks: the conventional preparation method of photothermal superhydrophobic coatings is solvent-mixed spray curing method. Under the conventional spray curing method, there are often defects such as large emissions of volatile organic compounds (VOCs), poor environmental protection, long curing time, low preparation efficiency, poor mechanical properties of coatings, and unstable anti-icing and de-icing performance. Summary of the Invention

[0006] To overcome the above shortcomings, this application provides a method for preparing a rapidly curing photothermal superhydrophobic coating, aiming to improve the problems existing in the preparation method using conventional spray curing.

[0007] This application provides a method for preparing a rapidly curing photothermal superhydrophobic coating, including the following preparation method:

[0008] S1. Preparation of polypyrrole / silica hybrid nanomaterials: Weigh 0.6-1g of nano-silica and add it to 200mL of deionized water in a beaker. Then weigh 0.4-0.8g of surfactant and add it to the beaker. After stirring evenly, add 250-500uL of pyrrole monomer and disperse it evenly. Finally, add 2.5-5mL of 0.5mol / L ferric chloride solution and stir for 8h to complete the reaction. After repeated filtration and washing with deionized water, dry in an 80°C oven and grind into powder to obtain polypyrrole / silica hybrid nanomaterials.

[0009] S2. Preparation of superhydrophobic modified polypyrrole / silica hybrid nanomaterials: 10 ml of deionized water, 90 ml of anhydrous ethanol, and 1 ml of concentrated hydrochloric acid were added to a flask and stirred at 40°C for 10 min. 1-1.5 g of polypyrrole / silica hybrid nanomaterials were added to the above solution and ultrasonically stirred for 30 min to form a dispersion. Then, 1-2 ml of FAS17 was added dropwise, and the mixture was stirred at 40°C for 24 h. The precipitate was obtained by centrifugation and washing. The precipitate was then ground into powder to obtain superhydrophobic modified polypyrrole / silica hybrid nanomaterials.

[0010] S3. Preparation of photocurable photothermal superhydrophobic coating: Weigh 5-10g of reactive diluent, add 1-2g of epoxy acrylate, and after it is completely dissolved, add 0.6-1g of superhydrophobic modified polypyrrole / silica hybrid nanomaterial and stir thoroughly. After the mixture is evenly dispersed, add 0.05-0.1g of photoinitiator and stir again until evenly mixed. After coating the obtained solution onto the substrate, irradiate it with a UV lamp to cure and form the desired photothermal superhydrophobic coating.

[0011] The preparation of superhydrophobic coatings via ultraviolet (UV) curing offers advantages such as rapid curing speed, low energy consumption, environmental friendliness, and superior coating performance, making it a promising direction for future coating research and development. Therefore, developing photothermal superhydrophobic coatings with rapid curing processes and excellent mechanical and anti-icing properties through UV curing holds significant research value and application prospects.

[0012] By covalently bonding hybrid materials with epoxy acrylate, a structural gradient of "superhydrophobic surface - highly cross-linked interior" is achieved. After 500 sandpaper abrasions, the water contact angle is still ≥150°, solving the problem of balancing mechanical properties and superhydrophobicity and breaking through the durability bottleneck of existing technologies.

[0013] In a preferred embodiment of the present invention, the nano-silica particles obtained in S1 are 25-50 nm in size, the reaction is carried out at 0°C, and mechanical stirring is performed at a stirring speed of 180 rpm for 8 hours; the particles are then repeatedly filtered and washed with deionized water 3 times.

[0014] In a preferred embodiment of the present invention, in S3, the reactive diluent is a mixture of tripropylene glycol diacrylate or trimethylolpropane triacrylate and 1,6-hexanediol diacrylate, and the photoinitiator is a compound of 2-hydroxy-2-methyl-1-phenyl-1-propanone or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0015] In a preferred embodiment of the invention, in step S3, the ultraviolet light energy can be obtained from a high-pressure mercury lamp, with an ultraviolet light energy of 300-500 mJ / cm². 2 Irradiation time: 5-10 min for curing.

[0016] In a preferred embodiment of the present invention, in step S1, the surfactant is sodium dodecylbenzenesulfonate, the sodium dodecylbenzenesulfonate has a purity ≥98%, and the mass ratio of sodium dodecylbenzenesulfonate to nano silica is (0.4-0.8):(0.6-1); the nano silica is hydrophilic fumed silica with a particle size of 20-50 nm and a specific surface area ≥200 m² / g; the beaker has a capacity of 500 mL.

[0017] In a preferred embodiment of the present invention, in step S2, the mass fraction of the concentrated hydrochloric acid is 36-38%, the volume ratio of deionized water, anhydrous ethanol and concentrated hydrochloric acid is 10:90:1; the ultrasonic stirring power is 200-300W, the frequency is 40kHz, and the particle size distribution span of the dispersion is ≤0.3.

[0018] In a preferred embodiment of the present invention, in step S2, the purity of the FAS17 is ≥97%, the dropping rate is 0.1-0.2 mL / min, the centrifugation washing is performed by centrifuging three times with anhydrous ethanol at a speed of 8000-10000 r / min, each centrifugation time is 5-8 min, and the precipitate is dried at a temperature of 60-70℃.

[0019] In a preferred embodiment of the present invention, in step S3, the coating method is spraying or scraping, the wet film thickness of the coating is 80-150 μm; the wavelength of the ultraviolet lamp is 365 nm, the power density is 80-120 mW / cm², the curing time is 5-10 min, and the dry film thickness of the coating after curing is 50-100 μm.

[0020] In a preferred embodiment of the present invention, the prepared photothermal superhydrophobic coating has a water contact angle ≥155°, a sliding angle ≤8°, and after 50 cycles in a temperature range of -30°C to 80°C, the water contact angle is still ≥150°, and the photothermal conversion efficiency decreases by ≤5%.

[0021] In a preferred embodiment of the present invention, in step S3, the substrate is pretreated before coating. The pretreatment steps include ultrasonic cleaning with acetone for 10-15 minutes, rinsing with deionized water, drying at 60°C, and then spraying an ethanol solution of silane coupling agent KH-570 with a mass fraction of 1-2% and air drying at room temperature for 30 minutes.

[0022] Beneficial effects:

[0023] 1. By using nano-silica as adsorption sites for pyrrole polymerization and adjusting the ratio of nano-silica to pyrrole, uniformly dispersed polypyrrole / silica hybrid nanomaterials can be obtained. Based on this, referring to the method of fluorine-modified nano-silica, superhydrophobic modified polypyrrole / silica hybrid nanomaterials can be obtained by hydrophobically modifying the polypyrrole / silica hybrid nanomaterials with fluorosilanes. These nanomaterials exhibit good hydrophobic properties and uniform dispersion in solvents, making them suitable as fillers for constructing superhydrophobic coatings.

[0024] 2. The polypyrrole photothermal superhydrophobic coating of the present invention is prepared by ultraviolet light curing. The curing method is fast and convenient, suitable for large-area and large-scale construction, easy to apply to different object surfaces, and also has good environmental protection properties.

[0025] 3. The photopolymer-cured polypyrrole photothermal superhydrophobic coating has excellent mechanical properties and significant de-icing ability. It overcomes the shortcomings of conventional spray curing methods for preparing photothermal superhydrophobic coatings, such as high volatile organic compound (VOC) emissions, poor environmental friendliness, long curing time, low preparation efficiency, poor mechanical properties, and unstable anti-icing performance. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained from these drawings without creative effort.

[0027] Figure 1 This is a diagram showing the contact angle and roll-off angle of the photothermal superhydrophobic coating provided in the embodiments of this application;

[0028] Figure 2 Photothermal temperature rise curve of the coating under light intensity of 1 kW / m² provided for embodiments of this application;

[0029] Figure 3 The low-temperature defrosting and de-icing performance diagram of the photothermal superhydrophobic coating provided for the embodiments of this application;

[0030] Figure 4 Microscopic morphology diagram of the photothermal superhydrophobic coating provided for embodiments of this application;

[0031] Figure 5 A diagram illustrating the abrasion resistance of the photothermal superhydrophobic coating provided for embodiments of this application.

[0032] Figure 6 Microscopic morphology diagrams of comparative coatings provided for embodiments of this application;

[0033] Figure 7 A diagram illustrating the abrasion resistance of a comparative coating provided for embodiments of this application. Detailed Implementation

[0034] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0035] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, "above," "over," and "on top" of the second feature includes the first feature directly above or diagonally above the second feature, or simply indicates that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature includes the first feature directly below or diagonally below the second feature, or simply indicates that the first feature is at a lower horizontal level than the second feature.

[0036] The technical solutions in the embodiments of this application will now be described with reference to the accompanying drawings.

[0037] Example 1:

[0038] Please see Figures 1-7 This invention provides a method for preparing a rapidly curing photothermal superhydrophobic coating, comprising the following preparation method:

[0039] S1. Preparation of polypyrrole / silica hybrid nanomaterials: 0.6 g of nano-silica (50 nm in size) was weighed and added to a 500 mL beaker with 200 mL of deionized water. Then, 0.5 g of sodium dodecylbenzenesulfonate surfactant was weighed and stirred with a magnetic stirrer. After thorough mixing, 250 μL of pyrrole monomer was added and dispersed evenly. Finally, 2.5 mL of 0.5 mol / L ferric chloride solution was added. The reaction was carried out at 0 °C with mechanical stirring at 180 rpm. After 8 hours, the stirring was stopped, and the reaction was complete. The nanomaterials were washed three times with deionized water under vacuum, dried in an 80 °C oven, and then ground into powder to obtain the polypyrrole / silica hybrid nanomaterials.

[0040] S2. Preparation of superhydrophobic modified polypyrrole / silica hybrid nanomaterials: 10 ml of deionized water, 90 ml of anhydrous ethanol, and 1 ml of concentrated hydrochloric acid were added to a flask and stirred at 40°C for 10 min. 1 g of polypyrrole / silica hybrid nanomaterials were added to the above solution and ultrasonically stirred for 30 min to form a dispersion. Then, 1 ml of FAS17 was added dropwise and stirred at 40°C for 24 h. The precipitate was obtained by centrifugation and washing. The precipitate was ground into powder to obtain superhydrophobic modified polypyrrole / silica hybrid nanomaterials.

[0041] S3. Preparation of photocurable superhydrophobic coating: Weigh 5g of tripropylene glycol diacrylate as an active diluent, add 1g of epoxy acrylate and dissolve completely. Then add 0.4g of superhydrophobic modified polypyrrole / silica hybrid nanomaterial and stir thoroughly. After uniform dispersion, add 0.05g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and stir again until uniform. After coating the above solution onto the substrate, it can be cured by irradiation with a UV lamp to form the desired photothermal superhydrophobic coating. The UV light energy can be obtained from a high-pressure mercury lamp, with a UV light energy of 300-500mJ / cm2. The irradiation curing time is 5-10 minutes.

[0042] In a specific embodiment of the present invention, in S2, the mass fraction of the concentrated hydrochloric acid is 36-38%, the volume ratio of deionized water, anhydrous ethanol and concentrated hydrochloric acid is 10:90:1; the ultrasonic stirring power is 200-300W, the frequency is 40kHz, and the particle size distribution span of the dispersion is ≤0.3.

[0043] In a specific embodiment of the present invention, in S2, the purity of the FAS17 is ≥97%, the dropping rate is 0.1-0.2 mL / min, the centrifugation washing is performed by centrifuging 3 times with anhydrous ethanol at a speed of 8000-10000 r / min, the centrifugation time is 5-8 min each time, and the precipitate drying temperature is 60-70℃.

[0044] In a specific embodiment of the present invention, in S3, the coating method is spraying or scraping, the wet film thickness of the coating is 80-150μm; the wavelength of the ultraviolet lamp is 365nm, the power density is 80-120mW / cm², the curing time is 5-10min, and the dry film thickness of the coating after curing is 50-100μm.

[0045] In a specific embodiment of the present invention, the prepared photothermal superhydrophobic coating has a water contact angle ≥159° and ≤1.5°. After 50 cycles in a temperature range of -30°C to 80°C, the water contact angle is still ≥150° and the photothermal conversion efficiency decreases by ≤5%.

[0046] In a specific embodiment of the present invention, in S3, the substrate is pretreated before coating. The pretreatment steps include ultrasonic cleaning with acetone for 10-15 minutes, rinsing with deionized water, drying at 60°C, and then spraying an ethanol solution of silane coupling agent KH-570 with a mass fraction of 1-2% and air drying at room temperature for 30 minutes.

[0047] Example 2:

[0048] Please see Figures 1-7 This invention provides a method for preparing a rapidly curing photothermal superhydrophobic coating, comprising the following preparation method:

[0049] S1. Preparation of polypyrrole / silica hybrid nanomaterials: 1g of nano-silica with a particle size of 25nm was weighed and added to a 500mL beaker with 200mL of deionized water. Then, 0.8g of sodium dodecylbenzenesulfonate surfactant was weighed and added to a magnetic stirrer. After stirring evenly, 500µL of pyrrole monomer was added and dispersed evenly. Finally, 5mL of 0.5mol / L ferric chloride solution was added. The reaction was carried out at 0℃ with mechanical stirring at 180rpm. After 8 hours, the stirring was turned off and the reaction was complete. The mixture was repeatedly filtered and washed three times with deionized water, dried in an 80°C oven, and then ground into powder to obtain polypyrrole / silica hybrid nanomaterials.

[0050] S2. Preparation of superhydrophobic modified polypyrrole / silica hybrid nanomaterials: 10 ml of deionized water, 90 ml of anhydrous ethanol, and 1 ml of concentrated hydrochloric acid were added to a flask and stirred at 40°C for 10 min. 1.5 g of polypyrrole / silica hybrid nanomaterials were added to the above solution and ultrasonically stirred for 30 min to form a dispersion. Then, 2 ml of FAS17 was added dropwise and stirred at 40°C for 24 h. The precipitate was obtained by centrifugation and washing. The precipitate was ground into powder to obtain superhydrophobic modified polypyrrole / silica hybrid nanomaterials.

[0051] S3. Preparation of photocurable photothermal superhydrophobic coating: Weigh 10g of tripropylene glycol diacrylate as an active diluent, add 2g of epoxy acrylate and dissolve completely. Then add 0.6g of superhydrophobic modified polypyrrole / silica hybrid nanomaterial and stir thoroughly. After uniform dispersion, add 0.1g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and stir again until uniform. After coating the above solution onto the substrate, it can be cured by irradiation with a UV lamp to form the desired photothermal superhydrophobic coating. The UV light energy can be obtained from a high-pressure mercury lamp, with a UV light energy of 300-500mJ / cm2. The irradiation curing time is 5-10min.

[0052] In a specific embodiment of the present invention, in S2, the mass fraction of the concentrated hydrochloric acid is 36-38%, the volume ratio of deionized water, anhydrous ethanol and concentrated hydrochloric acid is 10:90:1; the ultrasonic stirring power is 200-300W, the frequency is 40kHz, and the particle size distribution span of the dispersion is ≤0.3.

[0053] In a specific embodiment of the present invention, in S2, the purity of the FAS17 is ≥97%, the dropping rate is 0.1-0.2 mL / min, the centrifugation washing is performed by centrifuging 3 times with anhydrous ethanol at a speed of 8000-10000 r / min, the centrifugation time is 5-8 min each time, and the precipitate drying temperature is 60-70℃.

[0054] In a specific embodiment of the present invention, in S3, the coating method is spraying or scraping, the wet film thickness of the coating is 80-150μm; the wavelength of the ultraviolet lamp is 365nm, the power density is 80-120mW / cm², the curing time is 5-10min, and the dry film thickness of the coating after curing is 50-100μm.

[0055] In a specific embodiment of the present invention, the prepared photothermal superhydrophobic coating has a water contact angle ≥159° and ≤1.5°. After 50 cycles in a temperature range of -30°C to 80°C, the water contact angle is still ≥150° and the photothermal conversion efficiency decreases by ≤5%.

[0056] In a specific embodiment of the present invention, in S3, the substrate is pretreated before coating. The pretreatment steps include ultrasonic cleaning with acetone for 10-15 minutes, rinsing with deionized water, drying at 60°C, and then spraying an ethanol solution of silane coupling agent KH-570 with a mass fraction of 1-2% and air drying at room temperature for 30 minutes.

[0057] Example 3:

[0058] Please see Figures 1-7 This invention provides a method for preparing a rapidly curing photothermal superhydrophobic coating, comprising the following preparation method:

[0059] S1. Preparation of polypyrrole / silica hybrid nanomaterials: 0.8 g of nano-silica (50 nm in size) was weighed and added to a 500 mL beaker with 200 mL of deionized water. Then, 0.6 g of sodium dodecylbenzenesulfonate surfactant was weighed and stirred with a magnetic stirrer. After thorough mixing, 250 μL of pyrrole monomer was added and dispersed evenly. Finally, 3.5 mL of 0.5 mol / L ferric chloride solution was added. The reaction was carried out at 0 °C with mechanical stirring at 180 rpm. After 8 hours, the stirring was stopped, and the reaction was complete. The nanomaterials were washed three times with deionized water under vacuum, dried in an 80 °C oven, and then ground into powder to obtain the polypyrrole / silica hybrid nanomaterials.

[0060] S2. Preparation of superhydrophobic modified polypyrrole / silica hybrid nanomaterials: 10 ml of deionized water, 90 ml of anhydrous ethanol, and 1 ml of concentrated hydrochloric acid were added to a flask and stirred at 40°C for 10 min. 1.3 g of polypyrrole / silica hybrid nanomaterials were added to the above solution and ultrasonically stirred for 30 min to form a dispersion. Then, 1.5 ml of FAS17 was added dropwise and stirred at 40°C for 24 h. The precipitate was obtained by centrifugation and washing. The precipitate was ground into powder to obtain superhydrophobic modified polypyrrole / silica hybrid nanomaterials.

[0061] S3. Preparation of photocurable photothermal superhydrophobic coating: Weigh 8g of tripropylene glycol diacrylate as an active diluent, add 1g of epoxy acrylate and dissolve completely. Then add 0.5g of superhydrophobic modified polypyrrole / silica hybrid nanomaterial and stir thoroughly. After uniform dispersion, add 0.08g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and stir again until uniform. After coating the above solution onto the substrate, it can be cured by irradiation with a UV lamp to form the desired photothermal superhydrophobic coating. The UV light energy can be obtained from a high-pressure mercury lamp, with a UV light energy of 300-500mJ / cm2. The irradiation curing time is 5-10min.

[0062] In a specific embodiment of the present invention, in S2, the mass fraction of the concentrated hydrochloric acid is 36-38%, the volume ratio of deionized water, anhydrous ethanol and concentrated hydrochloric acid is 10:90:1; the ultrasonic stirring power is 200-300W, the frequency is 40kHz, and the particle size distribution span of the dispersion is ≤0.3.

[0063] In a specific embodiment of the present invention, in S2, the purity of the FAS17 is ≥97%, the dropping rate is 0.1-0.2 mL / min, the centrifugation washing is performed by centrifuging 3 times with anhydrous ethanol at a speed of 8000-10000 r / min, the centrifugation time is 5-8 min each time, and the precipitate drying temperature is 60-70℃.

[0064] In a specific embodiment of the present invention, in S3, the coating method is spraying or scraping, the wet film thickness of the coating is 80-150μm; the wavelength of the ultraviolet lamp is 365nm, the power density is 80-120mW / cm², the curing time is 5-10min, and the dry film thickness of the coating after curing is 50-100μm.

[0065] In a specific embodiment of the present invention, the prepared photothermal superhydrophobic coating has a water contact angle ≥159°, a sliding angle ≤1.5°, and after 50 cycles in a temperature range of -30°C to 80°C, the water contact angle is still ≥150°, and the photothermal conversion efficiency decreases by ≤5%.

[0066] In a specific embodiment of the present invention, in S3, the substrate is pretreated before coating. The pretreatment steps include ultrasonic cleaning with acetone for 10-15 minutes, rinsing with deionized water, drying at 60°C, and then spraying an ethanol solution of silane coupling agent KH-570 with a mass fraction of 1-2% and air drying at room temperature for 30 minutes.

[0067] The preparation of superhydrophobic coatings via ultraviolet (UV) curing offers advantages such as rapid curing speed, low energy consumption, environmental friendliness, and superior coating performance, making it a promising direction for future coating research and development. Therefore, developing photothermal superhydrophobic coatings with rapid curing processes and excellent mechanical and anti-icing properties through UV curing holds significant research value and application prospects.

[0068] Since polypyrrole and silica composites are mostly focused on adsorption or conductivity, they have not been used as photothermal-superhydrophobic bifunctional fillers. Furthermore, photothermal-superhydrophobic coatings often use Fe3O4 or titanium nitride as photothermal agents, which suffers from high cost and poor compatibility with resin matrices. This application, for the first time, uses a polypyrrole / silica hybrid material as the core functional filler. It utilizes the broad-spectrum photothermal absorption characteristics of polypyrrole (temperature rise up to 80℃ under 1 Sun illumination) and constructs a superhydrophobic substrate through the nano-rough structure of silica, achieving in-situ synergy between "photothermal conversion and micro / nano rough structure".

[0069] By adjusting the ratio of nano-silica to pyrrole monomers, using silica as the polymerization adsorption site, and combining the steric hindrance effect of surfactants, the problem of polypyrrole aggregation was solved. The hybrid material was dispersed in the resin with a particle size of 50-200 nm, and the dispersion uniformity was improved.

[0070] Existing photothermal superhydrophobic coatings mostly employ heat curing or solvent-based spraying, resulting in VOC emissions ≥50g / L. A few UV curing methods rely on fluorinated resin matrices, leading to high costs and poor mechanical properties. This application utilizes an epoxy acrylate-reactive diluent system, achieving a shorter UV curing time and significantly improved efficiency compared to heat curing. VOC emissions are ≤10g / L, and the coating hardness reaches 3H, far exceeding the existing 2H standard for UV-cured coatings.

[0071] By covalently bonding hybrid materials with epoxy acrylate, a structural gradient of "superhydrophobic surface - highly cross-linked interior" is achieved. After 500 sandpaper abrasions, the water contact angle is still ≥150°, solving the problem of balancing mechanical properties and superhydrophobicity and breaking through the durability bottleneck of existing technologies.

[0072] The photothermal superhydrophobic coating prepared by this technique exhibits excellent superhydrophobic properties, as shown in the attached figure. Figure 1 As shown, it maintains excellent liquid repellency to common liquids, with a water contact angle (CA) reaching 159° and a water roll-off angle (SA) of less than 1.5°. The coating also exhibits excellent photothermal properties; under illumination of 1 kW / m², the coating can heat up to 78.5°C within 10 minutes, as shown in the attached figure. Figure 2 As shown in the attached figure. At -10°C, de-icing and defrosting studies were conducted on the coating. It was found that under light intensity of 1 kW / m², the coating can quickly remove the frost and ice layers covering the surface, as shown in the attached figure. Figure 3 As shown, the photocured photothermal superhydrophobic coating exhibits excellent de-icing and defrosting properties.

[0073] Comparative example:

[0074] Steps S1 and S2 are the same. Step S3 does not use photocuring to cure the coating; instead, it uses solvent spraying. Specifically, 5g of ethyl acetate is used as a diluent, and 1g of epoxy acrylate is added and dissolved completely. Then, 0.4-0.6g of superhydrophobic modified polypyrrole / silica hybrid nanomaterials are added and stirred thoroughly until evenly dispersed. Finally, 0.1g of polyetheramine D400 is added as a curing agent and stirred again until homogeneous. The solution is then sprayed onto the substrate and dried in an 80°C oven for 2 hours to cure and form the desired photothermal superhydrophobic coating.

[0075] The coating cured by ultraviolet light exhibits a micro-nano structure in its surface filler and resin. The rapid ultraviolet curing method ensures a very tight bond between the two, as shown in the attached image. Figure 4 As shown in the figure. The study used a comparative experimental group, where UV curing was not employed; instead, polyetheramine D400 was added to the epoxy acrylic resin as a curing agent. The coating cured by this curing agent was the control group. The microstructure of the control group coating is shown in the figure. Figure 6As shown, its surface exhibits a micro-nano structure, but the filler and resin are not tightly bonded, resulting in a looser surface structure compared to the photocured coating. Sandpaper abrasion tests also reveal that the photocured superhydrophobic coating possesses superior mechanical durability; even after 500 sandpaper abrasion cycles, its surface retains its superhydrophobic state, as shown in the attached figure. Figure 5 As shown in the attached figure. In contrast, the coating in the control group began to lose its superhydrophobic properties after 270 sandpaper abrasions, as shown in the attached figure. Figure 7 As shown, rapid UV curing can significantly improve the mechanical durability of the coating.

[0076] The above description is merely an embodiment of this application and is not intended to limit the scope of protection of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of protection of this application. It should be noted that similar reference numerals and letters in the following figures indicate similar items; therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

Claims

1. A method for preparing a fast-curing photothermal superhydrophobic coating, characterized in that, The preparation method comprises the following steps: S1, preparation of polypyrrole / silica hybrid nanomaterial: 0.6-1 g of nanosilica is weighed and added to a beaker with 200 mL of deionized water, then 0.4-0.8 g of surfactant is weighed and added to the beaker and stirred, after uniform stirring, 250-500 uL of pyrrole monomer is added and dispersed uniformly, finally 2.5-5 mL of 0.5 mol / L ferric chloride solution is added, and stirring is carried out for 8 h until the reaction is completed; the product is repeatedly filtered and washed with deionized water, dried in an 80° oven, and ground into powder to obtain the polypyrrole / silica hybrid nanomaterial; S2, preparation of super-hydrophobic modified polypyrrole / silica hybrid nanomaterial: 10 mL of deionized water, 90 mL of anhydrous ethanol, and 1 mL of concentrated hydrochloric acid are added to a flask, stirred at a temperature of 40° for 10 min, 1-1.5 g of polypyrrole / silica hybrid nanomaterial is added to the above solution and ultrasonically stirred for 30 min to form a dispersion liquid, then 1-2 mL of FAS17 is added dropwise, and stirred at 40° for 24 h, and the precipitate is obtained by centrifugal washing; the product is ground into powder to obtain the super-hydrophobic modified polypyrrole / silica hybrid nanomaterial; S3, preparation of photocuring photo-thermal super-hydrophobic coating: 5-10 g of active diluent is weighed, 1-2 g of epoxy acrylate is added, after complete dissolution, 0.6-1 g of super-hydrophobic modified polypyrrole / silica hybrid nanomaterial is added and stirred thoroughly, after uniform stirring and dispersion, 0.05-0.1 g of photoinitiator is added and stirred again; the obtained solution is coated on a substrate, and irradiated and cured with a UV lamp to form the required photo-thermal super-hydrophobic coating.

2. The method of claim 1, wherein the method further comprises the step of applying a second layer of the light-heat superhydrophobic coating on the first layer of the light-heat superhydrophobic coating. In S1, the nanosilica particle size is 25-50 nm, the reaction temperature is 0°C, mechanical stirring is carried out at a stirring speed of 180 rpm for 8 h; the product is repeatedly filtered and washed with deionized water for 3 times.

3. The method of claim 1, wherein the method further comprises the step of applying a second layer of the light-heat superhydrophobic coating on the first layer of the light-heat superhydrophobic coating. In S3, the active diluent is a mixture of tripropyleneglycol diacrylate or trimethylolpropane triacrylate and 1,6-hexanediol diacrylate, and the photoinitiator is a complex of 2-hydroxy-2-methyl-1-phenyl-1-propanone or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

4. The method of claim 1, wherein the method further comprises the step of applying a second layer of the light-heat superhydrophobic coating on the first layer of the light-heat superhydrophobic coating. In S3, the UV light energy can be obtained from a high-pressure mercury lamp, the UV light energy is 300-500 mJ / cm2, and the irradiation time is 15-30 min.

5. The method of claim 1, wherein the method further comprises: In S1, the surfactant is sodium dodecyl benzene sulfonate, the purity of the sodium dodecyl benzene sulfonate is ≥98%, and the mass ratio of the sodium dodecyl benzene sulfonate to nanosilica is (0.4-0.8):(0.6-1); the nanosilica is hydrophilic fumed silica, the particle size is 20-50 nm, and the specific surface area is ≥200 m² / g; the beaker has a specification of 500 mL.

6. The method of claim 1, wherein the method further comprises: In S2, the mass fraction of the concentrated hydrochloric acid is 36-38%, the volume ratio of deionized water, anhydrous ethanol, and concentrated hydrochloric acid is 10:90:1; the ultrasonic stirring power is 200-300 W, the frequency is 40 kHz, and the dispersion liquid particle size distribution span is ≤0.

3.

7. The method of claim 1, wherein the method further comprises the step of applying a second layer of the light-heat superhydrophobic coating on the first layer of the light-heat superhydrophobic coating. In S2, the purity of the FAS 17 is ≥ 97%, the dropping rate is 0.1-0.2 mL / min; the centrifugal washing is carried out by using anhydrous ethanol, the rotation speed is 8000-10000 r / min, the centrifugal time is 5-8 min each time, and the drying temperature of the precipitate is 60-70℃.

8. The method of claim 1, wherein the method further comprises the step of applying a second layer of the light-heat superhydrophobic coating on the first layer of the light-heat superhydrophobic coating. In S3, the coating method is spraying or scraping, the wet film thickness of the coating is 80-150 μm; the wavelength of the ultraviolet lamp is 365 nm, the power density is 80-120 mW / cm², the curing time is 5-10 min, and the dry film thickness of the coating after curing is 50-100 μm.

9. The method of claim 1, wherein the method further comprises the step of applying a second layer of the light-heat superhydrophobic coating on the first layer of the light-heat superhydrophobic coating. The prepared photo-thermal super-hydrophobic coating has a water contact angle ≥ 155° and a sliding angle ≤ 8°, and after 50 cycles in the temperature range of-30℃ to 80℃, the water contact angle is still ≥ 150°, and the photo-thermal conversion efficiency attenuation is ≤ 5%.

10. The method of claim 1, wherein the method is a method of preparing a fast-curing photothermal superhydrophobic coating. In S3, the substrate is pretreated before coating, the pretreatment step comprises sequentially ultrasonic cleaning with acetone for 10-15 min, rinsing with deionized water, drying at 60℃, then spraying an ethanol solution of silane coupling agent KH-570, the mass fraction of the ethanol solution is 1-2%, and air drying at room temperature for 30 min.

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