A photothermal superhydrophobic coating and its preparation method

Abstract

This invention discloses a photothermal superhydrophobic coating and its preparation method, relating to the field of hydrophobic coating technology. It comprises a modified fluorosilicone resin solution, modified nanoscale carbon-based materials, functional additives, polypyrrole resin, adhesion promoters, etc. The invention uses polysiloxane and fluorinated monomers to polymerize a fluorosilicone block polymer, and introduces benzoxazine monomers into the structure as an anti-corrosion resin matrix to prepare a modified fluorosilicone resin solution. A photothermal layer is introduced by adding modified carbon-based materials, and a sprayable superhydrophobic coating is prepared by combining hydrophobic silica and filler additives. Furthermore, the coating utilizes the properties of carbon black and carbon nanotubes converting their own lattice vibrations into light energy, the hydrophobicity of nano-silica, and the addition of polypyrrole to the resin system to further ensure the photothermal performance of the coating. The surface energy of fluorosilicone elements and the ring-opening polymerization of benzoxazine resin itself give the coating excellent corrosion resistance, wear resistance, and weather resistance.

Description

Technical Field

[0001] This invention relates to the field of hydrophobic coating technology, specifically to a photothermal superhydrophobic coating and its preparation method. Background Technology

[0002] Surface icing is a common natural phenomenon; however, it often causes serious damage to infrastructure and industrial equipment. In particular, surface icing can significantly impact power transmission, air transport, wind turbines, and ocean-going vessels, potentially leading to energy waste, emergencies, and safety hazards. Traditional de-icing methods include mechanical de-icing, microwave de-icing, and manual de-icing, but these are generally inefficient and energy-intensive.

[0003] Superhydrophobic coatings, due to their micro- and nano-structured surfaces, can remove water droplets during the condensation stage, thus delaying ice nucleation and reducing ice accumulation. However, these micro- and nano-structures form a mechanical interlock with the ice, increasing the adhesion strength between the ice and the material surface, making it difficult to remove the ice under the influence of gravity, wind, and vibration. Meanwhile, traditional mechanical methods for de-icing superhydrophobic surfaces cause significant impacts due to physical contact, damaging the micro- and nano-structures and weakening the anti-icing function. Single hydrophobic surfaces have limitations in anti-icing; therefore, non-contact remote lighting methods are gentler and more durable, but their implementation is difficult. Photothermal materials have high photothermal conversion efficiency and no chemical pollution, offering advantages such as energy saving and environmental friendliness, and are gaining increasing attention in the field of anti-icing materials. Therefore, coatings combining photothermal anti-icing and superhydrophobic effects have broad application prospects; however, existing technologies rarely combine these two properties. Furthermore, existing superhydrophobic coatings suffer from poor corrosion resistance and insufficient wear and weather resistance.

[0004] Therefore, there is an urgent need to synthesize a photothermal superhydrophobic coating that can not only perform hydrophobic functions but also perform photothermal conversion, thus overcoming the shortcomings of superhydrophobic coatings which can only perform hydrophobic functions and cannot perform photothermal conversion, and can also increase the coating's corrosion resistance, wear resistance and weather resistance. Summary of the Invention

[0005] To address the above problems, the purpose of this invention is to provide a photothermal superhydrophobic coating and its preparation method.

[0006] To achieve the above objectives, the present invention employs the following technical solution: A photothermal superhydrophobic coating, by weight, is composed of the following raw materials: 30-40 parts of modified fluorosilicone resin solution, 20-30 parts of modified nano-scale carbon-based material, 3-5 parts of functional additives, 3-15 parts of polypyrrole resin, 0.1-0.8 parts of adhesion promoter, 0.05-0.1 parts of nano-silica, 15-25 parts of filler, and 25-35 parts of a first organic solvent; The modified fluorosilicone resin solution was prepared according to the following steps: Methacryloyloxypropyltrimethoxysilane, ester-containing benzoxazine monomer, fluorinated acrylate monomer and solvent ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 15-20 minutes, initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 75-85℃ and the reaction was carried out for 12-24 hours to obtain a reaction solution. The obtained reaction solution was placed at 30-40℃ and vacuum dried for 8-10 hours to obtain modified fluorosilicone resin. The obtained modified fluorosilicone resin was dissolved in a second organic solvent to prepare a modified fluorosilicone resin solution with a solid content of 30-60%. The fluorinated acrylic monomer is dodecyl fluoroheptyl methacrylate or / and perfluorobutyl ethyl methacrylate; The initiator is AIBN or BPO, and the amount of initiator is 0.1-2% of the monomer mass. The mass ratio of initiator to ethyl acetate in the initiator-ethyl acetate solution is 1:8-10. The mass ratio of the methacryloyloxypropyloxysilane, the ester-containing benzoxazine monomer, and the fluorinated acrylate monomer is 8~15:5~12:18~25; The amount of ethyl acetate solvent used is 50-60% of the total mass of the monomers; The second organic solvent is ethyl acetate or dichloromethane; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is carbon black or carbon nanotubes.

[0007] Preferably, the functional additive is two or three of the following: wetting and dispersing agent, defoamer, and leveling agent. More preferably, the wetting and dispersing agent is a nonionic wetting and dispersing agent or a fluorocarbon wetting agent, such as Genisperse 7742, Patcham® 9060, FC-5503, Silok® 7630, 4010, 505s; the defoamer is a mineral oil defoamer, a silicone defoamer, or a polyether defoamer, such as Skytech® SAT80, RB-5209, Rhodoline DF4226, 2503; and the leveling agent is a silicone oil leveling agent or a polyether leveling agent, such as FDG-513, WE-D8939, AMORSO-137, AFCONA3596, 3700, 2050.

[0008] Preferably, the adhesion promoter is a silane coupling agent Z-6121 or a titanate coupling agent; the titanate coupling agent is triisostearoyl titanate isopropyl or isopropyl tris(dioctylpyrophosphate) titanate.

[0009] Preferably, the filler is a mixture of two or more of the following: heavy calcium carbonate, talc, barium sulfate, sericite powder, and carbon black.

[0010] Preferably, the first organic solvent is one or more of butyl acetate, ethyl acetate, or dichloromethane.

[0011] Preferably, the specific preparation process of the modified nanoscale carbon-based material is as follows: The nanoscale carbon-based material was slowly added to a mixed strong acid in small amounts multiple times. The mixture was heated to 58-62°C under mechanical stirring and stirred for 12-24 hours. The mixture was then washed until neutral and dried to obtain the oxidized nanoscale carbon-based material. The obtained oxidized nanoscale carbon-based material was ultrasonically dispersed in ethanol, and a second silane coupling agent was added to it while stirring. The stirring was continued for 0.5 to 1 hour, filtered, washed with ethanol, and dried under vacuum to obtain the modified nanoscale carbon-based material. The mass ratio of nanoscale carbon-based material, mixed strong acid, and second silane coupling agent is 1:100~150:0.03~0.06; The mixed strong acid is obtained by mixing concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 100:40~50.

[0012] Preferably, the second silane coupling agent is one or more of silane coupling agents KH560, KH570 or KH550.

[0013] The present invention also includes a method for preparing a photothermal superhydrophobic coating, comprising the following steps: mixing 0.1-0.8 parts by weight of an adhesion promoter, 15-25 parts by weight of a filler and 25-35 parts by weight of a first organic solvent, grinding to below 40 μm, filtering, adding 30-40 parts by weight of a modified fluorosilicone resin solution, 3-15 parts by weight of a polypyrrole resin, 20-30 parts by weight of a modified nano-scale carbon-based material, 0.05-0.1 parts by weight of nano-silica, and 3-5 parts by weight of a functional additive, stirring and dispersing evenly to obtain a photothermal superhydrophobic coating.

[0014] The present invention has the following advantages over the prior art: The superhydrophobic coating for photothermal heating of this invention incorporates modified photothermal materials, and after drying, the coating surface possesses a micro / nano structure, exhibiting superhydrophobic properties. Firstly, this invention uses polysiloxane and fluorinated monomers to polymerize a fluorosilicone block polymer, and introduces benzoxazine monomers into the structure as an anti-corrosion resin matrix to prepare a modified fluorosilicone resin solution. A photothermal layer is introduced by adding modified carbon-based materials, combined with hydrophobic silica and fillers to prepare a sprayable superhydrophobic coating. Secondly, the coating utilizes the properties of carbon black, carbon nanotubes converting their own lattice vibrations into light energy, the hydrophobicity of nano-silica, and the addition of polypyrrole to the resin system to further ensure the coating's photothermal performance. The surface energy of fluorosilicone elements and the ring-opening polymerization of the benzoxazine resin itself give the coating excellent corrosion resistance, wear resistance, and weather resistance.

[0015] The photothermal superhydrophobic coating of this invention can be sprayed onto substrates of various materials and shapes, exhibiting strong adhesion and preventing cracking. This coating integrates multiple functions such as photothermal anti-icing, superhydrophobic de-icing, and long-term corrosion protection, meeting the anti-icing and adhesion requirements of different application scenarios and reducing reliance on multiple coatings and the cost of repeated application. This coating combines photothermal superhydrophobic de-icing and long-term corrosion protection properties into a multi-functional integrated product, and its operation is simple and controllable. Detailed Implementation

[0016] The purpose of this invention is to provide a photothermal superhydrophobic coating and its preparation method, which is achieved through the following technical solution: The following are some manufacturers of additives. Wetting and dispersing agents: Genisperse 7742 Nanjing Shangqin New Material Technology Co., Ltd., Patcham® 9060 Shierli Coatings, FC-5503 Guangdong Zhongxiang New Material Co., Ltd., Silok®7630 Silok New Material Co., Ltd., 4010 Evcona, 505s Guangzhou Siteyuan Chemical Co., Ltd.; Defoamers: Skytech® SAT80 (Zhonghaojing Polymer New Materials Co., Ltd.), RB-5209 (Leibang High-Tech Materials Co., Ltd.), Rhodoline DF4226 (Liantuo Blueprint). Leveling agents: FDG-513 Fangding New Materials Co., Ltd., WE-D8939 Anhui Jiazhi Xinno Chemical Co., Ltd., AMORSO-137 Jiji Yan Shandong New Materials Co., Ltd., AFCONA 3596 Evcona Polymer Co., Ltd., 3700 Evcona, 2050 Guangzhou Siteyuan Chemical Co., Ltd. Triisostearoyl titanate isopropyl triisostearoyl titanate, also known as triisostearoyl titanate isopropyl triisostearoyl titanate.

[0017] The polypyrrole resin is a commercially available common polypyrrole resin, which is sold by companies such as Xi'an Qiyue Biotechnology Co., Ltd. and Xi'an Ruixi Biotechnology Co., Ltd.

[0018] The ester-containing benzoxazine monomers were prepared based on Chapter 2 of the Master's thesis of Shandong University: Synthesis and Performance Study of Ester-Containing Benzoxazine and Its Polymers.

[0019] The concentrated sulfuric acid and concentrated nitric acid described in this invention are commercially available and conventional. Generally, the mass concentration of concentrated sulfuric acid is about 98%, and the mass concentration of concentrated nitric acid is about 68%.

[0020] The present invention will be further described below with reference to specific embodiments. Example 1

[0021] A photothermal superhydrophobic coating is composed of the following raw materials: 30 kg of modified fluorosilicone resin solution, 20 kg of modified nano-scale carbon-based material, 1 kg of wetting and dispersing agent Genisperse 7742, 2 kg of defoamer Skytech® SAT80, 3 kg of polypyrrole resin, 0.1 kg of silane coupling agent Z-6121, 0.05 kg of nano-silica, 5 kg of heavy calcium carbonate, 10 kg of talc, and 25 kg of butyl acetate; The modified fluorosilicone resin solution was prepared according to the following steps: 4 kg of methacryloxypropyltrimethoxysilane, 2.5 kg of benzoxazine monomer containing ester group, 9 kg of dodecafluoroheptyl methacrylate and 7.75 kg of ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 15 minutes, an initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 75°C and the reaction was carried out for 12 hours to obtain a reaction solution. The obtained reaction solution was placed at 30°C and vacuum dried for 8 hours to obtain modified fluorosilicone resin. Take 9 kg of the obtained modified fluorosilicone resin and dissolve it in 21 kg of ethyl acetate to obtain a modified fluorosilicone resin solution; The initiator-ethyl acetate solution was obtained by dissolving 15.5 g of AIBN in 124 g of ethyl acetate; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is carbon black. Example 2

[0022] A photothermal superhydrophobic coating is composed of the following raw materials: 40 kg of modified fluorosilicone resin solution, 30 kg of modified nano-sized carbon-based material, 3 kg of wetting and dispersing agent Patcham® 9060, 1 kg of defoamer RB-5209, 1 kg of leveling agent FDG-513, 15 kg of polypyrrole resin, 0.8 kg of isopropyl triisostearoyl titanate, 0.1 kg of nano-silica, 10 kg of barium sulfate, 15 kg of sericite powder, and 35 kg of ethyl acetate; The modified fluorosilicone resin solution was prepared according to the following steps: 7.5 kg of methacryloxypropyltrimethoxysilane, 6 kg of ester-containing benzoxazine monomer, 12.5 kg of perfluorobutyl ethyl methacrylate and 15.6 kg of ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 20 minutes, an initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 85°C and the reaction was carried out for 24 hours to obtain a reaction solution. The obtained reaction solution was placed at 40°C and vacuum dried for 10 hours to obtain modified fluorosilicone resin. Take 24 kg of the obtained modified fluorosilicone resin and dissolve it in 16 kg of dichloromethane to prepare a modified fluorosilicone resin solution; The initiator-ethyl acetate solution was obtained by dissolving 0.52 kg BPO in 5.2 kg ethyl acetate; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is carbon nanotubes. Example 3

[0023] A photothermal superhydrophobic coating is composed of the following raw materials: 32 kg of modified fluorosilicone resin solution, 22 kg of modified nano-scale carbon-based material, 1 kg of wetting and dispersing agent FC-5503, 1 kg of defoamer Rhodoline DF4226, 1.5 kg of leveling agent WE-D8939, 4 kg of polypyrrole resin, 0.2 kg of isopropyl tris(dioctyl pyrophosphate) titanate, 0.06 kg of nano-silica, 8 kg of sericite powder, 8 kg of carbon black, and 12 kg of dichloromethane; The modified fluorosilicone resin solution was prepared according to the following steps: 4 kg of methacryloxypropyltrimethoxysilane, 2.4 kg of benzoxazine monomer containing ester group, 4 kg of dodecafluoroheptyl methacrylate, 4 kg of perfluorobutyl ethyl methacrylate fluorinated acrylate monomer and 7.5 kg of ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 16 minutes, an initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 78°C and the reaction was carried out for 15 hours to obtain a reaction solution. The obtained reaction solution was placed at 32°C and vacuum dried for 8.5 hours to obtain modified fluorosilicone resin. 12.8 kg of the modified fluorosilicone resin was dissolved in 19.2 kg of ethyl acetate to obtain a modified fluorosilicone resin solution; The initiator-ethyl acetate solution was obtained by dissolving 0.072 kg AIBN in 0.648 kg ethyl acetate; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is carbon nanotubes, and the process specifically includes the following steps: 22 kg of carbon nanotubes were slowly added to 2310 kg of mixed strong acid in small amounts several times. The mixture was heated to 60 °C under mechanical stirring and stirred for 15 hours. After washing until neutral, the mixture was dried to obtain oxidized nanoscale carbon-based materials. The obtained oxidized nanoscale carbon-based material was ultrasonically dispersed in 180 kg of ethanol. 0.44 kg of silane coupling agent KH560 and 0.44 kg of silane coupling agent KH570 were added to the mixture while stirring. The mixture was stirred for 50 minutes, filtered, washed with ethanol, and dried under vacuum to obtain the modified nanoscale carbon-based material. The mixed strong acid is obtained by mixing concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 100:45. Example 4

[0024] A photothermal superhydrophobic coating is composed of the following raw materials: 38 kg of modified fluorosilicone resin solution, 26 kg of modified nano-scale carbon-based material, 1.1 kg of wetting and dispersing agent Silok® 7630, 1.1 kg of defoamer 2503, 1 kg of leveling agent AMORSO-137, 10 kg of polypyrrole resin, 0.4 kg of isopropyl tris(dioctyl pyrophosphate) titanate, 0.08 kg of nano silica, 5 kg of talc, 5 kg of barium sulfate, 10 kg of sericite powder, 14 kg of butyl acetate, and 14 kg of dichloromethane; The modified fluorosilicone resin solution was prepared according to the following steps: 4.5 kg of methacryloxypropyltrimethoxysilane, 4 kg of benzoxazine monomer containing ester group, 5.5 kg of dodecafluoroheptyl methacrylate and 5.5 kg of ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 18 minutes, an initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 80°C and the reaction was carried out for 15 hours to obtain a reaction solution. The obtained reaction solution was placed at 35°C and vacuum dried for 9 hours to obtain modified fluorosilicone resin. 19 kg of the obtained modified fluorosilicone resin was dissolved in 19 kg of dichloromethane to prepare a modified fluorosilicone resin solution. The initiator-ethyl acetate solution was obtained by dissolving 0.117 kg BPO in 1 kg ethyl acetate; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is nanoscale carbon black, and the specific process is as follows: 26 kg of nano-grade carbon black was slowly added to 2600 kg of mixed strong acid in small amounts several times. The mixture was heated to 58 °C under mechanical stirring and stirred for 24 hours. The mixture was then washed until neutral and dried to obtain oxidized nano-grade carbon black. The obtained oxidized nano-sized carbon black was ultrasonically dispersed in 250 kg of ethanol. 0.78 kg of silane coupling agent KH560 was added to the mixture while stirring. Stirring was continued for 0.5 hours. The mixture was then filtered, washed with ethanol, and dried under vacuum to obtain the modified nano-sized carbon-based material. The mixed strong acid is obtained by mixing concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 100:40. Example 5

[0025] A photothermal superhydrophobic coating is composed of the following raw materials: 34 kg of modified fluorosilicone resin solution, 25 kg of modified nano-scale carbon-based material, 1.4 kg of wetting and dispersing agent 4010, 1.2 kg of defoamer Skytech® SAT80, 1.2 kg of leveling agent AFCONA 3596, 6 kg of polypyrrole resin, 0.4 kg of silane coupling agent Z-6121, 0.07 kg of nano-silica, 6 kg of heavy calcium carbonate, 6 kg of sericite powder, 6 kg of carbon black, and 30 kg of ethyl acetate; The modified fluorosilicone resin solution was prepared according to the following steps: 4 kg of methacryloxypropyltrimethoxysilane, 3 kg of benzoxazine monomer containing ester group, 3 kg of dodecafluoroheptyl methacrylate, 4 kg of perfluorobutyl ethyl methacrylate and 7.7 kg of ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 19 minutes, an initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 78°C and the reaction was carried out for 20 hours to obtain a reaction solution. The obtained reaction solution was placed at 36°C and vacuum dried for 9 hours to obtain modified fluorosilicone resin. 11.9 kg of the obtained modified fluorosilicone resin was dissolved in 22.1 kg of dichloromethane to prepare a modified fluorosilicone resin solution; The initiator-ethyl acetate solution was obtained by dissolving 0.014 kg BPO in 0.14 kg ethyl acetate; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is carbon nanotubes, and the specific steps are as follows: 25 kg of carbon nanotubes were slowly added to 3750 kg of mixed strong acid in small amounts several times. The mixture was heated to 62 °C under mechanical stirring and stirred for 12 hours. The mixture was washed until neutral and dried to obtain oxidized carbon nanotubes. The obtained oxidized carbon nanotubes were ultrasonically dispersed in 200 kg of ethanol. 1.5 kg of silane coupling agent KH570 was added to the mixture while stirring. Stirring was continued for 1 hour. The mixture was then filtered, washed with ethanol, and dried under vacuum to obtain the modified nanoscale carbon-based material. The mixed strong acid is obtained by mixing concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 100:50. Example 6

[0026] A photothermal superhydrophobic coating is composed of the following raw materials: 35 kg of modified fluorosilicone resin solution, 25 kg of modified nano-sized carbon-based material, 1 kg of wetting and dispersing agent 505s, 2 kg of defoamer RB-5209, 1 kg of leveling agent AFCONA 3700, 8 kg of polypyrrole resin, 0.5 kg of isopropyl triisostearoyl titanate, 0.08 kg of nano-silica, 10 kg of talc, 10 kg of carbon black, 15 kg of ethyl acetate, and 15 kg of dichloromethane; The modified fluorosilicone resin solution was prepared according to the following steps: 4.5 kg of methacryloxypropyltrimethoxysilane, 4 kg of ester-containing benzoxazine monomer, 10 kg of fluorinated acrylate monomer and 10 kg of ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 18 minutes, an initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 82°C and the reaction was carried out for 20 hours to obtain a reaction solution. The obtained reaction solution was placed at 38°C and vacuum dried for 9 hours to obtain modified fluorosilicone resin. 15.75 kg of the obtained modified fluorosilicone resin was dissolved in 19.25 kg of ethyl acetate to prepare a modified fluorosilicone resin solution; The fluorinated acrylic monomer is dodecyl fluoroheptyl methacrylate or / and perfluorobutyl ethyl methacrylate; The initiator-ethyl acetate solution was obtained by dissolving 0.02 kg AIBN in 0.18 kg ethyl acetate; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is carbon black, and the process specifically includes the following steps: 25 kg of carbon black was slowly added to 2600 kg of mixed strong acid in small amounts several times. The mixture was heated to 60°C under mechanical stirring and stirred for 18 hours. The mixture was then washed until neutral and dried to obtain oxidized carbon black. The obtained oxidized carbon black was ultrasonically dispersed in 200 kg of ethanol. 1.25 kg of silane coupling agent KH550 was added to it while stirring. Stirring was continued for 45 minutes. The mixture was filtered, washed with ethanol, and dried under vacuum to obtain modified nanoscale carbon-based materials. The mixed strong acid is obtained by mixing concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 100:45. Example 7

[0027] The preparation method of the photothermal superhydrophobic coating described in Example 1 includes the following steps: Mix 5 kg of heavy calcium carbonate, 10 kg of talc, 0.1 kg of silane coupling agent Z-6121 and 25 kg of butyl acetate, grind to below 40 μm, filter, add 30 kg of modified fluorosilicone resin solution, 20 kg of modified nano-scale carbon-based material, 3 kg of polypyrrole resin, 0.05 kg of nano-silica, 1 kg of wetting and dispersing agent Genisperse 7742 and 2 kg of defoamer Skytech® SAT80, stir and disperse evenly to obtain a photothermal superhydrophobic coating. Example 8

[0028] The preparation method of the photothermal superhydrophobic coating described in Example 2 includes the following steps: 0.8 kg of triisostearoyl titanate isopropyl ester, 10 kg of barium sulfate, 15 kg of sericite powder and 35 kg of ethyl acetate were mixed and ground to below 40 μm. After filtration, 40 kg of modified fluorosilicone resin solution, 30 kg of modified nano-sized carbon-based material, 3 kg of wetting and dispersing agent Patcham® 9060, 1 kg of defoamer RB-5209, 1 kg of leveling agent FDG-513, 15 kg of polypyrrole resin and 0.1 kg of nano-silica were added and stirred to disperse evenly to obtain a photothermal superhydrophobic coating. Example 9

[0029] The preparation method of the photothermal superhydrophobic coating described in Example 3 includes the following steps: 0.2 kg of isopropyl tris(dioctyl pyrophosphoryloxy) titanate, 8 kg of sericite powder, 8 kg of carbon black and 12 kg of dichloromethane were mixed and ground to below 40 μm. After filtration, 32 kg of modified fluorosilicone resin solution, 22 kg of modified nano-sized carbon-based material, 1 kg of wetting and dispersing agent FC-5503, 1 kg of defoamer Rhodoline DF4226, 1.5 kg of leveling agent WE-D8939, 4 kg of polypyrrole resin and 0.06 kg of nano-silica were added and stirred and dispersed evenly to obtain a photothermal superhydrophobic coating. Example 10

[0030] The preparation method of the photothermal superhydrophobic coating described in Example 4 includes the following steps: 0.4 kg of isopropyl tris(dioctyl pyrophosphoryloxy) titanate, 5 kg of talc, 5 kg of barium sulfate, 10 kg of sericite powder, 14 kg of butyl acetate and 14 kg of dichloromethane were mixed and ground to below 40 μm. After filtration, 38 kg of modified fluorosilicone resin solution, 26 kg of modified nano-sized carbon-based material, 1.1 kg of wetting and dispersing agent Silok® 7630, 1.1 kg of defoamer 2503, 1 kg of leveling agent AMORSO-137, 10 kg of polypyrrole resin and 0.08 kg of nano-silica were added and stirred and dispersed evenly to obtain a photothermal superhydrophobic coating. Example 11

[0031] The preparation method of the photothermal superhydrophobic coating described in Example 5 includes the following steps: Mix 0.4 kg of silane coupling agent Z-6121, 6 kg of heavy calcium carbonate, 6 kg of sericite powder, 6 kg of carbon black, and 30 kg of ethyl acetate. Grind the mixture to a particle size below 40 μm, filter, and then add 34 kg of modified fluorosilicone resin solution, 25 kg of modified nano-sized carbon-based material, 1.4 kg of wetting and dispersing agent 4010, 1.2 kg of defoamer Skytech® SAT80, 1.2 kg of leveling agent AFCONA 3596, 6 kg of polypyrrole resin, and 0.07 kg of nano-silica. Stir and disperse evenly to obtain a photothermal superhydrophobic coating. Example 12

[0032] The preparation method of the photothermal superhydrophobic coating described in Example 6 includes the following steps: Mix 0.5 kg of triisostearoyl titanate isopropyl ester, 10 kg of talc, 10 kg of carbon black, 15 kg of ethyl acetate and 15 kg of dichloromethane, grind to below 40 μm, filter, add 35 kg of modified fluorosilicone resin solution, 25 kg of modified nano-sized carbon-based material, 1 kg of wetting and dispersing agent 505s, 2 kg of defoamer RB-5209, 1 kg of leveling agent AFCONA 3700 and 8 kg of polypyrrole resin, stir and disperse evenly to obtain a photothermal superhydrophobic coating.

[0033] The photothermal superhydrophobic coating of the present invention was first cured at 120°C for two hours after spraying (thickness of 100 micrometers), and then cured at 180°C for two hours to obtain the coating. The following tests were performed, and the results are shown in Table 1.

[0034] The procedure for detecting the surface temperature after 10 minutes of sun irradiation is as follows: use a 500W xenon lamp to simulate sunlight to irradiate the coating surface, and then measure the surface temperature of the coating after 10 minutes.

[0035] The surface contact angle was tested according to GB / T 30447-2013, the impact resistance test was conducted according to GB / T 1732-2020, and the salt spray resistance test was conducted according to GB10125-1997.

[0036] Table 1 Performance test results of the photothermal superhydrophobic coatings obtained in Examples 7-12 Example 7 149 51.5 Level 0 No abnormalities in the paint film qualified Example 8 150 52.4 Level 0 No abnormalities in the paint film qualified Example 9 153 54.9 Level 0 No abnormalities in the paint film qualified Example 10 156 60.5 Level 0 No abnormalities in the paint film qualified Example 11 158 62.8 Level 0 No abnormalities in the paint film qualified Example 12 155 61.4 Level 0 No abnormalities in the paint film qualified As can be seen from the results in Table 1, the photothermal superhydrophobic coating of the present invention has excellent hydrophobic properties, strong adhesion, and excellent mechanical properties of the coating film. Furthermore, the coating will heat up after being exposed to light and has photothermal properties. The ice that melts on the photothermal film can be easily removed from the superhydrophobic coating to avoid refreezing. This coating can be applied to de-icing of facilities such as pipelines, marine transportation, and offshore platforms.

Claims

1. A photothermal superhydrophobic coating, characterized in that: The product, by weight, is composed of the following raw materials: 30-40 parts of modified fluorosilicone resin solution, 20-30 parts of modified nano-scale carbon-based material, 3-5 parts of functional additives, 3-15 parts of polypyrrole resin, 0.1-0.8 parts of adhesion promoter, 0.05-0.1 parts of nano-silica, 15-25 parts of filler, and 25-35 parts of first organic solvent; The modified fluorosilicone resin solution was prepared according to the following steps: Methacryloyloxypropyltrimethoxysilane, ester-containing benzoxazine monomer, fluorinated acrylate monomer and solvent ethyl acetate were added to a reaction vessel. Nitrogen gas was introduced while stirring. After 15-20 minutes, initiator-ethyl acetate solution was added to the reaction vessel in several portions. After the addition was completed, the temperature was raised to 75-85℃ and the reaction was carried out for 12-24 hours to obtain a reaction solution. The obtained reaction solution was placed at 30-40℃ and vacuum dried for 8-10 hours to obtain modified fluorosilicone resin. The obtained modified fluorosilicone resin was dissolved in a second organic solvent to prepare a modified fluorosilicone resin solution with a solid content of 30-60%. The fluorinated acrylate monomer is dodecyl fluoroheptyl methacrylate or / and perfluorobutyl ethyl methacrylate; The initiator is AIBN or BPO, and the amount of initiator is 0.1-2% of the monomer mass. The mass ratio of initiator to ethyl acetate in the initiator-ethyl acetate solution is 1:8-10. The mass ratio of the methacryloyloxypropyltrimethoxysilane, the ester-containing benzoxazine monomer, and the fluorinated acrylate monomer is 8~15:5~12:18~25; The amount of ethyl acetate solvent used is 50-60% of the total mass of the monomers; The second organic solvent is ethyl acetate or dichloromethane; The modified nanoscale carbon-based material is obtained by modifying oxidized nanoscale carbon-based material with silane; the carbon-based material is carbon black or carbon nanotubes.

2. The photothermal superhydrophobic coating according to claim 1, characterized in that: The functional additive is two or three of the following: wetting and dispersing agent, defoamer, and leveling agent.

3. The photothermal superhydrophobic coating according to claim 1, characterized in that: The adhesion promoter is a silane coupling agent Z-6121 or a titanate coupling agent; the titanate coupling agent is triisostearoyl titanate isopropyl ester or isopropyl tris(dioctylpyrophosphate) titanate.

4. The photothermal superhydrophobic coating according to claim 1, characterized in that: The filler is a mixture of two or more of the following: heavy calcium carbonate, talc, barium sulfate, sericite powder, and carbon black.

5. The photothermal superhydrophobic coating according to claim 1, characterized in that: The first organic solvent is one or more of butyl acetate, ethyl acetate, or dichloromethane.

6. The photothermal superhydrophobic coating according to claim 2, characterized in that: The wetting and dispersing agent is a nonionic wetting and dispersing agent or a fluorocarbon wetting agent; the defoamer is a mineral oil defoamer, an organosilicon defoamer, or a polyether defoamer; the leveling agent is an organosilicon oil leveling agent or a polyether leveling agent.

7. The photothermal superhydrophobic coating according to claim 1, characterized in that: The specific preparation process of the modified nanoscale carbon-based material is as follows: The nanoscale carbon-based material was slowly added to a mixed strong acid in small amounts multiple times. The mixture was heated to 58-62°C under mechanical stirring and stirred for 12-24 hours. The mixture was then washed until neutral and dried to obtain the oxidized nanoscale carbon-based material. The obtained oxidized nanoscale carbon-based material was ultrasonically dispersed in ethanol, and a second silane coupling agent was added to it while stirring. The stirring was continued for 0.5 to 1 hour, filtered, washed with ethanol, and dried under vacuum to obtain the modified nanoscale carbon-based material. The mass ratio of nanoscale carbon-based material, mixed strong acid, and second silane coupling agent is 1:100~150:0.03~0.06; The mixed strong acid is obtained by mixing concentrated sulfuric acid and concentrated nitric acid in a mass ratio of 100:40~50.

8. The photothermal superhydrophobic coating according to claim 7, characterized in that: The second silane coupling agent is one or more of silane coupling agents KH560, KH570 or KH550.

9. The method for preparing a photothermal superhydrophobic coating according to claim 1, characterized in that: Includes the following steps: By weight, 0.1-0.8 parts of adhesion promoter, 15-25 parts of filler and 25-35 parts of first organic solvent are mixed, ground to below 40μm, filtered, and then 30-40 parts of modified fluorosilicone resin solution, 3-15 parts of polypyrrole resin, 20-30 parts of modified nano-scale carbon-based material, 0.05-0.1 parts of nano-silica and 3-5 parts of functional additives are added and stirred to disperse evenly to obtain a photothermal superhydrophobic coating.