Epoxy resin-based super self-cleaning coating material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of self-cleaning coatings, and particularly relates to an epoxy resin-based super self-cleaning coating material as well as a preparation method and application thereof. The epoxy resin based super self-cleaning coating material is prepared according to the following steps: carrying out catalytic addition reaction by taking polysulfide rubber and epoxy resin as raw materials to obtain a polysulfide rubber modified epoxy resin prepolymer; mixing the polysulfide rubber modified epoxy resin prepolymer with liquid silicone rubber, and adding a curing agent and amino-modified carbon black for cross-linking curing reaction to obtain a phase-separated polymer; and soaking the phase-separated polymer in ethyl acetate to obtain the polymer. The epoxy resin-based flexible super self-cleaning coating material provided by the invention has excellent mechanical, physical and chemical stability, can relieve icing on the surface of the coating to a great extent, and realizes active photo-thermal spontaneous deicing.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of self-cleaning coating, and particularly relates to an epoxy resin-based super self-cleaning coating material and a preparation method and application thereof. BACKGROUND

[0002] Since the concept of "superhydrophobicity" was proposed, the large-scale preparation and application of superhydrophobic coating materials have been the focus of attention of both the scientific research community and the industrial community. This kind of material with extreme hydrophobic and oleophilic properties has shown broad application prospects in many fields such as oil-water separation, intelligent devices, solar seawater desalination, microfluidic control, and ice, frost, dirt and corrosion prevention. Once widely used, it is expected to bring revolutionary changes to many industries. In order to realize the preparation of superhydrophobic coating materials with good mechanical stability, the prior art uses different technical means (such as femtosecond laser, 3D printing, imprinting or electro / chemical deposition) to design and prepare different types of superhydrophobic surfaces, and realizes their important applications in different fields. However, the above research methods usually rely on expensive equipment, the process is complex, and the compatibility with the substrate is poor. Once the local micro / nano structure is damaged, it is extremely challenging to repair or restore the local defects, often requiring the entire material to be replaced, thereby significantly reducing its practicability. At present, the most common strategy for preparing superhydrophobic coatings by solution method is to combine micro / nano particles with low surface energy substances, and then spray or spin coat them onto different substrate surfaces. However, the introduction of excess micro / nano particles in the solvent system will cause the mechanical properties of the coating to decrease, resulting in a significant reduction in the adhesion of the coating to the substrate, which is difficult to meet the actual demand. SUMMARY

[0003] To solve the above problems, the development of a flexible polymer-based super self-cleaning coating is the key to solving the above problems. In view of the above problems, the present application proposes a design based on amorphous polymers (polymer rubber modified epoxy resin (LPR-ER) and oleophilic liquid silicone rubber (LSR)), and then introduces functional building blocks (such as photo-thermal responsive carbon black nanoparticles), and a method for constructing an epoxy resin-based super self-cleaning micro / nano structure with excellent mechanical properties by combining phase separation strategy and swelling technology strategy, finally realizing the application of the stable super self-cleaning material in photo-thermal active deicing.

[0004] The specific technical scheme provided by the present application is as follows: The present application provides a preparation method of an epoxy resin-based super self-cleaning coating material, comprising the following steps: The epoxy resin is modified by catalytic addition reaction of the mercapto group in the polysulfide rubber and the epoxy group of the epoxy resin, to obtain a polysulfide rubber modified epoxy resin prepolymer; The polysulfide rubber modified epoxy resin prepolymer is mixed with liquid silicone rubber, and a curing agent and amino-modified carbon black are added to perform cross-linking and curing reaction to obtain a phase-separated polymer; The phase-separated polymer is soaked in ethyl acetate to obtain the epoxy resin-based super self-cleaning coating material.

[0005] As a preferred embodiment of the present application, the polysulfide rubber and the epoxy resin are used in a ratio of 3-4:1.

[0006] As a preferred embodiment of the present application, the liquid silicone rubber is a mixture of vinyl silicone oil and hydrogen-containing silicone oil in a mass ratio of 1:0.5-5.

[0007] As a preferred embodiment of the present application, the curing agent is an amine curing agent. The amine curing agent can fully react with the epoxy group of the polysulfide rubber modified epoxy resin prepolymer in the cross-linking and curing reaction.

[0008] Further preferably, the amine curing agent is diethylenetriamine.

[0009] More preferably, the mass ratio of the polysulfide rubber modified epoxy resin prepolymer to the diethylenetriamine is 9-12:1.

[0010] As a preferred embodiment of the present application, in the mixed system composed of the polysulfide rubber modified epoxy resin prepolymer, the liquid silicone rubber, the curing agent and the amino-modified carbon black, the mass fraction of the amino-modified carbon black is 5%-12%. The amino-modified carbon black can be better dispersed in the resin matrix. While obtaining super-hydrophobic properties, the addition of the amino-modified carbon black can endow the coating with excellent light-heat conversion ability.

[0011] As a preferred embodiment of the present application, the polysulfide rubber modified epoxy resin prepolymer is first mixed with liquid silicone rubber, and then the curing agent is added and mixed uniformly before the addition of the amino-modified carbon black. The final addition of the amino-modified carbon black can make it better dispersed in the resin matrix.

[0012] As a preferred embodiment of the present application, the cross-linking and curing reaction is performed at 50-70℃ for 5-7h.

[0013] Further preferably, before cross-linking and curing, the mixed system composed of the polysulfide rubber modified epoxy resin prepolymer, the liquid silicone rubber, the curing agent and the amino-modified carbon black is coated on a substrate, then compacted at 60℃ and 0.6 MPa, and then cured at 50-80℃ for 5-6.5h.

[0014] As a preferred embodiment of the present application, the reaction of the polysulfide rubber and the epoxy resin is carried out at 50-70 DEG C for 5-7 hours.

[0015] The substrate can be nylon cloth, glass, metal, etc. with a polar hydrophilic surface.

[0016] As a preferred embodiment of the present application, the soaking time of ethyl acetate is 40-50 min.

[0017] During the phase separation process, due to the difference in polarity, the polysulfide rubber modified epoxy resin (LPR-ER) and the liquid silicone rubber (vinyl silicone oil Vi-PDMS and hydrogen-containing silicone oil PMHS two components) will be phase separated during the curing process, and the two will form a certain interpenetrating network with each other, but due to the difference in volume shrinkage, after curing, micron-level protruding structures will be formed. Further, the obtained sample is immersed in an ethyl acetate solution for swelling treatment, since the ethyl acetate only swells the cured liquid silicone rubber and does not swell the cured epoxy system, the polysulfide rubber modified epoxy resin molecules only undergo limited swelling, while the flexible liquid silicone rubber swells to a higher degree, and the interpenetrating structure of the two limits the overall expansion degree, allowing only local movement of the molecular chain, and further forming many sub-micron or nanometer protrusions on the micron protrusion surface, and after sufficient drying, the super self-cleaning micro-nano structure is obtained.

[0018] The present application also provides an epoxy resin-based super self-cleaning coating material prepared according to the above method.

[0019] The present application also provides a use of the epoxy resin-based super self-cleaning coating material in photothermal spontaneous deicing.

[0020] As a preferred embodiment of the present application, the epoxy resin-based super self-cleaning coating material is used for ice prevention and removal in the fields of aircraft wings, wind power blades, satellite communication equipment, and high-voltage transmission lines.

[0021] The present application has the following advantages: 1. Thanks to the strong adhesion of the modified epoxy resin and the low surface energy of the liquid silicone rubber, the epoxy resin-based flexible super self-cleaning coating material provided by the application has excellent mechanical, physical and chemical stability, can resist 250 g sand impact test (sand height 1.5 m), 20 times of adhesive tape peeling test and acid, alkali and salt corrosion test within a certain time range. The above research results are mainly due to the following two aspects: one is that the modified epoxy resin and the liquid silicone rubber are still interpenetrated in the form of partial interpenetration while obtaining the micron structure through the phase separation strategy, and at the same time, the epoxy resin and the liquid silicone rubber can be used as a strong glue to adhere to the surface of the substrate, ensuring the stability of the coating; on the other hand, the liquid silicone rubber in the partial interpenetrating network structure has a large swelling, which forms a more dense structure on the surface of the microstructure while greatly reducing the surface energy of the system.

[0022] 2. It is found through the ice delay performance test of the coating surface that the droplet added on the surface of the coating prepared by the application completely freezes for 2526 s, and compared with the original glass surface without any coating modification, the freezing time of the droplet is prolonged by about 9.5 times, which greatly delays the surface icing. This is mainly due to the air layer between the droplet and the super-hydrophobic interface, which can hinder the heat transfer to a certain extent and delay the surface freezing process.

[0023] 3. It is proved through the photothermal deicing experiment that the ice droplet added on the coating prepared by the application gradually melts with the extension of the light time; and the ice droplet on the original glass surface does not melt, which shows that the sample prepared by the application can better realize the active photothermal self-deicing. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is the reaction process of the epoxy resin-based super self-cleaning coating material prepared by the application.

[0025] Figure 2 is the mechanical property test of the epoxy resin-based super self-cleaning coating material; a, sand impact experiment schematic diagram, b, sample surface contact angle and rolling angle change, c, adhesive tape peeling test schematic diagram, d, sample surface contact angle and rolling angle change, e, chemical stability test schematic diagram, f, sample surface contact angle and rolling angle change after acid immersion, g, sample surface contact angle and rolling angle change after alkali immersion, h, sample surface contact angle and rolling angle change after salt immersion.

[0026] Figure 3 is the apparent schematic diagram of the sample after phase separation (a) and swelling (b). Figure 4 is the ice delay performance test (a, b) and photothermal deicing test (c) of the epoxy resin-based super self-cleaning coating material. DETAILED DESCRIPTION

[0027] The present application is further described in detail by the following specific examples. The examples of the present application are given for illustration and description. They are not in any way intended to be exhaustive or to limit the present application to the forms disclosed. Many modifications and variations will occur to those of ordinary skill in the art. The implementation of an alternative embodiment is within the scope of the application. The examples were chosen and described in order to best explain the principles of the application and its practical application and to enable others skilled in the art to best utilize the application in various embodiments and with various modifications as are suited to the particular use contemplated.

[0028] In order to solve the problem of weak adhesion between coating and substrate surface, non-uniform surface of coating, improve the mechanical stability of the coating, realize its long-term usability, and obtain the micro-nano structure with uniform surface morphology, the present application provides a preparation method of epoxy resin-based super self-cleaning coating, comprising the following steps: The epoxy resin prepolymer modified by polysulfide rubber is obtained by catalytic addition reaction of the mercapto group in the polysulfide rubber and the epoxy group of the epoxy resin. The phase-separated polymer is obtained by mixing the epoxy resin prepolymer modified by polysulfide rubber with liquid silicone rubber, adding a curing agent and amino-modified carbon black for crosslinking and curing reaction. The phase-separated polymer is immersed in ethyl acetate to obtain an epoxy resin-based super self-cleaning coating material.

[0029] Benefiting from the strong adhesion of the modified epoxy resin and the low surface energy of the liquid silicone rubber, the epoxy resin-based flexible super self-cleaning coating material prepared by the present application has excellent mechanical, physical and chemical stability, and can greatly alleviate the icing on the surface of the coating and realize active photothermal self-icing.

[0030] The structural formulas of the epoxy resin (ER), polysulfide rubber (LPR), vinyl silicone oil (Vi-PDMS), hydrogen-containing silicone oil (PMHS), and curing agent diethylene triamine (DETA) used in the embodiments of the present application are as follows: Example 1 A preparation method of an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) are added to 5 ml of ethyl acetate solution, and stirred uniformly for 20 min, and then reacted at 60℃ for 6 h to obtain an epoxy resin prepolymer solution modified by polysulfide rubber (LPR-ER solution), and the reaction route is shown in Figure 1In the process, the proportion of polysulfide rubber and epoxy resin is controlled so that the mercapto group in the polysulfide rubber can only react with part of the epoxy functional group. The remaining epoxy functional group in the obtained prepolymer in the reaction is reacted with an amine curing agent in step (5).

[0031] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) were added to 5 ml of ethyl acetate solution, and stirred for 20 min to obtain a uniform mixture.

[0032] (3) The solution of step (1) was added dropwise to the solution of step (2), and 0.12 g of diethylenetriamine (DETA) was added as a curing agent for the modified epoxy resin (LPR-ER), and stirred for 20 min to obtain a uniform mixture.

[0033] (4) In order to obtain super-hydrophobic properties and at the same time impart excellent light-heat conversion ability to the coating, 0.39 g of amino-modified carbon black (CB) was added to the mixture solution obtained in step (3) and stirred to obtain a uniform mixture.

[0034] (5) The nylon cloth was washed with deionized water or ethanol, dried in an oven, and the solution obtained in step (4) was sprayed onto the surface of the washed and dried nylon cloth by spraying or scraping method, and the surface polymer was compacted by a hot press at 60 ℃ and 0.6 MPa, and then placed in a 60 ℃ oven for 6 h. At this time, the epoxy functional group of the polysulfide rubber modified epoxy resin can be cured with diethylenetriamine, and the vinyl silicone oil and hydrogen-containing silicone oil are cured, and the two high molecular systems are entangled in the respective reaction process, forming a "you have me, I have you" state. At the same time, due to the difference in polarity between the two high molecular systems, the polymer formed by the curing reaction is phase separated to obtain a certain microstructure, and the crosslinking and curing reaction is shown in Figure 1 In the middle b, c, the phase separation is shown in Figure 3 In the middle a

[0035] (6) The sample obtained by curing in step (5) was immersed in ethyl acetate solution for 45 min, and then dried to obtain an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and light-heat performance. In this process, the surface polymer of the sample swells, as shown in Figure 3 In the middle b.

[0036] Example 2 A preparation method of an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 0.9 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) were added to 5 ml of ethyl acetate solution, stirred thoroughly for 20 min to mix uniformly, and reacted at 60°C for 6 h to obtain a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution).

[0037] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) were added to 5 ml of ethyl acetate solution, and stirred thoroughly to mix uniformly.

[0038] (3) The solution of step (1) was added dropwise to the solution of step (2), and 0.11 g of diethylenetriamine (DETA) was added as a curing agent for the modified epoxy resin (LPR-ER), and stirred thoroughly to mix uniformly.

[0039] (4) While obtaining superhydrophobic properties, 0.39 g of amino-modified carbon black (CB) was added to the mixed solution obtained in step (3) to mix uniformly.

[0040] (5) The nylon cloth was cleaned with deionized water or ethanol, dried in an oven, and the solution obtained in step (4) was sprayed onto the surface of the cleaned and dried nylon cloth by spraying or blade coating, and the surface polymer was compacted by a hot press at 60°C and 0.6 MPa, and then placed in a 60°C oven for 6 h, during which the surface polymer of the sample underwent phase separation.

[0041] (6) The sample obtained by curing in step (5) was immersed in ethyl acetate solution for 45 min, and then dried to obtain an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and photothermal properties, during which the surface polymer of the sample swelled.

[0042] Example 3 A method for preparing an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) were added to 5 ml of ethyl acetate solution, stirred thoroughly for 20 min to mix uniformly, and reacted at 60°C for 6 h to obtain a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution).

[0043] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 3.75 g of hydrogen-containing silicone oil (PMHS) were added to 5 ml of ethyl acetate solution, and stirred thoroughly to mix uniformly.

[0044] (3) The solution of step (1) is added dropwise to the solution of step (2), and 0.11 g of diethylenetriamine (DETA) is added as a curing agent for the modified epoxy resin (LPR-ER) at the same time, and fully stirred and mixed.

[0045] (4) While obtaining super-hydrophobic properties, in order to endow the coating with excellent light-heat conversion ability, 0.39 g of amino-modified carbon black (CB) is added to the mixed solution obtained in step (3), and fully stirred and mixed.

[0046] (5) The nylon cloth is cleaned with deionized water or ethanol, dried in an oven, and the solution obtained in step (4) is sprayed onto the surface of the cleaned and dried nylon cloth by spraying or scraping, and the surface polymer is compacted by a hot press at 60°C and 0.6 MPa, and then placed in a 60°C oven for 6 hours, during which the surface polymer of the sample undergoes phase separation.

[0047] (6) The sample obtained after curing in step (5) is immersed in an ethyl acetate solution for 45 minutes, and then dried to obtain an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and light-heat properties, during which the surface polymer of the sample swells.

[0048] Example 4 A method for preparing an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) are added to 5 ml of ethyl acetate solution, fully stirred for 20 min to mix uniformly, and reacted at 60°C for 6 h to obtain a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution).

[0049] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.375 g of hydrogen-containing silicone oil (PMHS) are added to 5 ml of ethyl acetate solution, fully stirred and mixed uniformly.

[0050] (3) The solution of step (1) is added dropwise to the solution of step (2), and 0.11 g of diethylenetriamine (DETA) is added as a curing agent for the modified epoxy resin (LPR-ER) at the same time, and fully stirred and mixed.

[0051] (4) While obtaining super-hydrophobic properties, in order to endow the coating with excellent light-heat conversion ability, 0.39 g of amino-modified carbon black (CB) is added to the mixed solution obtained in step (3), and fully stirred and mixed.

[0052] (5) The nylon cloth is cleaned with deionized water or ethanol and dried in an oven. The solution obtained in step (4) is sprayed onto the surface of the cleaned and dried nylon cloth by spraying or blade coating. The surface polymer is compacted by a hot press at 60°C and 0.6 MPa. Then the sample is placed in a 60°C oven for 6 hours for curing. During this process, the polymer on the surface of the sample undergoes phase separation.

[0053] (6) The sample obtained in step (5) is immersed in an ethyl acetate solution for 45 minutes. After being taken out and dried, a flexible epoxy resin-based super self-cleaning coating material with excellent mechanical properties and photothermal properties is obtained. During this process, the polymer on the surface of the sample swells.

[0054] Example 5 A method for preparing an epoxy resin-based super self-cleaning coating includes the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) are added to 5 ml of ethyl acetate solution. After being stirred for 20 minutes, a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution) is obtained by reacting at 60°C for 6 hours.

[0055] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) are added to 5 ml of ethyl acetate solution. After being stirred, the mixture is uniformly mixed.

[0056] (3) The solution obtained in step (1) is added dropwise to the solution obtained in step (2). At the same time, 0.14 g of diethylenetriamine (DETA) is added as a curing agent for the modified epoxy resin (LPR-ER). After being stirred, the mixture is uniformly mixed.

[0057] (4) While obtaining super-hydrophobic properties, in order to endow the coating with excellent light-to-heat conversion ability, 0.39 g of amino-modified carbon black (CB) is added to the mixed solution obtained in step (3). After being stirred, the mixture is uniformly mixed.

[0058] (5) The nylon cloth is cleaned with deionized water or ethanol and dried in an oven. The solution obtained in step (4) is sprayed onto the surface of the cleaned and dried nylon cloth by spraying or blade coating. The surface polymer is compacted by a hot press at 60°C and 0.6 MPa. Then the sample is placed in a 60°C oven for 6 hours for curing. During this process, the polymer on the surface of the sample undergoes phase separation.

[0059] (6) The sample obtained in step (5) is immersed in an ethyl acetate solution for 45 minutes. After being taken out and dried, a flexible epoxy resin-based super self-cleaning coating material with excellent mechanical properties and photothermal properties is obtained. During this process, the polymer on the surface of the sample swells.

[0060] Example 6 A method for preparing an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) are added to 5 ml of ethyl acetate solution, fully stirred for 20 min to mix uniformly, and reacted at 50°C for 7 h to obtain a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution).

[0061] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) are added to 5 ml of ethyl acetate solution, fully stirred to mix uniformly.

[0062] (3) The solution of step (1) is added dropwise to the solution of step (2), and 0.11 g of diethylenetriamine (DETA) is added as a curing agent for the modified epoxy resin (LPR-ER), fully stirred, and mixed uniformly.

[0063] (4) While obtaining super-hydrophobic properties, in order to endow the coating with excellent light-heat conversion ability, 0.39 g of amino-modified carbon black (CB) is added to the mixed solution obtained in step (3), fully stirred to mix uniformly.

[0064] (5) The nylon cloth is cleaned with deionized water or ethanol, dried in an oven, and the solution obtained in step (4) is sprayed onto the surface of the cleaned and dried nylon cloth by spraying or scraping, and the surface polymer is compacted by a hot press at 60°C and 0.6 MPa, and then placed in a 60°C oven for 6 h, during which the surface polymer of the sample undergoes phase separation.

[0065] (6) The sample obtained by curing in step (5) is immersed in ethyl acetate solution for 45 min, and after drying, an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and light-heat properties is obtained, during which the surface polymer of the sample swells.

[0066] Example 7 A method for preparing an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) are added to 5 ml of ethyl acetate solution, fully stirred for 20 min to mix uniformly, and reacted at 70°C for 5 h to obtain a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution).

[0067] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) were added to 5 ml of ethyl acetate solution, and stirred sufficiently to mix uniformly.

[0068] (3) The solution of step (1) was added dropwise to the solution of step (2), and 0.11 g of diethylenetriamine (DETA) was added as a curing agent for the modified epoxy resin (LPR-ER), and stirred sufficiently to mix uniformly.

[0069] (4) While obtaining super-hydrophobic properties, in order to impart excellent light-heat conversion capability to the coating, 0.39 g of amino-modified carbon black (CB) was added to the mixed solution obtained in step (3), and stirred sufficiently to mix uniformly.

[0070] (5) The nylon cloth was cleaned with deionized water or ethanol, dried in an oven, and the solution obtained in step (4) was sprayed onto the surface of the cleaned and dried nylon cloth by spraying or blade coating, and the surface polymer was compacted by a hot press at 60°C and 0.6 MPa, and then placed in a 60°C oven for 6 h, during which the surface polymer of the sample was phase-separated.

[0071] (6) The sample obtained by curing in step (5) was immersed in an ethyl acetate solution for 45 min, and then dried to obtain an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and light-heat properties, during which the surface polymer of the sample was swollen.

[0072] Example 8 A method for preparing an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) were added to 5 ml of ethyl acetate solution, and stirred sufficiently for 20 min to mix uniformly, and reacted at 60°C for 6 h to obtain a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution).

[0073] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) were added to 5 ml of ethyl acetate solution, and stirred sufficiently to mix uniformly.

[0074] (3) The solution of step (1) was added dropwise to the solution of step (2), and 0.11 g of diethylenetriamine (DETA) was added as a curing agent for the modified epoxy resin (LPR-ER), and stirred sufficiently to mix uniformly.

[0075] (4) In order to obtain super-hydrophobic performance and excellent light-heat conversion ability of the coating, 0.39 g of amino-modified carbon black (CB) is added to the mixed solution obtained in step (3), and the mixture is stirred thoroughly.

[0076] (5) The nylon cloth is cleaned with deionized water or ethanol and dried in an oven. The solution obtained in step (4) is sprayed onto the surface of the cleaned and dried nylon cloth by spraying or scraping, and the surface polymer is compacted by a hot press under the conditions of 60°C and 0.6 MPa. Then the sample is placed in an oven at 80°C for 5 hours for curing, during which the polymer on the surface of the sample undergoes phase separation.

[0077] (6) The sample obtained in step (5) is immersed in an ethyl acetate solution for 45 minutes, and then dried to obtain an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and light-heat performance. During this process, the polymer on the surface of the sample swells.

[0078] Example 9 A method for preparing an epoxy resin-based super self-cleaning coating, comprising the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) are added to 5 ml of ethyl acetate solution, and the mixture is stirred thoroughly for 20 minutes. The mixture is reacted at 60°C for 6 hours to obtain a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution).

[0079] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) are added to 5 ml of ethyl acetate solution, and the mixture is stirred thoroughly.

[0080] (3) The solution obtained in step (1) is added dropwise to the solution obtained in step (2), and 0.11 g of diethylenetriamine (DETA) is added as a curing agent for the modified epoxy resin (LPR-ER). The mixture is stirred thoroughly.

[0081] (4) In order to obtain super-hydrophobic performance and excellent light-heat conversion ability of the coating, 0.39 g of amino-modified carbon black (CB) is added to the mixed solution obtained in step (3), and the mixture is stirred thoroughly.

[0082] (5) The nylon cloth is cleaned with deionized water or ethanol and dried in an oven. The solution obtained in step (4) is sprayed onto the surface of the cleaned and dried nylon cloth by spraying or scraping, and the surface polymer is compacted by a hot press under the conditions of 60°C and 0.6 MPa. Then the sample is placed in an oven at 80°C for 5 hours for curing, during which the polymer on the surface of the sample undergoes phase separation.

[0083] (6) The sample obtained by curing in step (5) is immersed in an ethyl acetate solution for 45 min, and after being taken out and dried, an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and photothermal properties is obtained. During this process, the polymers on the surface of the sample swell.

[0084] Example 10 A preparation method of an epoxy resin-based super self-cleaning coating material, which comprises the following steps: (1) 1.1 g of epoxy resin (ER) and 0.3 g of polysulfide rubber (LPR) are added to 5 ml of an ethyl acetate solution, and stirred uniformly for 20 min. Then, a polysulfide rubber-modified epoxy resin prepolymer solution (LPR-ER solution) is obtained by reacting at 60°C for 6 h.

[0085] (2) 0.75 g of vinyl silicone oil (Vi-PDMS) and 0.75 g of hydrogen-containing silicone oil (PMHS) are added to 5 ml of an ethyl acetate solution, and stirred uniformly.

[0086] (3) The solution in step (1) is added dropwise to the solution in step (2), and 0.11 g of diethylenetriamine (DETA) is added as a curing agent for the modified epoxy resin (LPR-ER). Then, the mixture is stirred uniformly.

[0087] (4) While obtaining super-hydrophobic properties, in order to endow the coating with excellent light-heat conversion ability, 0.39 g of amino-modified carbon black (CB) is added to the mixed solution obtained in step (3), and stirred uniformly.

[0088] (5) A nylon cloth is cleaned with deionized water or ethanol, and dried in an oven. The solution obtained in step (4) is sprayed or coated onto the surface of the cleaned and dried nylon cloth by spraying or coating, and the surface polymers are compacted by a hot press at 60°C and 0.6 MPa. Then, the sample is heated and cured in an oven at 60°C for 6 h. During this process, the polymers on the surface of the sample undergo phase separation.

[0089] (6) The sample obtained by curing in step (5) is immersed in an ethyl acetate solution for 50 min, and after being taken out and dried, an epoxy resin-based flexible super self-cleaning coating material with excellent mechanical properties and photothermal properties is obtained. During this process, the polymers on the surface of the sample swell.

[0090] Since examples 1-10 all prepared the epoxy resin-based flexible super self-cleaning coating material with the expected effect of the present application, and the effects are basically similar, only example 1 is taken as an example for effect description.

[0091] 1. Coating surface icing delay performance test A 5-microliter droplet of liquid was placed on the obtained epoxy resin-based flexible self-cleaning coating material. The freezing process was observed at intervals in an environment of -15 degrees Celsius. The results showed that the droplet took 2526 seconds to freeze completely, which was approximately 9.5 times longer than the original glass surface without any coating, significantly delaying surface freezing. Figure 4 a and b.

[0092] 2. Photothermal De-icing Experiment A photothermal de-icing experiment was conducted on the sample surface using a simulated solar exciter. Under a simulated solar intensity of 1 kW / m², the original glass substrate and the epoxy resin-based flexible self-cleaning coating material exhibited different photothermal responses, with temperatures reaching 36.5 °C and 59.4 °C, respectively, within 400 s. The epoxy resin-based flexible self-cleaning coating material containing ice droplets was then placed under a simulated solar intensity, and the melting process of the surface ice droplets was observed. The results showed that with prolonged illumination, the surface ice droplets gradually melted; however, the ice droplets on the original glass surface did not melt. This indicates that the epoxy resin-based flexible self-cleaning coating material prepared in this invention can effectively achieve active photothermal spontaneous de-icing. Figure 4 c.

[0093] 3. Mechanical stability performance test: 3.1 Sandfall Impact Test Quartz sand was evenly dropped from a height of 1.5m onto the sample surface at an inclination angle of 45°. The water contact angle and roll-off angle were measured for every 200g of quartz sand dropped, which constituted one cycle.

[0094] The results show that ( Figure 2 (a) and (b) After a 250 g drop impact test, the surface contact angle is approximately 145° and the roll-off angle is 14.5°.

[0095] 3.2 Tape peel test 3M coating adhesion test tape is attached to the sample surface. A 2 kg weight is rolled back and forth on the sample surface with the tape attached at a constant speed. The tape is then peeled off to test the superhydrophobicity of the sample. The superhydrophobicity of the surface is tested every 5 tape peeling cycles.

[0096] The results show that ( Figure 2 (c and d) After 20 tape peel tests, the surface contact angle still remained at 150°.

[0097] 3.3 Chemical stability test Use acid (pH=1), base (pH=14), and salt (W) NaCI The sample was immersed in water containing 26.47% (e.g., 26.47%) to simulate chemical resistance in different environments, and the surface superhydrophobic properties were measured at regular intervals.

[0098] The results show that (Fig. 6) Figure 2 After acid soaking for 3 h, base soaking for 2 h, and salt soaking for 12 h, the surface contact angle still remains at 150°.

[0099] Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art and related fields without creative labor shall belong to the protection scope of the present application.

Claims

1. A method for preparing an epoxy-based super- self-cleaning coating material, characterized by, The method comprises the following steps: The polysulfide rubber and epoxy resin are used as raw materials, and a catalytic addition reaction is carried out between the mercapto group in the polysulfide rubber and the epoxy group in the epoxy resin to obtain a polysulfide rubber modified epoxy resin prepolymer; The polysulfide rubber modified epoxy resin prepolymer is mixed with liquid silicone rubber, and a curing agent and amino modified carbon black are added to carry out crosslinking and curing reaction to obtain a phase-separated polymer; The phase-separated polymer is soaked in ethyl acetate to obtain the epoxy resin-based super self-cleaning coating material.

2. The production method according to claim 1, characterized by, The mass ratio of the polysulfide rubber and the epoxy resin is 3-4:

1.

3. The production method according to claim 1, characterized by, The liquid silicone rubber is a mixture of vinyl silicone oil and hydrogen-containing silicone oil in a mass ratio of 1:0.5-5.

4. The method of claim 1, wherein, The curing agent is an amine curing agent.

5. The preparation method according to claim 4, characterized in that, The amine curing agent is diethylenetriamine, and the mass ratio of the polysulfide rubber modified epoxy resin prepolymer to the diethylenetriamine is 9-12:

1.

6. The method of claim 1, wherein, In the mixed system composed of the polysulfide rubber modified epoxy resin prepolymer, the liquid silicone rubber, the curing agent and the amino modified carbon black, the mass fraction of the amino modified carbon black is 5%-12%.

7. The preparation method according to claim 1, characterized in that, The reaction between the polysulfide rubber and the epoxy resin is carried out at 50-70℃ for 5-7h; The crosslinking and curing reaction is carried out at 50-80℃ for 5-6.5h; The soaking time in ethyl acetate is 40-50min.

8. An epoxy resin-based super self-cleaning coating material prepared by the method according to any one of claims 1-7.

9. The use of the epoxy resin-based super self-cleaning coating material according to claim 8 in photothermal self-generation deicing.

10. Use according to claim 9, characterized in that, The epoxy resin-based super self-cleaning coating material is used for anti-icing and deicing of aircraft wings, wind power blades, satellite communication equipment and high-voltage transmission lines.

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