Self-healing super-hydrophobic corrosion-resistant composite coating as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of surface modification of super-hydrophobic materials, and particularly relates to a self-healing super-hydrophobic corrosion-resistant composite coating as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, polyether amine, microcrystalline wax emulsion and KH560 modified CeO2 to obtain a self-healing epoxy coating; the preparation method comprises the following steps: mixing perfluorodecanethiol, octavinyl polyhedral oligomeric silsesquioxane and a photoinitiator, carrying out a thiol-ene click reaction, and mixing with an ethanol solution to obtain a super-hydrophobic coating; and super-hydrophobic paint is deposited on the self-healing epoxy coating, and the self-healing super-hydrophobic corrosion-resistant composite coating is obtained. The self-healing super-hydrophobic corrosion-resistant composite coating has multi-environment response self-healing super-hydrophobic corrosion-resistant performance, the problem that a traditional corrosion-resistant coating is prone to corrosion after being damaged is solved, and the problems that an existing super-hydrophobic coating is poor in durability and limited in self-repairing capacity, and a shape memory coating is prone to failure in a corrosion environment are solved.

Description

Technical Field

[0001] The present invention relates to the field of electrochemistry technology, and particularly relates to a self-healing superhydrophobic corrosion-resistant composite coating, a preparation method thereof and an application thereof. Background Art

[0002] Corrosion pervades all fields of the national economy. From daily life to industrial and agricultural production, from cutting-edge science and technology to national defense industry, wherever materials are used, there are corrosion problems. Protecting the substrate with polymer protective coatings is one of the most widely used technologies in material anti-corrosion. Traditional organic anti-corrosion coatings are widely used in the field of corrosion protection due to their good compactness, which can isolate corrosive media from contacting metals. However, coating damage will lead to direct contact between corrosive media and the substrate surface. As time goes by, the electrolyte solution will penetrate the coating and reach the metal substrate, resulting in corrosion.

[0003] The micro-nano structures existing on the bionic superhydrophobic surface can capture a layer of air between the coating and the corrosive medium, thereby effectively reducing the contact area and contact time between the coating and the corrosive medium. However, most superhydrophobic coatings are easily scratched physically or even damaged by gentle finger touch, which leads to the loss of superhydrophobic properties and the protective air cushion at the solid-liquid interface. By enhancing the inherent durability of the super-dual hydrophobic coating or endowing the superhydrophobic coating with self-healing ability, the superhydrophobicity can be maintained from being damaged.

[0004] As is well known, self-repairing superhydrophobic coatings are rare and mainly constructed on fabrics. The common strategy for manufacturing self-repairing superhydrophobic coatings is to introduce self-healing reagents into the coatings. Once the coating is damaged, the self-healing reagents will be released and repair the damage. This self-healing strategy is applicable to chemical damage, but is usually ineffective for physical damage because the release of self-healing reagents cannot repair micron or nano-structural damage.

[0005] In addition, the introduced self-healing reagents will affect the inherent properties of the superhydrophobic coating. Shape memory polymer coatings have good compactness and can restore their original shape under heating conditions after being deformed by external forces, and have self-healing ability for physical damage. Therefore, they are widely used in many fields, including the corrosion protection of metal alloys. However, this single shape memory polymer coating itself has hydrophilicity and has a small porosity. When the shape memory polymer coating contacts corrosive media such as seawater, the corrosive media can penetrate into the interior of the coating through the voids and then contact the protected metal substrate. Although it can provide protection in the short term, in the long run, it will still cause serious corrosion of the metal. Summary of the Invention

[0006] Aiming at the problems existing in the prior art, the present invention provides a self-healing superhydrophobic corrosion-resistant composite coating, a preparation method thereof and an application thereof. The present invention uses bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, polyetheramine, microcrystalline wax emulsion and KH560-modified CeO 2 as raw materials, and a self-healing epoxy coating is prepared by a blending method; a mixture of perfluorodecanethiol and octavinyl silsesquioxane is subjected to a thiol-ene click reaction under the action of a photoinitiator to obtain a superhydrophobic coating; finally, the self-healing epoxy coating is immersed in the superhydrophobic coating to obtain a self-healing superhydrophobic corrosion-resistant composite coating. The self-healing superhydrophobic corrosion-resistant composite coating of the present invention has the properties of multi-environment-responsive self-healing, superhydrophobic, self-cleaning and corrosion-resistant, which not only overcomes the problem that traditional anti-corrosion coatings are prone to cause the penetration of corrosive media after damage, but also solves the problems of poor physical durability of existing superhydrophobic coatings, limited self-healing ability and easy failure of shape memory polymer coatings in a long-term corrosive environment.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] The first object of the present invention is to provide a preparation method of a self-healing superhydrophobic corrosion-resistant composite coating, comprising the following steps:

[0009] S1. Clean the substrate, remove surface grease and floating dust pollutants, and then dry it to obtain a pretreated substrate.

[0010] S2. Preparation of the self-healing epoxy coating:

[0011] Suspend the silane coupling agent KH560 in a suspension and mix it with CeO 2 to carry out a substitution reaction to obtain KH560-modified CeO 2 ; wherein, the silane coupling agent KH560 contains a glycerol ether bond and three methoxy groups, and the methoxy groups can undergo hydrolysis to replace the hydroxyl groups on the surface of CeO 2 and endow CeO 2 with a glycerol ether bond. Bisphenol A diglycidyl ether also contains a glycerol ether bond. According to the principle of similar compatibility, CeO 2 with the same group has better compatibility during doping and can better exert its performance.

[0012] Mix the shape memory polymer bisphenol A diglycidyl ether, the diluent neopentyl glycol diglycidyl ether, the crosslinking agent polyetheramine, the microcrystalline wax emulsion and KH560-modified CeO 2 The bisphenol A diglycidyl ether and the neopentyl glycol diglycidyl ether initiate an epoxy ring-opening reaction through the amino group of the polyetheramine, gradually forming a crosslinked network, and reacting with the microcrystalline wax emulsion and KH560-modified CeO 2After being uniformly mixed, the synergistic effect of the two epoxy resins and the crosslinking action of the polyetheramine jointly improve the mechanical properties of the self-healing epoxy coating, and finally form a stable three-dimensional thermosetting network structure to obtain the self-healing epoxy coating.

[0013] S3. Preparation of superhydrophobic coating:

[0014] Perfluorodecanethiol, octavinylsilsesquioxane and photoinitiator 2,2-dimethoxy-2-phenylacetophenone are mixed, and thiol-ene click reaction is carried out under the action of the photoinitiator to obtain fluorinated vinyl silsesquioxane nanoparticles.

[0015] The fluorinated vinyl silsesquioxane nanoparticles are mixed with an ethanol solution to obtain a superhydrophobic coating.

[0016] S4. Preparation of self-healing superhydrophobic corrosion-resistant composite coating:

[0017] After the self-healing epoxy coating is applied, it is cured to form a self-healing epoxy coating; a superhydrophobic coating is deposited on the self-healing epoxy coating, and after drying, an addition reaction occurs between the epoxy matrix of the bottom self-healing epoxy coating and the vinyl matrix of the surface superhydrophobic coating under the action of the photoinitiator to obtain a self-healing superhydrophobic corrosion-resistant composite coating.

[0018] Preferably, the mass ratio of bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, polyetheramine, microcrystalline wax emulsion and KH560-modified CeO 2 is 1-10:1-10:1-10:10-100:10-100; bisphenol A diglycidyl ether is a thermoplastic epoxy resin, which plays a key role in the self-healing performance of the thermal field, neopentyl glycol diglycidyl ether is a diluent, polyetheramine is a crosslinking agent, and equimolar ratio can give full play to the effects of each component to form an effective crosslinked network structure; the dosage of KH560-modified CeO 2 is obtained from experiments, and the anti-corrosion protection performance of the self-healing superhydrophobic corrosion-resistant composite coating is greatly improved under this addition amount; if the dosage of KH560-modified CeO 2 is too small, the improvement of the anti-corrosion protection performance of the self-healing superhydrophobic corrosion-resistant composite coating is not obvious, and the self-healing performance of CeO 2 itself cannot be exerted; if the dosage of KH560-modified CeO 2 is too large, it will affect the self-healing performance of the epoxy resin and the anti-corrosion performance of the self-healing superhydrophobic corrosion-resistant composite coating.

[0019] Preferably, the mass ratio of perfluorodecanethiol, octavinylsilsesquioxane, and 2,2-dimethoxy-2-phenylacetophenone is 3 to 150:1 to 50:0.1 to 5; perfluorodecanethiol, as a fluorinated modifier providing low surface energy, imparts superhydrophobic properties to octavinylsilsesquioxane particles; at this ratio, the eight vinyl functional groups of octavinylsilsesquioxane can be completely subjected to thiol-ene click reaction to provide the best grafting effect; if the amount of perfluorodecanethiol is too much, it will float on the surface, and due to the too low surface energy and excessive residual amount, the octavinylsilsesquioxane will agglomerate and adhere; if the amount of perfluorodecanethiol is too little, the effective thiol-ene click reaction cannot be completed, and effective hydrophobic properties cannot be provided; 2,2-dimethoxy-2-phenylacetophenone, as a photoinitiator, should not be too high in content itself. It can promote the occurrence of substitution reactions but will not be consumed. After the reaction, it will be mixed with fluorinated vinylsilsesquioxane nanoparticles and is not easy to remove.

[0020] Preferably, the conditions for the thiol-ene click reaction are: under ultraviolet lamp irradiation, react at 10°C to 30°C for 0.5 h to 2 h. The thiol-ene click reaction usually occurs in a relatively mild environment. The solvent is dichloromethane, which is very volatile and has a boiling point of 39°C. If the temperature is too high, the solvent will volatilize too quickly and the reaction will not be able to proceed; if the temperature is too low, the reaction rate will be slow. The reaction time of 0.5 h to 2 h is an ideal reaction time obtained from experiments. If the time is too short, the reaction is incomplete and an effective superhydrophobic coating cannot be formed; long-term exposure to ultraviolet light will cause other side reactions, such as the oxidation of thiol to disulfide or the polymerization of ethylene, affecting the purity and yield of fluorinated vinylsilsesquioxane nanoparticles. At the same time, too long reaction time will consume more energy, cause the light source to age or be damaged, and increase the maintenance cost.

[0021] Preferably, the silane coupling agent KH560 suspension is prepared according to the following steps:

[0022] Mix the silane coupling agent KH560, γ-glycidoxypropyltrimethoxysilane, and n-butanol to obtain the silane coupling agent KH560 suspension; in the silane coupling agent KH560 suspension, the mass concentration of γ-glycidoxypropyltrimethoxysilane is 10 g / L to 100 g / L.

[0023] Preferably, the mass-to-volume ratio of the silane coupling agent KH560 to CeO 2 is 1 to 5:2 to 10; this concentration range is relative to CeO 2 . If the concentration of the silane coupling agent KH560 is too high, the amount of unreacted CeO 2 for grafting will be too much, affecting the performance of the self-healing superhydrophobic corrosion-resistant composite coating. If the concentration of the silane coupling agent KH560 is too low, the grafting effect will be poor, and CeO 2The dispersion is not good enough and agglomeration is likely to occur, which affects the performance of the self-healing superhydrophobic and corrosion-resistant composite coating.

[0024] Preferably, the addition reaction is drying at room temperature under light conditions.

[0025] Preferably, when preparing the self-healing epoxy coating, the conditions of the substitution reaction are: drying at 80°C to 150°C for 1h to 6h; since the boiling point of n-butanol is 76°C and it is not easy to volatilize at room temperature, if the temperature is too low, n-butanol is difficult to volatilize and cannot be dried; if the temperature is too high, it will affect the stability of the fluorinated modified chain and the performance of the self-healing super-hydrophobic corrosion-resistant composite coating. If the temperature is too high, the fluorinated molecular modified chain segment of the octavinyl cage silsesquioxane is prone to thermal degradation, resulting in molecular chain breakage, causing the coating to lose its super-hydrophobic properties. This phenomenon does occur in experimental tests, and its thermal stability does not exceed 150°C.

[0026] Preferably, the microcrystalline wax emulsion is prepared according to the following steps:

[0027] The microcrystalline wax is melted and mixed with a dispersant to obtain a microcrystalline wax emulsion; wherein the mass ratio of the microcrystalline wax to sodium dodecylbenzene sulfonate is 10-100:1-10; sodium dodecylbenzene sulfonate, as a commonly used dispersant, can improve the dispersibility of the microcrystalline wax; too much dispersant will increase its proportion in the self-healing super-hydrophobic corrosion-resistant composite coating, making the dispersion effect of the self-healing epoxy coating worse, affecting the comprehensive performance of the self-healing super-hydrophobic corrosion-resistant composite coating; too little dispersant will cause the microcrystalline wax to easily agglomerate after cooling, which is not conducive to the corrosion protection of the self-healing super-hydrophobic corrosion-resistant composite coating.

[0028] Preferably, the curing conditions are: curing at 25°C to 60°C for 2h to 48h; the self-healing epoxy coating is in a condensed state, and after curing, the cohesion of the self-healing epoxy coating is released to ensure its protective performance; the glass transition temperature of the self-healing epoxy coating is 60°C. If the temperature is too high or the curing time is too short, the cohesion of the self-healing epoxy coating cannot be completely released, which not only affects the performance of the self-healing epoxy coating, but also causes the self-healing epoxy coating to peel off due to excessive cohesion; if the temperature is too low, the self-healing epoxy coating cannot complete curing.

[0029] Preferably, the mass volume ratio of the fluorinated vinyl cage silsesquioxane nanoparticles to the ethanol solution is 1 g to 10 g: 10 mL to 100 mL.

[0030] Preferably, the thickness of the self-healing epoxy coating is 5 μm to 2000 μm; if the thickness is too low, the protection and self-healing properties cannot be achieved; if the thickness is too high, the self-healing epoxy coating is prone to fall off due to excessive cohesion.

[0031] Preferably, the drying treatment conditions are: drying at room temperature for 0.5 h to 1 h.

[0032] Preferably, the substrate is selected from metals, ceramics, cement, concrete or fabrics.

[0033] Preferably, the coating method is selected from spraying, dip coating or knife coating.

[0034] The second object of the present invention is to provide a self-healing superhydrophobic and corrosion-resistant composite coating prepared by the above preparation method.

[0035] The third object of the present invention is to provide the application of the above self-healing superhydrophobic and corrosion-resistant composite coating in the preparation of fabric preservatives, ice inhibition and anti-icing agents or self-cleaning agents.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] 1. The present invention provides a preparation method of a self-healing superhydrophobic and corrosion-resistant composite coating. A suspension of silane coupling agent KH560 is mixed with CeO 2 for a substitution reaction to obtain CeO modified by KH560 2 ; Shape memory polymer bisphenol A diglycidyl ether, diluent neopentyl glycol diglycidyl ether, crosslinking agent polyetheramine, and microcrystalline wax emulsion The microcrystalline wax emulsion is composed of microcrystalline wax and sodium dodecylbenzenesulfonate. Sodium dodecylbenzenesulfonate is a dispersant and CeO modified by KH560 2 are mixed. The epoxy ring-opening reaction of bisphenol A diglycidyl ether and neopentyl glycol diglycidyl ether is initiated by the amino group of polyetheramine to gradually form a crosslinked network to obtain a self-healing epoxy coating, which is mixed uniformly with the microcrystalline wax emulsion and CeO modified by KH560 2 to obtain a self-healing epoxy coating; Perfluorodecanethiol, octavinylcage silsesquioxane and photoinitiator 2,2-dimethoxy-2-phenylacetophenone are mixed, and a thiol-ene click reaction is carried out under the action of the photoinitiator to obtain fluorinated vinyl cage silsesquioxane nanoparticles; The fluorinated vinyl cage silsesquioxane nanoparticles are mixed with an ethanol solution to obtain a superhydrophobic coating; After the self-healing epoxy coating is applied, a curing treatment is carried out to form a self-healing epoxy coating; After the self-healing epoxy coating is applied, a curing treatment is carried out to form a self-healing epoxy coating; The superhydrophobic coating is deposited on the self-healing epoxy coating, and after drying treatment, an addition reaction occurs between the epoxy matrix of the bottom self-healing epoxy coating and the vinyl matrix of the top superhydrophobic coating under the action of the photoinitiator to obtain a self-healing superhydrophobic and corrosion-resistant composite coating. The self-healing superhydrophobic and corrosion-resistant composite coating of the present invention has the properties of multi-environment-responsive self-healing, superhydrophobic self-cleaning and corrosion resistance, which not only overcomes the problem that traditional anti-corrosion coatings are prone to corrosion medium penetration after damage, but also solves the problems of poor physical durability (poor corrosion resistance), limited self-healing ability, single repair method of existing superhydrophobic coatings, and easy failure (poor resistance to acids, alkalis and salts) of shape memory polymer coatings after long-term exposure to a corrosive environment.

[0038] 2. The present invention first uses bisphenol A diglycidyl ether as a shape memory polymer and dopes it with KH560 modified CeO with good dispersibility. 2 The self-healing epoxy coating was prepared by blending. The thermal field self-healing properties of bisphenol A diglycidyl ether and CeO 2 Center 2+ OH in the environment - The reaction generates Ce(OH) with excellent corrosion resistance 3+ or Ce(OH) 4+ And form a protective film, jointly give the ability of self-healing super-hydrophobic corrosion-resistant composite coating to self-repair in thermal field and corrosive medium after being damaged. Meanwhile, using perfluorodecanethiol and octavinyl cage type silsesquioxane as raw materials, a super-hydrophobic coating is prepared, which can effectively isolate the immersion of corrosive medium, thereby preventing the coating from being polluted. The present invention introduces self-healing and super-hydrophobic mechanism into self-healing super-hydrophobic corrosion-resistant composite coating, plays the synergistic effect between each, and realizes the self-repairing super-hydrophobic surface that can work normally under different external environments of high temperature, low temperature, acid and alkali.

[0039] 3. In the self-healing super-hydrophobic corrosion-resistant composite coating of the present invention, the self-healing epoxy coating is used as the bottom layer, and the super-hydrophobic coating is used as the surface layer. Under the action of the photoinitiator, an addition reaction occurs between the epoxy matrix composed of bisphenol A diglycidyl ether and neopentyl glycol diglycidyl ether in the bottom layer and the vinyl matrix of the fluorinated vinyl cage silsesquioxane in the surface layer. This reaction results in the two being bonded together through an ether bond (-O-CH 2 -CH 2 -) is closely combined to form a high-strength interfacial bonding force. This combination of the bottom layer and the surface layer not only enhances the overall strength of the material, but also achieves a performance improvement through synergy, the so-called 1+1>2 effect. When the bottom coating undergoes self-healing, it can drive the movement of the surface coating, thereby restoring the super-hydrophobic performance of the damaged part. In particular, the three healing mechanisms of the self-healing super-hydrophobic corrosion-resistant composite coating of the present invention can be triggered at the same time, so that the self-healing super-hydrophobic corrosion-resistant composite coating of the present invention has multi-environment response self-healing, super-hydrophobic and self-cleaning excellent performance, can achieve low surface energy materials and surface roughness structure of the synchronous repair, even long-term immersion in severe acid, alkali and salt corrosion environment can also maintain effective anti-corrosion performance, can achieve chemical damage and mechanical damage after self-healing.

[0040] 3. The preparation method of the self-healing super-hydrophobic corrosion-resistant composite coating provided by the present invention has simple process and high economic benefit.

[0041] 4. Apply the self-healing superhydrophobic and corrosion-resistant composite coating prepared by the present invention to a fabric. Octavinyl silsesquioxane particles with a nano-papillary structure are in-situ grafted on the fabric surface. After being modified with vinyl-terminated polydimethylsiloxane, the contact angle of water in the air is greater than 150°, the rolling angle is less than 10°, it has self-healing properties, excellent superhydrophobicity, and is resistant to corrosion by acids, alkalis, and salts. In addition to being applied to the field of anti-corrosion on the surface of the substrate, it can also be applied to the fields of ice inhibition and anti-icing, and self-cleaning. Description of the Drawings

[0042] Figure 1 Surface morphology diagrams of SHEP, SHEP+KH560-CeO 2 , FPOSS, SHEP+KH560-CeO 2 +FPOSS prepared in Example 1, where a is SHEP, b is SHEP+KH560-CeO 2 , c is FPOSS, d is SHEP+KH560-CeO 2 +FPOSS.

[0043] Figure 2 Contact angle result diagram of SHEP+KH560-CeO 2 +FPOSS in Example 1.

[0044] Figure 3 Self-healing performance result diagram of SHEP+KH560-CeO 2 +FPOSS prepared in Example 1, where a is before scratch healing, b is after scratch healing.

[0045] Figure 4 Long-term anti-corrosion performance result diagram of SHEP+KH560-CeO 2 prepared in Example 1, where a is the impedance modulus curve during long-term immersion in 3.5% NaCl, b is the dynamic polarization curve during long-term immersion in 3.5% NaCl, c is the impedance modulus curve during long-term immersion in 1 mol / L NaOH, and d is the dynamic polarization curve during long-term immersion in 1 mol / L NaOH.

[0046] Figure 5 Long-term anti-corrosion performance result diagram of SHEP+KH560-CeO 2 +FPOSS prepared in Example 1, where a is the impedance modulus curve during long-term immersion in 3.5% NaCl, b is the phase angle diagram during long-term immersion in 3.5% NaCl, c is the dynamic polarization curve during long-term immersion in 3.5% NaCl, d is the impedance modulus curve during long-term immersion in 1 mol / L NaOH, e is the phase angle diagram during long-term immersion in 1 mol / L NaOH, and f is the dynamic polarization curve during long-term immersion in 1 mol / L NaOH.

[0047] Figure 6 For the self-healing long-term anti-corrosion performance result diagram of SHEP+KH560-CeO 2 +FPOSS in Example 1, where a is the impedance modulus curve during long-term immersion in 3.5% NaCl, b is the phase angle diagram during long-term immersion in 3.5% NaCl, c is the dynamic polarization curve during long-term immersion in 3.5% NaCl, d is the impedance modulus curve during long-term immersion in 1 mol / L NaOH, e is the phase angle diagram during long-term immersion in 1 mol / L NaOH, and f is the dynamic polarization curve during long-term immersion in 1 mol / L NaOH. Detailed implementation manners

[0048] Next, the technical solutions of the present invention will be clearly and completely described in conjunction with the data in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0049] It should be noted that the professional terms used in the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the protection scope of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be obtained through market purchase or prepared by existing methods. Among them, γ-glycidoxypropyltrimethoxysilane is denoted as KH560; cerium dioxide is denoted as CeO 2 ; bisphenol A diglycidyl ether is denoted as BADGE; neopentyl glycol diglycidyl ether is denoted as NGDE; polyetheramine is denoted as D230; octavinylcage silsesquioxane is denoted as OVPOSS; 2,2-dimethoxy-2-phenylacetophenone is denoted as DMPA.

[0050] In the prior art, although polymer protective coatings and bionic superhydrophobic surfaces have achieved certain results in material anti-corrosion, there are still many technical defects. Although traditional organic anti-corrosion coatings have good compactness and can effectively isolate corrosive media from contacting metals, once the coating is damaged, the corrosive media will directly contact the substrate surface, resulting in corrosion. While bionic superhydrophobic surfaces can reduce the contact area and time with corrosive media by capturing an air layer through micro-nano structures, their physical durability is poor and they are easily scratched or even damaged by slight touch, thus losing the superhydrophobic property and the protective air cushion. In addition, self-healing superhydrophobic coatings are relatively rare and are mainly constructed on fabrics. Their self-healing strategies are usually ineffective for physical damage, and the introduced self-healing reagents will affect the inherent properties of the coating. Although shape memory polymer coatings have the ability to self-heal physical damage, due to the hydrophilicity of a single shape memory polymer coating itself and the porosity of the shape memory polymer coating, it will gradually fail under long-term immersion in corrosive media, leading to severe corrosion of the metal.

[0051] In view of the above technical defects, the present invention provides a preparation method of a self-healing superhydrophobic corrosion-resistant composite coating, comprising the following steps: suspending a silane coupling agent KH560 solution and CeO 2 mixing them to carry out a substitution reaction to obtain KH560-modified CeO 2 ; mixing a shape memory polymer bisphenol A diglycidyl ether, a diluent neopentyl glycol diglycidyl ether, a crosslinking agent polyetheramine, a microcrystalline wax emulsion and KH560-modified CeO 2 mixing them, and the bisphenol A diglycidyl ether and the neopentyl glycol diglycidyl ether initiate an epoxy ring-opening reaction through the amino group of the polyetheramine to gradually form a crosslinked network, and mix uniformly with the microcrystalline wax emulsion and KH560-modified CeO 2 to obtain a self-healing epoxy coating; mixing perfluorodecanethiol, octavinylcage silsesquioxane and a photoinitiator 2,2-dimethoxy-2-phenylacetophenone, and carrying out a thiol-ene click reaction under the action of the photoinitiator to obtain fluorinated vinylcage silsesquioxane nanoparticles; mixing the fluorinated vinylcage silsesquioxane nanoparticles with an ethanol solution to obtain a superhydrophobic coating; coating the self-healing epoxy coating and then carrying out a curing treatment to form a self-healing epoxy coating; depositing the superhydrophobic coating on the self-healing epoxy coating, and after drying treatment, an addition reaction occurs between the epoxy matrix of the bottom self-healing epoxy coating and the vinyl matrix of the top superhydrophobic coating under the action of the photoinitiator to obtain a self-healing superhydrophobic corrosion-resistant composite coating.

[0052] The self-healing superhydrophobic and corrosion-resistant composite coating of the present invention has the properties of multi-environment-responsive self-healing, superhydrophobicity, self-cleaning, and corrosion resistance. Moreover, the superhydrophobic coating prepared by mixing fluorinated vinyl cage-like silsesquioxane nanoparticles with an ethanol solution in the present invention can effectively block the contact between the self-healing epoxy coating and corrosive media, thereby avoiding the corrosion of the metal substrate. The present invention not only overcomes the problem that traditional anti-corrosion coatings are prone to corrosion medium penetration after damage but also solves the problems of poor physical durability, limited self-repair ability, single repair method of existing superhydrophobic coatings, and the easy failure of shape memory polymer coatings after long-term exposure to a corrosive environment.

[0053] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0054] Example 1

[0055] A preparation method of a self-healing superhydrophobic and corrosion-resistant composite coating includes the following steps:

[0056] S1. Clean the magnesium alloy substrate, remove surface grease and floating dust pollutants, and then dry it to obtain a pretreated substrate.

[0057] S2. Preparation of self-healing epoxy coating:

[0058] Add 3.5 g of KH560 to a mixed solution prepared from 45 g of n-butanol and 5 g of deionized water, and magnetically stir for 30 min to obtain a suspension with a KH560 concentration of 70 g / L. Then, add 5 g of CeO 2 , continue to magnetically stir for 30 min, and then dry at 80 °C for 6 h to obtain KH560-modified CeO 2 .

[0059] After melting 1 g of microcrystalline wax at 10 g / L at 80 °C, add 0.1 g of sodium dodecylbenzenesulfonate at 1 g / L, and magnetically stir for 10 min to form a microcrystalline wax emulsion; at the same time, magnetically stir and mix an equimolar amount of 4.56 g of BADGE, 2.96 g of NGDE, 2.55 g of D230, and the microcrystalline wax emulsion to obtain a clear solution, denoted as SHEP; add 1 g of KH560-modified CeO 2 at 50 g / L to the clear solution, and magnetically stir for 30 min to obtain a self-healing epoxy coating, denoted as SHEP+KH560-CeO 2 , and set aside.

[0060] S3. Preparation of superhydrophobic coating:

[0061] 0.3 g of perfluorodecanethiol at 30 g / L was added to a dichloromethane solution containing 1 g of OVPOSS at 10 g / L and 0.1 g of DMPA at 1 g / L. After irradiation under an ultraviolet lamp for 15 min, it was washed with dichloromethane and dried to obtain fluorinated vinyl cage-shaped silsesquioxane nanoparticles, namely FPOSS nanoparticles. The FPOSS nanoparticles were added to an ethanol solution and ultrasonicated for 20 min to obtain a superhydrophobic coating, denoted as FPOSS, for standby.

[0062] S4. Preparation of self-healing superhydrophobic corrosion-resistant composite coating:

[0063] The self-healing epoxy coating was applied to the pretreated substrate and cured at 50 °C for 24 h to form a self-healing epoxy coating, i.e., the bottom layer coating, with a thickness of 100 μm. Then, a coating containing 20 g / L of FPOSS was applied to the substrate and dried under normal temperature conditions under light to obtain a self-healing superhydrophobic corrosion-resistant composite coating, denoted as SHEP+KH560-CeO 2 +FPOSS.

[0064] Example 2

[0065] A preparation method of a self-healing superhydrophobic corrosion-resistant composite coating includes the following steps:

[0066] S1. The magnesium alloy substrate was cleaned, and after removing surface grease and floating dust pollutants, it was dried to obtain a pretreated substrate.

[0067] S2. Preparation of self-healing epoxy coating:

[0068] 2 g of KH560 was added to a mixed solution prepared from 40 g of n-butanol and 10 g of deionized water, and magnetically stirred for 30 min to obtain a suspension with a KH560 concentration of 40 g / L. Then, 3 g of CeO 2 was added to the suspension, and after continuing to magnetically stir for 10 min, it was dried at 90 °C for 5 h to obtain KH560-modified CeO 2 .

[0069] 3 g of microcrystalline wax at 30 g / L was melted at 85 °C, 0.3 g of sodium dodecylbenzenesulfonate at 3 g / L was added, and magnetically stirred for 5 min to form a microcrystalline wax emulsion. At the same time, an equimolar amount of 13.68 g of BADGE, 8.88 g of NGDE, 7.68 g of D230, and the microcrystalline wax emulsion were mixed by magnetic stirring to obtain a clear solution, denoted as SHEP. 1 g of KH560-modified CeO 2 at 50 g / L was added to the clear solution, and magnetically stirred for 60 min to obtain a self-healing epoxy coating, denoted as SHEP+KH560-CeO 2 , for standby.

[0070] S3. Preparation of superhydrophobic coating:

[0071] Add 0.3 g of 3 g / L perfluorodecanethiol to a dichloromethane solution containing 1 g of 1 g / L OVPOSS and 0.1 g of 0.1 g / L DMPA. After irradiating under ultraviolet light for 10 min, wash with dichloromethane and dry to obtain fluorinated vinyl cage-like silsesquioxane nanoparticles, namely FPOSS nanoparticles. Add the FPOSS nanoparticles to an ethanol solution and ultrasonicate for 10 min to obtain a superhydrophobic coating, denoted as FPOSS, for standby.

[0072] S4. Preparation of self-healing superhydrophobic corrosion-resistant composite coating:

[0073] Coat the self-healing epoxy coating on the pretreated substrate and cure at 25 °C for 48 h to form a self-healing epoxy coating, i.e., the bottom layer coating, with a thickness of 5 μm. Then, coat the substrate with 5 g / L of FPOSS and dry under normal temperature in the light condition to obtain a self-healing superhydrophobic corrosion-resistant composite coating, denoted as SHEP+KH560-CeO 2 +FPOSS.

[0074] The contact angle of 3.5% NaCl water droplets on the surface of the prepared SHEP+KH560-CeO 2 +FPOSS is 168°, indicating that the surface of the prepared fabric has superhydrophobicity. The initial impedance modulus of the coating is 2.21×10 -10 Ω, the phase angle is -8.39, the corrosion voltage is -1.21 V, and the corrosion current density is 7.54×10 -12 A / cm 2 ; After soaking in 3.5% NaCl solution for 60 days, the impedance modulus of the coating is 1.31×10 -5 Ω, the phase angle is -1.05, the corrosion voltage is -1.51 V, and the corrosion current density is 1.32×10 -9 A / cm 2 ; The impedance modulus and corrosion current density still maintain at relatively high values, demonstrating good long-term corrosion protection performance. After self-healing, SHEP+KH560-CeO 2 +FPOSS is soaked in 3.5% NaCl solution for 60 days, the impedance modulus of the coating is 9.14×10 -4 Ω, the phase angle is -1.69, the corrosion voltage is -1.53 V, and the corrosion current density is 5.12×10 -9 A / cm 2 ; The impedance modulus and corrosion current density still maintain at relatively high values, demonstrating good long-term self-healing corrosion protection performance.

[0075] Example 3

[0076] A preparation method of a self-healing superhydrophobic and corrosion-resistant composite coating, comprising the following steps:

[0077] S1. Clean the magnesium alloy substrate, remove surface grease and floating dust pollutants, and then dry it to obtain a pretreated substrate.

[0078] S2. Preparation of the self-healing epoxy coating:

[0079] Add 1.5 g of KH560 to a mixed solution prepared from 35 g of n-butanol and 15 g of deionized water, and magnetically stir for 30 min to obtain a suspension with a KH560 concentration of 30 g / L. Then, add 2 g of CeO 2 , continue to magnetically stir for 50 min, and then dry at 100 °C for 4 h to obtain KH560-modified CeO 2 .

[0080] Melt 5 g of microcrystalline wax at 50 g / L at 90 °C, add 0.5 g of sodium dodecylbenzenesulfonate at 5 g / L, and magnetically stir for 15 min to form a microcrystalline wax emulsion; meanwhile, magnetically stir and mix an equimolar amount of 22.8 g of BADGE, 14.8 g of NGDE, 12.75 g of D230 and the microcrystalline wax emulsion to obtain a clear solution, denoted as SHEP; add 1.5 g of KH560-modified CeO 2 at 80 g / L to the clear solution, and magnetically stir for 60 min to obtain a self-healing epoxy coating, denoted as SHEP+KH560-CeO 2 , and set aside for later use.

[0081] S3. Preparation of the superhydrophobic coating:

[0082] Add 5 g of perfluorodecanethiol at 50 g / L to a dichloromethane solution of 1.5 g of OVPOSS at 15 g / L and 0.15 g of DMPA at 1.5 g / L, irradiate under an ultraviolet lamp for 20 min, then wash with dichloromethane and dry to obtain fluorinated vinyl cage-like silsesquioxane nanoparticles, namely FPOSS nanoparticles; add the FPOSS nanoparticles to an ethanol solution and ultrasonically treat for 30 min to obtain a superhydrophobic coating, denoted as FPOSS, and set aside for later use.

[0083] S4. Preparation of the self-healing superhydrophobic and corrosion-resistant composite coating:

[0084] Coat the self-healing epoxy coating on the pretreated substrate and cure it at 30 °C for 40 h to form a self-healing epoxy coating, i.e., the bottom layer coating, with a thickness of 500 μm; then, coat the substrate with FPOSS containing 5 g / L, and dry it under normal temperature conditions under light to obtain a self-healing superhydrophobic and corrosion-resistant composite coating, denoted as SHEP+KH560-CeO 2 +FPOSS.

[0085] The contact angle of 3.5% NaCl water droplets on the prepared SHEP+KH560-CeO 2 +FPOSS surface is 167°, indicating that the surface of the prepared fabric has superhydrophobicity. The initial impedance modulus of the coating is 1.21×10 -10 Ω, the phase angle is -15.39, the corrosion voltage is -1.31V, and the corrosion current density is 2.54×10 -12 A / cm 2 ; After soaking in 3.5% NaCl solution for 60 days, the impedance modulus of the coating is 2.31×10 -5 Ω, the phase angle is -3.05, the corrosion voltage is -1.53V, and the corrosion current density is 1.82×10 -9 A / cm 2 ; The impedance modulus and the corrosion current density still remain at relatively high values, demonstrating good long-term corrosion protection performance. After SHEP+KH560-CeO 2 +FPOSS self-heals and is soaked in 3.5% NaCl solution for 60 days, the impedance modulus of the coating is 3.14×10 -4 Ω, the phase angle is -5.24, the corrosion voltage is -1.50V, and the corrosion current density is 3.21×10 -9 A / cm 2 ; The impedance modulus and the corrosion current density still remain at relatively high values, demonstrating good long-term self-healing corrosion protection performance.

[0086] Example 4

[0087] A preparation method of a self-healing superhydrophobic and corrosion-resistant composite coating, comprising the following steps:

[0088] S1. Clean the magnesium alloy substrate, remove the surface grease and floating dust pollutants, and then dry it to obtain a pretreated substrate.

[0089] S2. Preparation of the self-healing epoxy coating:

[0090] Add 2.5 g of KH560 to a mixed solution prepared from 42 g of n-butanol and 8 g of deionized water, stir magnetically for 50 min to obtain a suspension with a KH560 concentration of 50 g / L, and then add 3.5 g of CeO 2 to the suspension, continue to stir magnetically for 50 min, and then dry at 120°C for 2 h to obtain KH560-modified CeO 2 .

[0091] Melt 7 g of microcrystalline wax at 95 °C, add 0.7 g of sodium dodecylbenzenesulfonate (7 g / L), and stir magnetically for 20 min to form a microcrystalline wax emulsion; simultaneously, mix an equimolar amount of 31.92 g of BADGE, 20.72 g of NGDE, 17.85 g of D230 and the microcrystalline wax emulsion by magnetic stirring to obtain a clear solution, denoted as SHEP; add 2 g of KH560-modified CeO 2 , stir magnetically for 100 min to obtain a self-healing epoxy coating, denoted as SHEP+KH560-CeO 2 , and set aside for later use.

[0092] S3. Preparation of superhydrophobic coating:

[0093] Add 10 g of perfluorodecanethiol (100 g / L) to a dichloromethane solution of 3 g of OVPOSS (30 g / L) and 0.3 g of DMPA (3 g / L), irradiate under ultraviolet light for 25 min, then wash with dichloromethane and dry to obtain fluorinated vinyl cage-like silsesquioxane nanoparticles, namely FPOSS nanoparticles; add the FPOSS nanoparticles to an ethanol solution and ultrasonicate for 40 min to obtain a superhydrophobic coating, denoted as FPOSS, and set aside for later use.

[0094] S4. Preparation of self-healing superhydrophobic corrosion-resistant composite coating:

[0095] Coat the self-healing epoxy coating on the pretreated substrate and cure at 40 °C for 30 h to form a self-healing epoxy coating, i.e., the bottom layer coating, with a thickness of 1000 μm; then, coat the substrate with FPOSS containing 60 g / L and dry under normal temperature in the light condition to obtain a self-healing superhydrophobic corrosion-resistant composite coating, denoted as SHEP+KH560-CeO 2 +FPOSS.

[0096] The contact angle of 3.5% NaCl water droplets on the prepared SHEP+KH560-CeO 2 +FPOSS surface is 169°, indicating that the prepared fabric surface has superhydrophobicity. The initial impedance modulus of the coating is 6.51×10 -10 Ω, the phase angle is -11.24, the corrosion voltage is -1.22 V, and the corrosion current density is 4.24×10 -12 A / cm 2 ; after soaking in 3.5% NaCl solution for 60 days, the impedance modulus of the coating is 1.74×10 -5 Ω, the phase angle is -2.54, the corrosion voltage is -1.55 V, and the corrosion current density is 1.14×10 -9 A / cm 2; The impedance modulus and corrosion current density still remain at relatively high values, demonstrating good long-term anti-corrosion performance. SHEP+KH560-CeO 2 +FPOSS After self-healing and immersion in 3.5% NaCl solution for 60 days, the impedance modulus of the coating is 8.54×10 -4 Ω, the phase angle is -4.85, the corrosion voltage is -1.54V, and the corrosion current density is 1.52×10 -9 A / cm 2 ; The impedance modulus and corrosion current density still remain at relatively high values, demonstrating good long-term self-healing anti-corrosion performance.

[0097] Example 5

[0098] A preparation method of a self-healing superhydrophobic corrosion-resistant composite coating includes the following steps:

[0099] S1. Clean the magnesium alloy substrate, remove surface grease and floating dust pollutants, and then dry it to obtain a pretreated substrate.

[0100] S2. Preparation of the self-healing epoxy coating:

[0101] Add 5g of KH560 to a mixed solution prepared from 47g of n-butanol and 3g of deionized water, stir magnetically for 60 min to obtain a suspension with a KH560 concentration of 100 g / L. Then add 7g of CeO 2 , continue to stir magnetically for 60 min, and then dry at 150°C for 1 h to obtain KH560-modified CeO 2 .

[0102] Melt 10g of 100g / L microcrystalline wax at 100°C, add 1g of 10g / L sodium dodecylbenzenesulfonate, and stir magnetically for 30 min to form a microcrystalline wax emulsion; at the same time, mix an equimolar amount of 45.6g of BADGE, 29.6g of NGDE, 25.5g of D230 and the microcrystalline wax emulsion by magnetic stirring to obtain a clear solution, denoted as SHEP; add 3g of 100g / L KH560-modified CeO 2 to the clear solution, stir magnetically for 120 min to obtain a self-healing epoxy coating, denoted as SHEP+KH560-CeO 2 , and set aside.

[0103] S3. Preparation of the superhydrophobic coating:

[0104] 15 g of 150 g / L perfluorodecanethiol was added to a dichloromethane solution of 5 g of 50 g / L OVPOSS and 0.5 g of 5 g / L DMPA. After irradiating under an ultraviolet lamp for 30 min, it was washed with dichloromethane and dried to obtain fluorinated vinyl cage-like silsesquioxane nanoparticles, namely FPOSS nanoparticles. The FPOSS nanoparticles were added to an ethanol solution and ultrasonicated for 60 min to obtain a superhydrophobic coating, denoted as FPOSS, for standby use.

[0105] S4. Preparation of self-healing superhydrophobic corrosion-resistant composite coating:

[0106] The self-healing epoxy coating was coated on the pretreated substrate and cured at 60 °C for 2 h to form a self-healing epoxy coating, namely the bottom layer coating, with a thickness of 2000 μm. Then, the coating containing 100 g / L of FPOSS was coated on the substrate and dried under normal temperature in the light condition to obtain a self-healing superhydrophobic corrosion-resistant composite coating, namely the surface layer coating denoted as SHEP+KH560-CeO 2 +FPOSS.

[0107] The contact angle of 3.5% NaCl water droplets on the prepared SHEP+KH560-CeO 2 +FPOSS surface was 169°, indicating that the prepared fabric surface had superhydrophobicity. The initial impedance modulus of the coating was 9.51×10 -10 Ω, the phase angle was -15.32, the corrosion voltage was -1.20 V, and the corrosion current density was 9.52×10 -12 A / cm 2 ; After soaking in 3.5% NaCl solution for 60 days, the impedance modulus of the coating was 2.14×10 -5 Ω, the phase angle was -4.21, the corrosion voltage was -1.56 V, and the corrosion current density was 2.51×10 -9 A / cm 2 ; The impedance modulus and corrosion current density still remained at relatively high values, demonstrating good long-term corrosion protection performance. After self-healing of SHEP+KH560-CeO 2 +FPOSS and soaking in 3.5% NaCl solution for 60 days, the impedance modulus of the coating was 9.24×10 -4 Ω, the phase angle was -3.54, the corrosion voltage was -1.51 V, and the corrosion current density was 3.24×10 -9 A / cm 2 ; The impedance modulus and corrosion current density still remained at relatively high values, demonstrating good long-term self-healing corrosion protection performance.

[0108] It can be seen from Figure 1 Figure a in that the SHEP coating has a dense surface; It can be seen from Figure 1Figure b shows that there are many nanoparticles on the coating surface, indicating that KH560-CeO 2 is successfully doped into the SHEP coating; From Figure 1 Figure c, it can be seen that the FPOSS coating is very rough and has many nanopores; From Figure 1 Figure d, it can be seen that the surface microstructure of SHEP+KH560-CeO 2 +FPOSS is similar to that of the FPOSS coating. The combination of the SHEP+KH560-CeO 2 coating and the FPOSS coating endows SHEP+KH560-CeO 2 +FPOSS bilayer with the advantages of a compact SHEP+KH560-CeO 2 bottom layer and a rough FPOSS top layer.

[0109] From Figure 2 it can be obtained that the contact angle of 3.5% NaCl water droplets on the surface of SHEP+KH560-CeO 2 +FPOSS prepared in Example 1 is 170°, which indicates that SHEP+KH560-CeO 2 +FPOSS prepared in Example 1 has superhydrophobicity.

[0110] From Figure 3 Figure a, it can be seen that when SHEP+KH560-CeO 2 +FPOSS is severely scratched by a 4 mm knife, 37 scratches appear on the bottom layer of SHEP+KH560-CeO 2 +FPOSS, and 185 scratches appear on the FPOSS surface layer, seriously affecting the protective performance of SHEP+KH560-CeO 2 +FPOSS for metals. Observing Figure 3 Figure b, it can be seen that after triggering the shape memory self-healing performance by heating at 80 °C for 30 min, the bottom layer of SHEP+KH560-CeO 2 +FPOSS is almost completely healed, only 9 shallow scratches are left, and the scratches on the FPOSS coating are reduced by 3 times under the drive of the SHEP+KH560-CeO 2 coating to 52, and it still has superhydrophobicity, reflecting the good synergistic self-healing performance of SHEP+KH560-CeO 2 +FPOSS.

[0111] From Figure 4 it can be obtained that the initial impedance modulus of SHEP+KH560-CeO 2 is 2.39×10 -6 Ω, the initial corrosion voltage is -1.48 V, and the corrosion current density is 1.95×10 -9 A / cm2 ; After being immersed in 3.5% NaCl solution for 60 days, the impedance modulus of SHEP+KH560-CeO 2 is 6.3×10 -3 Ω, the corrosion voltage is -1.52V, and the corrosion current density is 4.64×10 -6 A / cm 2 ; After being immersed in 1mol / L NaOH solution for 60 days, the impedance modulus of SHEP+KH560-CeO 2 is 9.41×10 -4 Ω, the corrosion voltage is -1.53V, and the corrosion current density is 2.48×10 -7 A / cm 2 ; The impedance modulus and corrosion current density still remain at relatively high values, indicating that SHEP+KH560-CeO 2 has good long-term corrosion resistance.

[0112] It is obtained from Figure 5 that the initial impedance modulus of SHEP+KH560-CeO 2 +FPOSS is 2.41×10 -10 Ω, the phase angle is -10.39, the corrosion voltage is -1.14V, and the corrosion current density is 8.61×10 -12 A / cm 2 ; After being immersed in 3.5% NaCl solution for 60 days, the impedance modulus of SHEP+KH560-CeO 2 +FPOSS is 1.53×10 -5 Ω, the phase angle is -2.06, the corrosion voltage is -1.48V, and the corrosion current density is 1.54×10 -9 A / cm 2 ; After being immersed in 1mol / L NaOH solution for 60 days, the impedance modulus of SHEP+KH560-CeO 2 +FPOSS is 1.75×10 -4 Ω, the phase angle is -3.85, the corrosion voltage is -1.6V, and the corrosion current density is 1.49×10 -9 A / cm 2 ; The impedance modulus and corrosion current density still remain at relatively high values, demonstrating the good long-term corrosion resistance of SHEP+KH560-CeO 2 +FPOSS. And compared with the SHEP+KH560-CeO 2 bottom coating, the initial corrosion resistance (initial impedance modulus) has increased by 4 orders of magnitude, the initial corrosion voltage has shifted positively by 0.34V, and the initial corrosion current density has increased by 3 orders of magnitude. After 60 days of immersion experiment, its long-term corrosion resistance has been significantly improved compared with the bottom coating.

[0113] It is obtained that Figure 6 after SHEP + KH560 - CeO 2 + FPOSS is immersed in 3.5% NaCl solution for 60 days, the impedance modulus of SHEP + KH560 - CeO 2 + FPOSS is 9.41×10 -4 Ω, the phase angle is -3.69, the corrosion voltage is -1.52 V, and the corrosion current density is 5.33×10 -9 A / cm 2 ; after being immersed in 1 mol / L NaOH solution for 60 days, the impedance modulus of SHEP + KH560 - CeO 2 + FPOSS is 3.2×10 -4 Ω, the phase angle is -2.46, the corrosion voltage is -1.49 V, and the corrosion current density is 4.83×10 -8 A / cm 2 ; the impedance modulus and the corrosion current density still remain at relatively high values, reflecting the good long-term self-healing anti-corrosion performance of SHEP + KH560 - CeO 2 + FPOSS.

[0114] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications once they learn the basic creative concept. Therefore, the appended claims are intended to be construed as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.

Claims

1. A method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating, characterized in that: The following steps are involved: The silane coupling agent KH560 suspension is mixed with CeO2 to carry out a substitution reaction to obtain KH560-modified CeO2; The shape memory polymer bisphenol A diglycidyl ether, the diluent neopentyl glycol diglycidyl ether, the crosslinking agent polyetheramine, the microcrystalline wax emulsion and the KH560 modified CeO2 are mixed, and the bisphenol A diglycidyl ether and the neopentyl glycol diglycidyl ether initiate the epoxy ring-opening reaction through the amino group of the polyetheramine to gradually form a crosslinking network, and are evenly mixed with the microcrystalline wax emulsion and the KH560 modified CeO2 to obtain a self-healing epoxy coating; Perfluorodecanethiol, octavinyl cage silsesquioxane and a photoinitiator 2,2-dimethoxy-2-phenylacetophenone are mixed, and a thiol-ene click reaction is carried out under the action of the photoinitiator to obtain fluorinated vinyl cage silsesquioxane nanoparticles; The fluorinated vinyl cage-type silsesquioxane nanoparticles are mixed with an ethanol solution to obtain a superhydrophobic coating; After the self-healing epoxy coating is applied, a curing treatment is performed to form a self-healing epoxy coating; A super hydrophobic coating is deposited on the self-healing epoxy coating, and after drying, under the action of a photoinitiator, an addition reaction occurs between the epoxy matrix of the bottom self-healing epoxy coating and the vinyl matrix of the surface super hydrophobic coating to obtain a self-healing super hydrophobic corrosion-resistant composite coating.

2. The method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating according to claim 1, characterized in that: The mass ratio of bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, polyetheramine, microcrystalline wax emulsion and KH560-modified CeO2 is 1-10:1-10:1-10:10-100:10-100.

3. The method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating according to claim 1, characterized in that: The mass ratio of perfluorodecanethiol, octavinyl cage-type silsesquioxane and 2,2-dimethoxy-2-phenylacetophenone is 3-150:1-50:0.1-5.

4. The method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating according to claim 1, characterized in that: The conditions for the thiol-ene click reaction are: reacting at 10°C to 30°C for 0.5h to 2h under ultraviolet light.

5. The method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating according to claim 1, characterized in that: The mass ratio of silane coupling agent KH560 to CeO2 is 1-5:2-10.

6. The method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating according to claim 1, characterized in that: The microcrystalline wax emulsion was prepared according to the following steps: The microcrystalline wax is melted and mixed with a dispersant to obtain a microcrystalline wax emulsion; wherein the mass ratio of the microcrystalline wax to the dispersant is 10-100:1-10.

7. The method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating according to claim 1, characterized in that: The addition reaction is drying at room temperature under light conditions.

8. The method for preparing a self-healing super-hydrophobic corrosion-resistant composite coating according to claim 1, characterized in that: The thickness of the self-healing epoxy coating is 5 μm to 2000 μm.

9. A self-healing super-hydrophobic and corrosion-resistant composite coating prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the self-healing super-hydrophobic corrosion-resistant composite coating according to claim 9 in the preparation of a fabric preservative, an ice inhibitor or an anti-icing agent.

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