A super-amphiphobic anti-wax epoxy composite coating and its preparation method and application

Abstract

The present invention discloses a super-amphiphobic anti-waxing epoxy composite coating, as well as a preparation method and application thereof. The preparation method comprises first modifying nano-silica with fluorine-containing silane to obtain fluorine-containing silane-modified nano-silica, then preparing a fluorine-containing modifier with an epoxy group through a mercapto-ene click reaction, and blending the modified epoxy resin with the epoxy resin to obtain a modified epoxy resin. Finally, the fluorine-containing silane-modified nano-silica and the modified epoxy resin are blended to obtain a composite coating. The composite coating prepared by the composite coating has water and diesel contact angles greater than 150°, a rolling angle less than 5°, super-amphiphobic properties, an anti-waxing efficiency of ≥75%, an adhesion of the coating less than Class 1, a salt spray resistance time greater than 1200 hours, and good stability.

Description

Technical Field

[0001] The invention belongs to the technical field of coating material development, and relates to a super-amphiphobic anti-waxing epoxy composite coating, a preparation method and an application thereof. Background Art

[0002] Crude oil, known as the lifeblood of industry, is a vital industrial material widely used in energy, synthetics, and many other fields. Crude oil has a high wax content, typically exceeding 20% ​​and sometimes reaching 40%. Wax deposition is often caused by temperature fluctuations during oil production. During crude oil extraction and transportation, heat is lost to the surrounding environment. When the temperature of the crude oil drops to the wax precipitation point, the paraffin in the oil begins to crystallize, precipitate, and aggregate, depositing around the well walls or on pipeline surfaces. This reduces oil production, causes considerable economic losses, and even poses potential safety risks to oil production. Therefore, understanding the characteristics of paraffin deposition and developing optimal wax removal and prevention measures are crucial for ensuring safe crude oil production and reducing operational energy consumption.

[0003] At present, people have developed many methods for removing and preventing wax. Among them, anti-wax coating technology has the advantages of low cost, high efficiency, and a wide range of applications. It is an ideal anti-wax strategy. Chinese patent CN201510396002.1 provides a "type of oil gel coating for oil pipeline anti-waxing and its coating preparation method". The oil gel is applied to the oil pipeline to form a coating. The oil gel coating can absorb small molecular components in the petroleum and form a lubricating layer on the inner wall of the pipeline, thereby reducing the adhesion of paraffin precipitated from the petroleum to the inner wall of the pipeline, which can greatly reduce the waxing phenomenon on the inner wall of the pipeline. However, due to the low mechanical strength of the gel itself, the stability and service life of its coating are poor. Chinese patent CN202011227327.4 discloses "a bionic oil pipeline coating and its preparation method". It uses the surface of the classic pufferfish as a basic research model to prepare a hydrophilic and oleophobic oil pipeline coating with good anti-waxing effect. However, during long-term contact, the petroleum will destroy the water film, causing contamination of the coating surface, thereby reducing its stability. Summary of the Invention

[0004] In response to the problems existing in the prior art, the present invention provides a super-amphiphobic anti-waxing epoxy composite coating and its preparation method and application, thereby solving the technical problems of poor stability and short service life of coating materials in the prior art.

[0005] The present invention is achieved through the following technical solutions:

[0006] A method for preparing a super-amphiphobic anti-wax epoxy composite coating comprises the following steps:

[0007] Mixing a fluorine-containing silane modifier with an alcohol aqueous solution to carry out a hydrolysis reaction to obtain a hydrolysis solution of the fluorine-containing silane modifier, adding a nano-silica dispersion to the hydrolysis solution of the fluorine-containing silane modifier, stirring and reacting, and obtaining fluorine-containing silane-modified nano-silica;

[0008] Pentaerythritol mercaptopropionate, glycidyl methacrylate and a fluorine-containing modifier with a double bond are dispersed in acetone, ultrasonically dispersed, a photoinitiator is added, stirred and dispersed uniformly, the reaction system is placed under ultraviolet light, stirred and reacted to obtain a fluorine-containing modifier with an epoxy group, and the fluorine-containing modifier with an epoxy group is uniformly mixed with an epoxy resin to obtain a modified epoxy resin;

[0009] After the modified epoxy resin and the fluorine-containing silane-modified nano-silica are mixed, a curing agent, a catalyst and a leveling agent are added, and the mixture is stirred evenly to prepare the super-amphiphobic anti-wax epoxy composite material.

[0010] Preferably, the particle size of the nano-silicon dioxide is 15 to 500 nm.

[0011] Preferably, during the hydrolysis reaction, the reaction temperature is 20-30° C. and the reaction time is 1-2 h.

[0012] Preferably, the fluorine-containing silane modifier is mixed with an alcohol aqueous solution to carry out a hydrolysis reaction, and then nano-silica is added and stirred for reaction at 40-60° C. for 4-8 hours.

[0013] Preferably, the ratio of the nano-silica particles to the fluorine-containing silane modifier is (0.5-5):(0.1-1) in parts by mass.

[0014] Preferably, the ratio of pentaerythritol mercaptopropionate, glycidyl methacrylate and double-bond fluorine-containing modifier is (10-20):(10-60):(10-60) in parts by mass.

[0015] Preferably, the ratio of the epoxy-containing fluorine-containing modifier to the epoxy resin is (0.1-1):(0.4-4) in parts by mass.

[0016] Preferably, in parts by mass, the ratio of the modified epoxy resin, fluorinated silane-modified silica, curing agent, catalyst and leveling agent is (10-20):(3-10):(8-16):(0.02-0.04):(0.1-0.3).

[0017] A super-amphiphobic anti-wax epoxy composite coating is prepared by the above method.

[0018] The above-mentioned super-amphiphobic anti-wax epoxy composite coating is used in oil pipelines.

[0019] Compared with the prior art, the present invention has the following beneficial technical effects:

[0020] The invention discloses a preparation method of a super-amphiphobic anti-waxing epoxy composite coating. First, nano-silica is surface-modified by a fluorinated silane modifier to obtain fluorinated silane-modified nano-silica. This process not only reduces the surface energy of the silica, but also enhances its compatibility with the epoxy resin. Secondly, pentaerythritol mercaptopropionate, glycidyl methacrylate, a double-bonded fluorinated modifier, and a photoinitiator are reacted to generate a fluorinated modifier with an epoxy group. The modifier can undergo a cross-linking reaction with the epoxy resin to obtain a modified epoxy resin with extremely low surface energy. The fluorinated modifier with an epoxy group is blended with the epoxy resin to ensure good compatibility between the two while giving the resin system extremely low surface energy, thereby maintaining good adhesion, water resistance, and corrosion resistance. Finally, the modified epoxy resin is mixed with the fluorinated silane-modified nano-silica, and a curing agent, a catalyst, and a leveling agent are added. The final super-amphiphobic anti-waxing epoxy composite material is obtained by uniformly stirring. ; The addition of hydrophobically modified nanoparticles in this process not only further reduces the surface energy of the coating, but also enhances the super-amphiphobic properties of the coating through its micro-nano structure. Fluorosilane-modified nano-silica is added to the epoxy resin as a filler, which significantly improves the mechanical strength, hardness and wear resistance of the epoxy resin, and improves the thermal stability of the epoxy resin, reduces the thermal expansion coefficient, and enables the material to maintain good stability and durability under extreme temperatures; In summary, the present invention uses fluorine-modified epoxy resin to reduce its surface energy, and introduces fluorine-modified SiO2 nanoparticles to further reduce the surface energy of its epoxy composite material, while constructing a micro-nano rough structure on its coating surface and improving the mechanical properties of its material. The low surface energy and "air film" effect formed are utilized to develop a super-amphiphobic epoxy resin-based anti-wax coating with low surface energy and micro-nano rough structure, good stability and excellent mechanical properties. The coating has excellent hydrophobicity and oleophobicity, and can significantly improve the anti-waxing performance of the substrate.

[0021] Furthermore, the particle size of the nano-silica is 15 to 500 nm. First, the smaller the particle size of the nano-silica, the larger its specific surface area. The increase in specific surface area is conducive to improving the reactivity and adsorption capacity of the material, allowing it to combine with more surface modifiers; secondly, the small particle size and good dispersibility of the nano-silica help it to be evenly mixed with other materials, thereby improving the overall performance of the composite material; finally, this size helps to construct a micro-nano rough surface structure, further improving the hydrophobic and oleophobic properties of the material.

[0022] Furthermore, during the hydrolysis reaction, the reaction temperature is 20 to 30°C and the reaction time is 1 to 2 hours. This temperature range helps maintain the stability of the reaction system. Although high temperature can accelerate the reaction rate, it can also lead to an increase in side reactions or decomposition of the product, while low temperature may slow the reaction rate too much, which is not conducive to production efficiency. The reaction time of 1 to 2 hours is sufficient for the reactants to fully contact and undergo a hydrolysis reaction, while avoiding product degradation or impurity generation that may result from a long reaction time. Under appropriate temperature and time conditions, the hydrolysis reaction can proceed more efficiently, thereby improving the yield of the product.

[0023] Furthermore, the fluorinated silane modifier is mixed with an alcohol aqueous solution for a hydrolysis reaction, and after the nano-silica is added, the reaction is stirred at 40 to 60° C. for 4 to 8 hours. First, this temperature range is conducive to the chemical reaction between the fluorinated silane modifier and the nano-silica, ensuring that the reaction proceeds at an appropriate rate while avoiding side reactions or product degradation that may be caused by high temperature. The stirring reaction time of 4 to 8 hours ensures sufficient contact and reaction between the reactants, and sufficient time allows the fluorinated silane to evenly cover the surface of the nano-silica to form a stable modified layer. Secondly, the introduction of fluorinated silane can significantly reduce the surface energy of nano-silica, making it more hydrophobic and oleophobic. This modification effect is crucial to improving the super-amphiphobic properties of the coating. At the same time, the dispersion of the modified nano-silica in the resin will be improved, which will help reduce agglomeration and improve the uniformity and stability of the coating. Finally, the introduction of nano-silica can enhance the mechanical strength, hardness and wear resistance of the coating. After modification with fluorinated silane, these properties will be further improved, making the coating more durable when subjected to external impact and wear.

[0024] Furthermore, in terms of mass fraction, the ratio of the nano-silica particles to the fluorinated silane modifier is (0.5-5):(0.1-1). First, by adjusting the ratio of the nano-silica particles to the fluorinated silane modifier, the coverage and distribution state of the modifier on the surface of the nano-particles can be precisely controlled, which helps to achieve different degrees of surface modification effects and meet the needs of different application scenarios; secondly, an appropriate amount of fluorinated silane modifier can ensure that a uniform and dense modified layer is formed on the surface of the nano-silica particles, which not only improves the dispersibility and stability of the nano-particles, but also significantly improves their hydrophobic and oleophobic properties; finally, too much modifier may cause the modified layer to be too thick, affecting the original properties of the nano-particles, while too little modifier may not form an effective modified layer and cannot achieve the expected modification effect.

[0025] Furthermore, in parts by mass, the ratio of pentaerythritol mercaptopropionate, glycidyl methacrylate and fluorine-containing modifier with double bonds is (10-20):(10-60):(10-60). First, pentaerythritol mercaptopropionate provides cross-linking points and enhances reactivity with other components. Its appropriate addition helps to improve the overall strength and durability of the material; glycidyl methacrylate can bring good adhesion and weather resistance to the material; the fluorine-containing group on the fluorine-containing modifier with double bonds gives the material excellent hydrophobic and oleophobic properties, and the presence of the double bond enables it to participate in the polymerization reaction and enhance the intermolecular bonding force; secondly, this ratio setting enables the final product to have a variety of excellent properties, such as high strength, good weather resistance, excellent hydrophobic and oleophobic properties, etc.; finally, the appropriate ratio helps to evenly mix the components during the reaction, reduce the reaction unevenness caused by local concentration being too high or too low, which helps to improve the uniformity and stability of the product.

[0026] Furthermore, in terms of mass fraction, the ratio of the fluorine-containing modifier with an epoxy group to the epoxy resin is (0.1-1):(0.4-4). First, the fluorine element in the fluorine-containing modifier with an epoxy group can give the material excellent hydrophobic and oleophobic properties, which is of great significance for improving the material's stain resistance, self-cleaning and weather resistance. At the same time, the epoxy group can undergo a cross-linking reaction with the epoxy resin to further enhance the surface properties of the material; secondly, an appropriate amount of fluorine-containing modifier is added to the epoxy resin to increase the cross-linking density without significantly reducing the original properties of the epoxy resin, which helps to improve the mechanical strength, heat resistance and chemical corrosion resistance of the material.

[0027] Furthermore, in parts by mass, the ratio of the modified epoxy resin, fluorinated silane-modified silica, curing agent, catalyst and leveling agent is (10-20): (3-10): (8-16): (0.02-0.04): (0.1-0.3). First, as a matrix material, the modified epoxy resin provides good mechanical properties and chemical stability, and its ratio range ensures the basic performance of the formula; the fluorinated silane-modified silica not only enhances the mechanical strength of the material, but also gives the material excellent hydrophobic and oleophobic properties through the modification of the fluorinated silane. Improved weather resistance and stain resistance; an appropriate amount of curing agent ensures that the epoxy resin can be fully cured under appropriate conditions to form a stable cross-linked network; a small amount of catalyst accelerates the curing reaction, shortens the production cycle, and ensures the uniformity and completeness of the curing reaction; an appropriate amount of leveling agent improves the fluidity and wettability of the coating, which helps to form a smooth and uniform coating during the coating process; secondly, by adjusting the proportion of each component within a reasonable range, the production cost can be minimized while ensuring product performance, which is of great significance for improving the market competitiveness of the product.

[0028] At the same time, the present invention also discloses a super-amphiphobic anti-waxing epoxy composite coating prepared by the above method. The epoxy composite coating obtained by the composite coating not only has good super-amphiphobic performance (water contact angle can reach ≥172°, glycerol contact angle can reach ≥159°, butanediol contact angle can reach ≥155°, rolling angle is less than 5°, diesel contact angle can reach ≥152°), but also has excellent acid and alkali resistance. It can still achieve super-amphiphobicity after being immersed in different pH solutions for 24 hours. Therefore, the coating has excellent corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 A schematic flow chart of the method for preparing the super-amphiphobic anti-wax epoxy composite coating of the present invention;

[0031] Figure 2 The contact angle test results of the super-amphiphobic anti-waxing epoxy composite coating surface prepared in Example 1 of the present invention with solutions of different pH values ​​(pH values ​​are 3, 5, 7, 9, and 11, respectively);

[0032] Figure 3 These are the appearance pictures of coatings prepared using E54 (pure epoxy resin), F-EP (modified epoxy resin) prepared by the present invention, and super-amphiphobic anti-waxing epoxy composite materials before and after 1260 hours of salt spray testing. DETAILED DESCRIPTION

[0033] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0034] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0035] Herein, all features such as values, amounts, amounts, and concentrations defined in numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to include and specifically disclose all possible subranges and individual values ​​within the range (including integers and fractions).

[0036] In this document, unless otherwise specified, “include,” “including,” “contains,” “has” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0037] In this document, for the sake of brevity, not all possible combinations of the various technical features in each embodiment or example are described. Therefore, as long as there are no contradictions in the combination of these technical features, the various technical features in each embodiment or example can be combined in any way, and all possible combinations should be considered to be within the scope of this specification.

[0038] like Figure 1 As shown, the present invention provides a method for preparing a super-amphiphobic anti-waxing epoxy composite coating, comprising the following steps:

[0039] S1: mixing a fluorine-containing silane modifier with an alcohol aqueous solution for hydrolysis reaction to obtain a hydrolysis solution of the fluorine-containing silane modifier, adding a nano-silica dispersion to the hydrolysis solution of the fluorine-containing silane modifier, stirring and reacting, and obtaining fluorine-containing silane-modified nano-silica;

[0040] Specifically: 0.1 to 1 part of a fluorinated silane modifier is added to a mixture of 10 to 20 parts of ethanol and water (mass ratio 7:2) and dispersed evenly. The mixture is then placed in a magnetic stirrer and reacted at 20 to 30°C for 1 to 2 hours to obtain a hydrolyzed solution of the fluorinated silane modifier. Next, 0.5 to 5 parts of 15 to 500 nm SiO2 are uniformly dispersed in 50 to 100 parts of ethanol to obtain a SiO2 dispersion. Next, the SiO2 dispersion is added to the hydrolyzed solution of the fluorinated silane modifier and reacted in a water bath at 40 to 60°C for 4 to 8 hours. After the reaction is completed, the mixture is filtered and washed three times with anhydrous ethanol. Finally, the mixture is dried under vacuum at 60°C for 3 to 5 hours to obtain fluorinated silane-modified nano-SiO2 (F-SiO2).

[0041] Wherein, the fluorine-containing silane modifier is one or more of perfluorodecyltriethoxysilane, perfluorooctyltriethoxysilane, and perfluorohexyltriethoxysilane;

[0042] S2: dispersing pentaerythritol mercaptopropionate, glycidyl methacrylate, and a fluorine-containing modifier with a double bond in acetone, ultrasonically dispersing, adding a photoinitiator, stirring and dispersing uniformly, placing the reaction system under ultraviolet light, stirring and reacting to obtain a fluorine-containing modifier with an epoxy group, and uniformly mixing the fluorine-containing modifier with an epoxy group with an epoxy resin to obtain a modified epoxy resin;

[0043] Specifically, 10-20 parts by mass of pentaerythritol mercaptopropionate, 10-60 parts of glycidyl methacrylate, and 10-60 parts of a fluorine-containing modifier with a double bond are ultrasonically dispersed in 50-100 parts of acetone. 0.1-2 parts of a photoinitiator are then added, stirred until uniformly dispersed, and irradiated under a UV lamp at 20-40°C for 1-3 hours. The product is then subjected to rotary evaporation to remove the acetone solvent, yielding a fluorine-containing modifier with an epoxy group. 5-10 parts of the fluorine-containing modifier with an epoxy group are then mixed with 5-40 parts of an epoxy resin to yield a modified epoxy resin.

[0044] Wherein, the fluorine-containing modifier with double bonds is one or more of perfluorodecyl acrylate, tridecafluorooctyl methacrylate, tridecafluorooctyl acrylate, perfluoroalkyl methacrylate, and perfluoroalkyl vinyl ether;

[0045] The photoinitiator is one or more of 2,2-bismethoxy-2-phenylacetophenone, 4-methylbenzophenone, and 2-hydroxy-2-methyl-1-phenyl-1-propanone;

[0046] The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and polyphenol glycidyl ether epoxy resin;

[0047] S3: After mixing the modified epoxy resin and the fluorine-containing silane-modified nano-silica, a curing agent, a catalyst and a leveling agent are added, and the mixture is stirred evenly to obtain the super-amphiphobic anti-wax epoxy composite material.

[0048] Specifically, first, by weight, 10-20 parts of modified epoxy resin are dispersed in 20-50 parts of ethanol, and then 3-10 parts of fluorinated silane-modified silica are added and stirred for 10-40 minutes. Next, 8-16 parts of curing agent, 0.02-0.04 parts of catalyst, and 0.1-0.3 parts of leveling agent are added and stirred evenly to produce a super-amphiphobic anti-wax epoxy composite coating.

[0049] Among them, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and polyphenol glycidyl ether epoxy resin; the curing agent is one or more of methyltetrahydrophthalic anhydride, polyamide 651, low molecular weight polyamide T31, 1,6-hexanediamine, and maleic anhydride; the catalyst is one or more of tetrabutylammonium chloride, tetrabutylammonium bromide, DMP-30 (2,4,6-tris(dimethylaminomethyl)phenol), and 2-ethyl-4-methylimidazole; the leveling agent is one or more of GD210 (purchased from Guangzhou Xinguan Chemical Technology Co., Ltd.), SRE-3450A (purchased from Guangzhou Dongfugui Chemical Raw Materials Co., Ltd.), and SKY (purchased from Kaiyin Chemical Technology Co., Ltd.).

[0050] When using this coating, it is sprayed on the surface of the substrate by spraying method, and the sprayed coating thickness is about 20μm. After curing, a super-amphiphobic anti-waxing epoxy composite coating can be obtained. The curing process adopts gradient temperature increase and is cured in the range of 60 to 170°C.

[0051] After testing, the water and diesel contact angles of the epoxy composite coating prepared by the present invention are greater than 150°, and the rolling angle is less than 5°. It can be seen that the epoxy composite coating has super-amphiphobic properties. At the same time, the anti-waxing efficiency is ≥75%. Even after a series of wear and tear, the contact angle changes very little and the super-amphiphobic properties are not lost. Even under strong acid and strong alkali conditions (pH range 1 to 14), it still has good super-amphiphobic properties. At the same time, according to the national standard GB / T-9286-2021, the adhesion of the coating is less than level 1, and the salt spray resistance time is greater than 1200h.

[0052] The calculation of anti-waxing efficiency is as follows:

[0053]

[0054] Wherein, w1 is the wax deposition amount without coating, and w2 is the wax deposition amount after coating.

[0055] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0056] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and "ratio" indicates weight ratio.

[0057] Example 1

[0058] 1) Fluorosilane-modified nanosilica

[0059] First, 0.1 parts of perfluorooctyltriethoxysilane was added to a mixture of 10 parts of ethanol and water, dispersed evenly, and then reacted in a magnetic stirrer at 25°C for 1 hour to obtain a hydrolyzed solution of the fluorinated silane modifier. Next, 0.5 parts of 100nm SiO2 were evenly dispersed in 50 parts of ethanol to obtain a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolyzed solution and incubated in a 40°C water bath for 8 hours. After the reaction, the solution was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 5 hours to obtain fluorinated silane-modified SiO2 (F-SiO2).

[0060] 2) Preparation of modified epoxy resin

[0061] 10 parts of pentaerythritol mercaptopropionate, 20 parts of glycidyl methacrylate, and 20 parts of tridecafluorooctyl acrylate were ultrasonically dispersed in 50 parts of acetone. 0.1 part of 2,2-bismethoxy-2-phenylpropiophenone was added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 25°C for 2 hours. The acetone solvent was then removed by rotary evaporation to obtain a fluorinated modifier with epoxy groups. Five parts of the fluorinated epoxy resin modifier was then mixed with 10 parts of bisphenol A epoxy resin to obtain a modified epoxy resin.

[0062] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0063] Disperse 10 parts of modified epoxy resin in 20 parts of ethanol, add 3 parts of fluorinated silane-modified silica and stir for 30 minutes. Then, add 8 parts of methyltetrahydrophthalic anhydride, 0.02 parts of tetrabutylammonium chloride and 0.1 parts of GD210 and stir evenly. Finally, spray the super-amphiphobic anti-waxing epoxy composite coating on the surface of the metal steel plate. The curing process is: 120℃ / 4min+130℃ / 5min+140℃ / 6min+150℃ / 7min+170℃ / 30min.

[0064] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 172°, a diesel contact angle of 152° (rolling angle 4°), an anti-wax rate of 75%, a coating adhesion of level 0, and a salt spray resistance of 1260 hours.

[0065] Example 2

[0066] 1) Fluorosilane-modified nanosilica

[0067] First, 0.5 parts of perfluorooctyltriethoxysilane were added to a mixture of 10 parts of ethanol and water, dispersed evenly, and then reacted in a magnetic stirrer at 21°C for 2 hours to obtain a hydrolysis solution of the fluorosilane modifier. Next, 3 parts of 100nm SiO2 were evenly dispersed in 70 parts of ethanol to obtain a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolysis solution of the fluorosilane modifier and incubated in a 50°C water bath for 7 hours. After the reaction, the mixture was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 3 hours to obtain fluorosilane-modified SiO2 (F-SiO2).

[0068] 2) Preparation of modified epoxy resin

[0069] 10 parts of pentaerythritol mercaptopropionate, 20 parts of glycidyl methacrylate, and 20 parts of tridecafluorooctyl acrylate were ultrasonically dispersed in 50 parts of acetone. 0.1 part of 2,2-bismethoxy-2-phenylpropiophenone was added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 30°C for 1.5 hours. The acetone solvent was then removed by rotary evaporation to obtain a fluorinated modifier with epoxy groups. Five parts of the fluorinated epoxy resin modifier was then mixed with 10 parts of bisphenol A epoxy resin to obtain a modified epoxy resin.

[0070] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0071] Disperse 10 parts of modified epoxy resin in 20 parts of ethanol, add 4 parts of fluorinated silane-modified silica and stir for 30 minutes. Next, add 8 parts of methyltetrahydrophthalic anhydride, 0.02 parts of tetrabutylammonium bromide and 0.1 parts of GD210 and stir evenly. Finally, spray the super-amphiphobic anti-waxing epoxy composite coating on the surface of the glass plate. The curing process is: 120℃ / 4min+130℃ / 5min+140℃ / 6min+150℃ / 7min+170℃ / 30min.

[0072] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 173°, a diesel contact angle of 154° (rolling angle 4°), an anti-wax rate of 79%, a coating adhesion of level 0, and a salt spray resistance of 1308 hours.

[0073] Example 3

[0074] 1) Fluorosilane-modified nanosilica

[0075] First, 1 part perfluorooctyltriethoxysilane was added to a mixture of 15 parts ethanol and water, dispersed evenly, and then reacted in a magnetic stirrer at 27°C for 1 hour to obtain a hydrolysis solution of the fluorosilane modifier. Next, 5 parts of 300nm SiO2 were evenly dispersed in 100 parts of ethanol to obtain a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolysis solution of the fluorosilane modifier and incubated in a 60°C water bath for 4 hours. After the reaction, the mixture was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 4 hours to obtain fluorosilane-modified SiO2 (F-SiO2).

[0076] 2) Preparation of modified epoxy resin

[0077] 10 parts of pentaerythritol mercaptopropionate, 30 parts of glycidyl methacrylate, and 10 parts of perfluorodecyl acrylate were ultrasonically dispersed in 50 parts of acetone. 0.2 parts of 2,2-bismethoxy-2-phenylpropiophenone were added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 25°C for 2 hours. The acetone solvent was then removed by rotary evaporation to obtain a fluorinated modifier with epoxy groups. Seven parts of the fluorinated epoxy resin modifier was then mixed with 15 parts of bisphenol A epoxy resin to obtain a modified epoxy resin.

[0078] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0079] Disperse 15 parts of modified epoxy resin in 30 parts of ethanol, then add 5 parts of fluorinated silane-modified silica and stir for 40 minutes. Next, add 6 parts of polyamide 651, 0.015 parts of DMP-30, and 0.2 parts of SKY and stir until evenly combined. Finally, spray the super-amphiphobic, anti-wax epoxy composite coating onto the wood surface. The curing process is: 60°C / 30 minutes + 70°C / 20 minutes + 120°C / 10 minutes.

[0080] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 175°, a diesel contact angle of 157° (rolling angle 4°), an anti-wax rate of 89%, a coating adhesion of level 0, and a salt spray resistance of 1674 hours.

[0081] Example 4

[0082] 1) Fluorosilane-modified nanosilica

[0083] First, 0.1 parts of perfluorooctyltriethoxysilane were added to a mixture of 10 parts of ethanol and water, dispersed evenly, and then placed in a magnetic stirrer at 25°C for 2 hours to produce a hydrolysis solution of the fluorosilane modifier. Next, 0.5 parts of 300nm SiO2 were evenly dispersed in 50 parts of ethanol to produce a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolysis solution of the fluorosilane modifier and incubated in a 40°C water bath for 8 hours. After the reaction, the mixture was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 5 hours to obtain fluorosilane-modified SiO2 (F-SiO2).

[0084] 2) Preparation of modified epoxy resin

[0085] 10 parts of pentaerythritol mercaptopropionate, 30 parts of glycidyl methacrylate, and 10 parts of perfluorodecyl acrylate were ultrasonically dispersed in 50 parts of acetone. 0.3 parts of 4-methylbenzophenone were added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 30°C for 1.5 hours. The product was then subjected to rotary evaporation to remove the acetone solvent, yielding a fluorinated modifier with epoxy groups. Seven parts of the fluorinated epoxy resin modifier was then mixed with 15 parts of bisphenol A epoxy resin to yield a modified epoxy resin.

[0086] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0087] Disperse 15 parts of modified epoxy resin in 30 parts of ethanol, then add 5 parts of fluorinated silane-modified silica and stir for 40 minutes. Next, add 6 parts of low-molecular-weight polyamide T31, 0.015 parts of DMP-30, and 0.2 parts of SRE-3450A and stir until evenly combined. Finally, spray the super-amphiphobic, anti-wax epoxy composite coating onto a steel plate. Curing process: 60°C / 2h + 100°C / 30min.

[0088] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 168°, a diesel contact angle of 151° (rolling angle 5°), an anti-wax rate of 77%, a coating adhesion of level 0, and a salt spray resistance of 1274 hours.

[0089] Example 5

[0090] 1) Fluorosilane-modified nanosilica

[0091] First, 1 part perfluorooctyltriethoxysilane was added to a mixture of 15 parts ethanol and water, dispersed evenly, and then reacted in a magnetic stirrer at 27°C for 1 hour to obtain a hydrolysis solution of the fluorosilane modifier. Next, 5 parts of 500nm SiO2 were evenly dispersed in 100 parts of ethanol to obtain a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolysis solution of the fluorosilane modifier and incubated in a 60°C water bath for 4 hours. After the reaction, the mixture was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 4 hours to obtain fluorosilane-modified SiO2 (F-SiO2).

[0092] 2) Preparation of modified epoxy resin

[0093] 10 parts of pentaerythritol mercaptopropionate, 20 parts of glycidyl methacrylate, and 20 parts of perfluorodecyl acrylate were ultrasonically dispersed in 50 parts of acetone. 0.5 parts of 4-methylbenzophenone were added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 40°C for 1 hour. The acetone solvent was then removed by rotary evaporation to obtain a fluorinated modifier with epoxy groups. Five parts of the fluorinated epoxy resin modifier was then mixed with 10 parts of bisphenol A epoxy resin to obtain a modified epoxy resin.

[0094] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0095] Disperse 15 parts of modified epoxy resin in 30 parts of ethanol, then add 4 parts of fluorinated silane-modified silica and stir for 40 minutes. Next, add 6 parts of low-molecular-weight polyamide T31, 0.015 parts of tetrabutylammonium bromide, and 0.2 parts of SKY and stir thoroughly. Finally, spray the super-amphiphobic, anti-wax epoxy composite coating onto the cement board surface. Curing process: 60°C / 2h + 100°C / 30min.

[0096] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 174°, a diesel contact angle of 156° (rolling angle 3°), an anti-wax rate of 90%, a coating adhesion of level 1, and a salt spray resistance of 1709 hours.

[0097] Example 6

[0098] 1) Fluorosilane-modified nanosilica

[0099] First, 0.5 parts of perfluorodecyltriethoxysilane were added to a mixture of 10 parts of ethanol and water, dispersed evenly, and then reacted in a magnetic stirrer at 21°C for 2 hours to obtain a hydrolysis solution of the fluorosilane modifier. Next, 3 parts of 100nm SiO2 were evenly dispersed in 70 parts of ethanol to obtain a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolysis solution of the fluorosilane modifier and incubated in a 50°C water bath for 7 hours. After the reaction, the mixture was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 3 hours to obtain fluorosilane-modified SiO2 (F-SiO2).

[0100] 2) Preparation of modified epoxy resin

[0101] 10 parts of pentaerythritol mercaptopropionate, 20 parts of glycidyl methacrylate, and 20 parts of perfluorodecyl acrylate were ultrasonically dispersed in 50 parts of acetone. 1 part of 4-methylbenzophenone was added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 35°C for 1 hour. The acetone solvent was then removed by rotary evaporation to obtain a fluorinated modifier with epoxy groups. Five parts of the fluorinated epoxy resin modifier was then mixed with 10 parts of bisphenol F epoxy resin to obtain a modified epoxy resin.

[0102] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0103] Disperse 15 parts of modified epoxy resin in 30 parts of ethanol, then add 6 parts of fluorinated silane-modified silica and stir for 40 minutes. Next, add 6 parts of maleic anhydride, 0.015 parts of 2-ethyl-4-methylimidazole, and 0.2 parts of GD210 and stir until uniform. Finally, spray the super-amphiphobic, anti-wax epoxy composite coating onto the surface of a fiberglass reinforced plastic sheet. Curing process: 60°C / 4 hours.

[0104] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 170°, a diesel contact angle of 153° (rolling angle 5°), an anti-wax rate of 84%, a coating adhesion of level 0, and a salt spray resistance of 1874 hours.

[0105] Example 7

[0106] 1) Fluorosilane-modified nanosilica

[0107] First, 0.1 parts of perfluorodecyltriethoxysilane were added to a mixture of 10 parts of ethanol and water, dispersed evenly, and then placed in a magnetic stirrer at 25°C for 1 hour to produce a hydrolysis solution of the fluorosilane modifier. Next, 0.5 parts of 300nm SiO2 were evenly dispersed in 50 parts of ethanol to produce a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolysis solution of the fluorosilane modifier and incubated in a 40°C water bath for 8 hours. After the reaction, the mixture was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 5 hours to obtain fluorosilane-modified SiO2 (F-SiO2).

[0108] 2) Preparation of modified epoxy resin

[0109] 5 parts of pentaerythritol mercaptopropionate, 10 parts of glycidyl methacrylate, and 10 parts of tridecafluorooctyl methacrylate were ultrasonically dispersed in 25 parts of acetone. 0.1 part of 4-methylbenzophenone was added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 30°C for 2 hours. The acetone solvent was then removed by rotary evaporation to obtain a fluorinated modifier with epoxy groups. 5 parts of the fluorinated epoxy resin modifier was then mixed with 10 parts of bisphenol F epoxy resin to obtain a modified epoxy resin.

[0110] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0111] Disperse 10 parts of modified epoxy resin in 20 parts of ethanol, then add 5 parts of fluorinated silane-modified silica and stir for 40 minutes. Next, add 8 parts of 1,6-hexanediamine and 0.1 parts of GD210 and stir until evenly mixed. Finally, spray the super-amphiphobic, anti-wax epoxy composite coating onto a steel plate. Curing process: room temperature for 5 hours.

[0112] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 167°, a diesel contact angle of 150° (rolling angle 5°), an anti-wax rate of 75%, a coating adhesion of level 0, and a salt spray resistance of 1299 hours.

[0113] Example 8

[0114] 1) Fluorosilane-modified nanosilica

[0115] First, 1 part perfluorodecyltriethoxysilane was added to 15 parts of an ethanol-water mixture and dispersed evenly. The mixture was then placed in a magnetic stirrer and reacted at 27°C for 1 hour to obtain a hydrolysis solution of the fluorosilane modifier. Next, 5 parts of 500nm SiO2 were evenly dispersed in 100 parts of ethanol to obtain a SiO2 dispersion. Next, the dispersed nano-SiO2 was added to the hydrolysis solution of the fluorosilane modifier and incubated in a 60°C water bath for 4 hours. After the reaction, the mixture was filtered and washed with anhydrous ethanol. Finally, it was dried under vacuum at 60°C for 4 hours to obtain fluorosilane-modified SiO2 (F-SiO2).

[0116] 2) Preparation of modified epoxy resin

[0117] 20 parts of pentaerythritol mercaptopropionate, 60 parts of glycidyl methacrylate, and 20 parts of tridecafluorooctyl methacrylate were ultrasonically dispersed in 100 parts of acetone. 2 parts of 4-methylbenzophenone were added and stirred until uniformly dispersed. The mixture was then exposed to ultraviolet light at 40°C for 1 hour. The product was then subjected to rotary evaporation to remove the acetone solvent, yielding a fluorinated modifier with epoxy groups. 10 parts of the fluorinated epoxy resin modifier was then mixed with 30 parts of bisphenol A epoxy resin to yield a modified epoxy resin.

[0118] 3) Preparation of super-amphiphobic anti-wax epoxy composite coating

[0119] Disperse 10 parts of modified epoxy resin in 20 parts of ethanol, then add 5 parts of fluorinated silane-modified silica and stir for 40 minutes. Next, add 8 parts of maleic anhydride, 0.02 parts of DMP-30, and 0.1 parts of SRE-3450A and stir until uniform. Finally, spray the super-amphiphobic, anti-wax epoxy composite coating onto the surface of a fiberglass reinforced plastic sheet. Curing process: 100°C / 2 hours.

[0120] The super-amphiphobic anti-wax epoxy composite coating prepared in this example has a water contact angle of 176°, a diesel contact angle of 158° (rolling angle 3°), an anti-wax rate of 93%, a coating adhesion of level 0, and a salt spray resistance of 2022 hours.

[0121] In order to further test the stability of the superphobic performance of the super-amphiphobic anti-waxing epoxy composite coating prepared by the present invention, the contact angle of the super-amphiphobic anti-waxing epoxy composite coating surface prepared by embodiment 1 of the present invention was measured using solutions with different pH values ​​(pH values ​​were 3, 5, 7, 9, and 11, respectively). The test results are shown in FIG. Figure 2 As can be seen from the figure, the super-amphiphobic anti-waxing epoxy composite coating prepared in Example 1 of the present invention has a water contact angle greater than 150° in different pH solutions, and a rolling angle less than 5°, that is, the super-amphiphobic anti-waxing epoxy composite coating prepared in the present invention has good dual super-hydrophobic (super-hydrophobic and super-oleophobic) effects in a wide pH range and good stability.

[0122] In addition, in order to further verify the stability of the corrosion resistance of the super-amphiphobic anti-waxing epoxy composite coating prepared by the present invention, a 1260-h salt spray test was carried out using E54 (pure epoxy resin), F-EP (modified epoxy resin) prepared in Example 1 of the present invention, and a coating prepared with a super-amphiphobic anti-waxing epoxy composite material. The degree of corrosion of the grid edge was observed before and after the salt spray test. It can be seen from the figure that the super-amphiphobic anti-waxing epoxy composite coating prepared by the present invention did not show a large amount of corrosion after 1260 hours of salt spray, and had good corrosion resistance stability.

[0123] Example 9

[0124] A method for preparing a super-amphiphobic anti-wax epoxy composite coating comprises the following steps:

[0125] S1: In parts by mass, 0.1 parts of fluorinated silane modifier is added to a mixture of 10 parts of ethanol and water (mass ratio 7:2) and dispersed evenly, then placed in a magnetic stirrer and reacted at 20°C for 1 hour to obtain a hydrolysis solution of the fluorinated silane modifier. Next, 0.5 parts of 15nm SiO2 are uniformly dispersed in 50 parts of ethanol to obtain a SiO2 dispersion. Secondly, the SiO2 dispersion is added to the hydrolysis solution of the fluorinated silane modifier and reacted in a 40°C water bath for 8 hours. After the reaction is completed, it is filtered and washed 3 times with anhydrous ethanol. Finally, it is dried under vacuum at 60°C for 3 hours to obtain fluorinated silane-modified nano-SiO2 (F-SiO2).

[0126] Wherein, the fluorine-containing silane modifier is perfluorodecyltriethoxysilane;

[0127] S2: Ultrasonically disperse 10 parts by mass of pentaerythritol mercaptopropionate, 10 parts by mass of glycidyl methacrylate, and 10 parts by mass of a fluorinated modifier with a double bond in 50 parts by mass of acetone. Add 0.1 parts by mass of a photoinitiator, stir until uniformly dispersed, and irradiate the mixture under a UV lamp at 20°C for 1 hour. The product is then subjected to rotary evaporation to remove the acetone solvent, yielding a fluorinated modifier with an epoxy group. Five parts by mass of the fluorinated modifier with an epoxy group are then mixed with five parts by mass of an epoxy resin to yield a modified epoxy resin.

[0128] The double-bond fluorine-containing modifier is a mixture of perfluorodecyl acrylate and tridecafluorooctyl methacrylate; the photoinitiator is 2,2-bismethoxy-2-phenylacetophenone; and the epoxy resin is bisphenol A epoxy resin.

[0129] S3: First, disperse 10 parts by mass of modified epoxy resin in 20 parts by mass of ethanol, then add 3-10 parts of fluorinated silane-modified silica and stir for 10 minutes. Next, add 8 parts of curing agent, 0.02 parts of catalyst, and 0.1 parts of leveling agent and stir evenly to produce a super-amphiphobic, anti-wax epoxy composite coating.

[0130] Wherein, the epoxy resin is bisphenol A epoxy resin; the curing agent is methyltetrahydrophthalic anhydride; and the catalyst is tetrabutylammonium chloride.

[0131] Example 10

[0132] A method for preparing a super-amphiphobic anti-wax epoxy composite coating comprises the following steps:

[0133] S1: In parts by mass, add 1 part of fluorinated silane modifier to a mixture of 20 parts of ethanol and water (mass ratio 7:2) and disperse evenly, then place in a magnetic stirrer and react at 30°C for 1 hour to obtain a hydrolysis solution of the fluorinated silane modifier. Next, take 5 parts of 500nm SiO2 and evenly disperse them in 100 parts of ethanol to obtain a SiO2 dispersion. Secondly, add the SiO2 dispersion to the hydrolysis solution of the fluorinated silane modifier and react in a 60°C water bath for 4 hours. After the reaction, filter and wash 3 times with anhydrous ethanol. Finally, dry under vacuum at 60°C for 3 hours to obtain fluorinated silane-modified nano-SiO2 (F-SiO2). Among them, the fluorinated silane modifier is perfluorooctyltriethoxysilane;

[0134] S2: In parts by mass, 20 parts of pentaerythritol mercaptopropionate, 60 parts of glycidyl methacrylate and 60 parts of fluorine-containing modifier with double bonds are uniformly dispersed by ultrasonication in 100 parts of acetone, and 2 parts of photoinitiator are added, stirred until uniformly dispersed, and illuminated at 40°C under ultraviolet lamp for 1 hour. The product is subjected to rotary evaporation to remove the acetone solvent to obtain a fluorine-containing modifier with epoxy groups. Then, 10 parts of the fluorine-containing modifier with epoxy groups are mixed with 40 parts of epoxy resin to obtain a modified epoxy resin. Among them, the fluorine-containing modifier with double bonds is a mixture of tridecafluorooctyl acrylate, perfluoroalkyl methacrylate and perfluoroalkyl vinyl ether; the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone; and the epoxy resin is bisphenol F epoxy resin;

[0135] S3: Disperse 20 parts by mass of modified epoxy resin in 50 parts by mass of ethanol, then add 10 parts of fluorinated silane-modified silica and stir for 40 minutes. Next, add 16 parts of curing agent, 0.04 parts of catalyst, and 0.3 parts of leveling agent, and stir evenly to produce a super-amphiphobic, anti-waxing epoxy composite coating. The epoxy resin is bisphenol F-type epoxy resin; the curing agent is a mixture of 1,6-hexanediamine and maleic anhydride; and the catalyst is 2-ethyl-4-methylimidazole.

[0136] Example 11

[0137] A method for preparing a super-amphiphobic anti-wax epoxy composite coating comprises the following steps:

[0138] S1: In parts by mass, 0.5 parts of fluorinated silane modifier are added to a mixture of 15 parts of ethanol and water (mass ratio 7:2) and dispersed evenly, and then placed in a magnetic stirrer to react at 25°C for 1.5 hours to obtain a hydrolysis solution of the fluorinated silane modifier. Next, 2 parts of 200nm SiO2 are evenly dispersed in 80 parts of ethanol to obtain a SiO2 dispersion. Secondly, the SiO2 dispersion is added to the hydrolysis solution of the fluorinated silane modifier and reacted in a 50°C water bath for 6 hours. After the reaction, it is filtered and washed 3 times with anhydrous ethanol. Finally, it is dried under vacuum at 60°C for 4 hours to obtain fluorinated silane-modified nano-SiO2 (F-SiO2). Among them, the fluorinated silane modifier is perfluorohexyltriethoxysilane;

[0139] S2: In parts by mass, 15 parts of pentaerythritol mercaptopropionate, 30 parts of glycidyl methacrylate and 40 parts of a fluorine-containing modifier with a double bond are uniformly dispersed by ultrasonication in 80 parts of acetone, and 1.5 parts of a photoinitiator are added, stirred until uniformly dispersed, and irradiated under a UV lamp at 30°C for 2 hours. The product is subjected to rotary evaporation to remove the acetone solvent to obtain a fluorine-containing modifier with an epoxy group. Then, 8 parts of the fluorine-containing modifier with an epoxy group are mixed with 20 parts of an epoxy resin to obtain a modified epoxy resin. Among them, the fluorine-containing modifier with a double bond is a perfluoroalkyl vinyl ether; the photoinitiator is 4-methylbenzophenone; and the epoxy resin is a polyphenol-type glycidyl ether epoxy resin;

[0140] S3: Disperse 15 parts by mass of modified epoxy resin in 30 parts by mass of ethanol, then add 7 parts of fluorinated silane-modified silica and stir for 30 minutes. Next, add 15 parts of curing agent, 0.03 parts of catalyst, and 0.2 parts of leveling agent, and stir evenly to produce a super-amphiphobic, anti-wax epoxy composite coating. The epoxy resin is a polyphenol-based glycidyl ether epoxy resin; the curing agent is 1,6-hexanediamine; and the catalyst is DMP-30.

[0141] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

[0142] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a super-amphiphobic anti-waxing epoxy composite coating, characterized in that: The following steps are involved: Mixing a fluorine-containing silane modifier with an alcohol aqueous solution to carry out a hydrolysis reaction to obtain a hydrolysis solution of the fluorine-containing silane modifier, adding a nano-silica dispersion to the hydrolysis solution of the fluorine-containing silane modifier, stirring and reacting, and obtaining fluorine-containing silane-modified nano-silica; Pentaerythritol mercaptopropionate, glycidyl methacrylate and a fluorine-containing modifier with a double bond are dispersed in acetone, ultrasonically dispersed, a photoinitiator is added, stirred and dispersed uniformly, the reaction system is placed under ultraviolet light, stirred and reacted to obtain a fluorine-containing modifier with an epoxy group, and the fluorine-containing modifier with an epoxy group is uniformly mixed with an epoxy resin to obtain a modified epoxy resin; After the modified epoxy resin and the fluorine-containing silane-modified nano-silica are mixed, a curing agent, a catalyst and a leveling agent are added, and the mixture is stirred evenly to prepare the super-amphiphobic anti-waxing epoxy composite coating.

2. The method for preparing a super-amphiphobic anti-waxing epoxy composite coating according to claim 1, wherein: The particle size of the nano-silicon dioxide is 15 to 500 nm.

3. The method for preparing a super-amphiphobic anti-waxing epoxy composite coating according to claim 1, wherein: During the hydrolysis reaction, the reaction temperature is 20-30° C. and the reaction time is 1-2 hours.

4. The method for preparing a super-amphiphobic anti-waxing epoxy composite coating according to claim 1, wherein: The fluorine-containing silane modifier is mixed with an alcohol aqueous solution to carry out a hydrolysis reaction, and after the nano-silica is added, the mixture is stirred and reacted at 40-60° C. for 4-8 hours.

5. The method for preparing a super-amphiphobic anti-waxing epoxy composite coating according to claim 1, wherein: Calculated by mass, the ratio of the nano-silica particles to the fluorine-containing silane modifier is (0.5-5):(0.1-1).

6. The method for preparing a super-amphiphobic anti-waxing epoxy composite coating according to claim 1, wherein: Calculated by mass, the ratio of pentaerythritol mercaptopropionate, glycidyl methacrylate and double-bond fluorine-containing modifier is (10-20): (10-60): (10-60).

7. The method for preparing a super-amphiphobic anti-waxing epoxy composite coating according to claim 1, wherein: Calculated by mass, the ratio of the fluorine-containing modifier with epoxy group to the epoxy resin is (0.1-1):(0.4-4).

8. The method for preparing a super-amphiphobic anti-waxing epoxy composite coating according to claim 1, wherein: In parts by mass, the ratio of the modified epoxy resin, fluorinated silane-modified silica, curing agent, catalyst and leveling agent is (10-20):(3-10):(8-16):(0.02-0.04):(0.1-0.3).

9. A super-amphiphobic anti-wax epoxy composite coating, characterized in that: It is prepared by the method according to any one of claims 1 to 8.

10. Use of the super-amphiphobic anti-wax epoxy composite coating according to claim 9 in oil pipelines.

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