Super-hydrophobic oleophobic epoxy anticorrosive wear-resistant powder coating and preparation method thereof

Abstract

The invention relates to the technical field of coating preparation, and provides a super-hydrophobic oleophobic epoxy anticorrosive wear-resistant powder coating and a preparation method thereof. According to the coating, phenolic epoxy resin and bisphenol A epoxy resin are used as matrix resin, phenolic hydroxyl resin is used as a curing agent, super-hydrophobic / oleophobic carbon nanotubes are used as a modifier, ethylene-tetrafluoroethylene copolymer and polyamide resin are used as flexibilizers, super-hydrophobic / oleophobic nano silicon dioxide powder and super-hydrophobic hollow glass beads are used as fillers, and the super-hydrophobic / oleophobic nano silicon dioxide powder and the super-hydrophobic hollow glass beads are used as fillers. The super-hydrophobic and oleophobic epoxy anti-corrosion wear-resistant powder coating is prepared by taking an inorganic pigment as a coloring agent through the steps of material preparation, premixing, melt extrusion, tabletting, cooling, crushing and sieving under the cooperation of various functional assistants. The powder coating is subjected to electrostatic spraying (40-70 KV), the coating film thickness is about 350 microns, and the powder coating is cured into a film after being subjected to hydrophobic / oleophobic min at 180 DEG C / 5 min or 230 DEG C / 1.5 under the baking condition of 180 DEG C / 5 min. The contact angles of oil drops and water drops can reach 160 degrees and 161 degrees respectively, and the rolling angles are 2 degrees and 1 degree respectively.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating and its preparation method. Background Technology

[0002] Superhydrophobic / oleophobic coatings are widely used in military and civilian industries due to their properties such as superhydrophobicity / oleophobicity, anti-icing, self-cleaning, corrosion resistance, and wear resistance. The surface characteristics of superhydrophobic / oleophobic coatings are a high water / oil contact angle (typically >150°) and a low contact hysteresis (or droplet roll-off angle, typically <10°). Superhydrophobic / oleophobic coatings can prevent both icing on solid surfaces and the adhesion of oil. Superhydrophobic / oleophobic, self-cleaning coatings offer advantages such as water saving, energy saving, and environmental protection, and are increasingly attracting widespread attention, making them one of the current hot topics in materials science research.

[0003] Superhydrophobic surfaces are naturally occurring materials found in nature, such as plant leaves and petals, insect wings, and bird feathers. These surfaces possess a self-cleaning function, meaning that surface contaminants like dust can be carried away by rolling water droplets without leaving any trace. Numerous experimental and theoretical studies have shown a correlation between reduced ice adhesion and superhydrophobic surfaces; they can prevent supercooled water from forming ice, exhibiting anti-icing properties. In addition to their significant hydrophobicity, superhydrophobic surfaces can also reduce the accumulation of snow and ice on their surfaces, and may even completely prevent ice formation on solid surfaces.

[0004] Oleophobic wettability is key to superhydrophobicity. The wettability of a solid surface is mainly determined by two factors: surface roughness and surface energy. There are three main approaches to constructing superhydrophobic surfaces: (1) Constructing micron-nano scale rough structures on the surface of low surface energy materials; (2) Low surface energy modification is performed on the rough surface, that is, the substrate is modified with low surface material. (3) The construction of low surface energy microstructure and low surface energy modification are combined to reduce surface energy while increasing roughness, thus taking into account both surface stability and microstructure controllability.

[0005] With the strict implementation of environmental protection laws, pollution-free and environmentally friendly multifunctional coatings have developed rapidly. Thermosetting epoxy powder coatings, due to their 100% solids content, ability to achieve thick film requirements in a single spray, automated hot-melt curing in production lines, and safety, efficiency, and pollution-free properties, have played a crucial role in coating protection. However, current powder coatings on the market suffer from poor pollution resistance, weather resistance, abrasion resistance, and corrosion resistance, especially their low tolerance in harsh environments. The market urgently needs superhydrophobic / oleophobic, anti-icing, abrasion-resistant, and corrosion-resistant multifunctional powder coatings, which are still in the exploratory and research and development stage. In particular, mature technologies are lacking in fields requiring long-term use in harsh environments such as high-voltage power lines, power plants, aircraft, ships, wind turbine wings, high-speed rail, oil (natural gas) pipelines, drilling water injection pipes, building steel reinforcement and cables, seawater desalination, and condensation heat transfer. Summary of the Invention

[0006] To address the shortcomings of existing powder coatings on the market, such as poor stain resistance, poor weather resistance, poor abrasion resistance, poor corrosion resistance, and especially low tolerance in harsh environments, the technical solution of this invention is as follows: On one hand, the present invention provides a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, which, by weight parts, comprises the following components: 10-30 parts of phenolic epoxy resin, 10-30 parts of bisphenol A epoxy resin, 10-15 parts of phenolic hydroxyl resin curing agent, 1-4 parts of superhydrophobic / oleophobic carbon nanotubes, 2-5 parts of ethylene-tetrafluoroethylene copolymer, 2-5 parts of polyamide resin, 5-10 parts of superhydrophobic / oleophobic nano silica powder, 5-8 parts of superhydrophobic hollow glass microspheres, 3-5 parts of aluminum tripolyphosphate, 1-5 parts of inorganic pigment, 0.8-1.2 parts of leveling agent, 0.8-1.2 parts of wetting accelerator, 0.3-0.5 parts of benzoin, 0.5-0.7 parts of curing accelerator, 0.8-1.5 parts of special functional additive No. 1, and 1.5-3.0 parts of special functional additive No. 2.

[0007] Preferably, the inorganic pigment includes one or more of titanium dioxide, iron oxide, ceramic pigments, and carbon black; The leveling agent is an acrylic leveling agent adsorbed by silica; The curing accelerator is 2-methylimidazole; The special functional additive No. 1 is edge covering agent T-80; The special functional additive No. 2 is a solid lubricant containing graphite or molybdenum disulfide.

[0008] On the other hand, the present invention provides a method for preparing a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, which includes the following steps: S1, Preparation of superhydrophobic / oleophobic carbon nanotubes; S2, Preparation of superhydrophobic / oleophobic nano silica powder; S3. Preparation of superhydrophobic hollow glass microspheres; S4. Finished Product Preparation: Specifically includes... S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

[0009] The raw materials for preparing superhydrophobic / oleophobic carbon nanotubes include the following components by mass percentage: 88-95 parts anhydrous ethanol, 1-2 parts ammonia, 3-5 parts deionized water, 0.5-1.5 parts multi-walled carbon nanotubes, 0.5-1 part tetraethyl orthosilicate, and 1-2 parts fluorosilane.

[0010] The raw materials for preparing superhydrophobic / oleophobic nano silica powder include the following components by mass percentage: 62-78 parts anhydrous ethanol, 3-5 parts ammonia, 15-25 parts silica sol, 2-4 parts tetraethyl orthosilicate, and 2-4 parts fluorosilane.

[0011] The raw materials for preparing superhydrophobic hollow glass microspheres include the following components by mass percentage: 71-80 parts anhydrous ethanol, 4-6 parts deionized water, 1-3 parts fluorosilane, and 15-20 parts hollow glass microspheres.

[0012] Preferably, in S1, the preparation of superhydrophobic / oleophobic carbon nanotubes specifically includes: S11. Under a 35℃ water bath, anhydrous ethanol, ammonia, deionized water, and multi-walled carbon nanotubes were added to a beaker and ultrasonically dispersed for 0.5 h. Under medium-speed stirring, tetraethyl orthosilicate was added dropwise to the solution and reacted for 1 h. Finally, fluorosilane was added dropwise to the solution and stirred for 24 h to obtain a superhydrophobic coating solution. S12. Place the above superhydrophobic coating solution in an oven at 80°C. After the solvent has completely evaporated, take out the remaining low surface energy modified carbon nanotubes, grind them with a mortar and pestle, and sieve them to obtain superhydrophobic / oleophobic carbon nanotube powder.

[0013] Preferably, in S2, the preparation of superhydrophobic / oleophobic nano-silica powder specifically includes: S21. Weigh the anhydrous ethanol according to the proportion and add it to the dispersion tank. Add ammonia water under medium-low speed stirring and stir for 10 min. Slowly add silica sol dropwise. After the addition is complete, switch to high speed stirring for 10 min. Then, slowly add tetraethyl orthosilicate and fluorosilane dropwise under medium-low speed stirring. Seal the solution and stir at 1500 r / min for 24 h to obtain the modified nano silica coating. S22. Place the above modified nano-silica coating in an oven at 80°C. After the compatibilizer has completely evaporated, take out the remaining low surface energy modified SiO2 powder, grind it with a mortar and pestle, and sieve it to obtain superhydrophobic / oleophobic nano-silica powder.

[0014] Preferably, in step S3, the preparation of superhydrophobic hollow glass microspheres specifically includes: adding anhydrous ethanol to a dispersion vessel, adding deionized water while stirring, mixing evenly, adding fluorosilane, stirring evenly, adding hollow glass microspheres, heating to 60℃-70℃, continuing to stir for 4 hours, filtering, washing with water, and drying in an oven at 80-100℃; thus obtaining superhydrophobic hollow glass microspheres.

[0015] Compared with the prior art, the present invention provides a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating and its preparation method, which has the following beneficial effects: The main characteristics of superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coatings are as follows: The coating has a short gelation time, fast curing speed, and high coating efficiency; it has high hardness, good toughness, wear resistance, bending resistance, and resistance to thermal shock; it has excellent superhydrophobic / oleophobic properties, corrosion resistance, and wear resistance; it has good adhesion and excellent electrical and thermal conductivity; it has excellent cathodic disbondment resistance, resistance to chemicals, sewage, and seawater corrosion; it is safe and non-toxic in production, does not pollute the environment, and is beneficial to human health; fusion-bonded epoxy powder coatings are easy to apply, do not require a primer, can be applied in a single thick coat, and cure quickly, which is conducive to assembly line operations, easy to inspect and repair, and easy to control coating quality. Attached Figure Description

[0016] Figure 1 This invention provides a flowchart of a method for preparing a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating; Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] This invention provides a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, the composition of which, by mass fraction, includes the following components: 10-30 parts phenolic epoxy resin, 10-30 parts bisphenol A epoxy resin, 10-15 parts phenolic hydroxyl resin curing agent, 1-4 parts superhydrophobic / oleophobic carbon nanotubes, 2-5 parts ethylene-tetrafluoroethylene copolymer, 2-5 parts polyamide resin, 5-10 parts superhydrophobic / oleophobic nano silica powder, 5-8 parts superhydrophobic hollow glass microspheres, 3-5 parts aluminum tripolyphosphate, 1-5 parts inorganic pigment, 0.8-1.2 parts leveling agent, 0.8-1.2 parts wetting accelerator, 0.3-0.5 parts benzoin, 0.5-0.7 parts curing accelerator, 0.8-1.5 parts special functional additive No. 1, and 1.5-3.0 parts special functional additive No. 2.

[0019] The above-mentioned method for preparing superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coatings is as follows: Figure 1 As shown, it includes the following steps: S1, Preparation of superhydrophobic / oleophobic carbon nanotubes.

[0020] S2, Preparation of superhydrophobic / oleophobic nano silica powder.

[0021] S3. Preparation of superhydrophobic hollow glass microspheres.

[0022] S4. Finished Product Preparation: Specifically includes... S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

[0023] The phenolic epoxy resin mentioned is JECP-01A phenolic epoxy resin from Changshu Jiafa Chemical Co., Ltd. It is a light yellow transparent granular or flaky solid with an epoxy value of 0.105-0.115 mol / 100g, an epoxy equivalent of 850-950 g / mol, and a softening point of 95-115℃. Its molecular structure contains polyfunctional epoxy groups, resulting in high crosslinking density with the matching curing agent, high hardness, good toughness, fast curing speed, good chemical resistance, abrasion resistance, flexural resistance, thermal shock resistance, excellent cathodic disbondment properties, and electrical insulation.

[0024] The bisphenol A epoxy resin, model E12, is a commonly used medium- to high-molecular-weight solid epoxy resin in the industry, with an epoxy equivalent of 714-1111 g / mol, an epoxy value of 0.09-0.14 mol / 100g, and a softening point of 85-95℃. It has good chemical stability, high bonding strength, and excellent electrical properties.

[0025] The phenolic hydroxyl resin, model JECP-02B, is a curing agent from Changshu Jiafa Chemical Co., Ltd. It has an OH equivalent of 280-320, a softening point of 90-100℃, and a gel time / s (180℃) of 30-35. It incorporates some multifunctional activities and long-chain structures into the molecular structure of the terminal hydroxyl macromolecular polymer curing agent, giving the cured product both excellent adhesion and excellent flexibility. This curing agent has a similar structure to epoxy resin and good compatibility with epoxy resin, resulting in good flexibility in the cured product.

[0026] The fluorosilane is selected from one of perfluorodecyltriethoxysilane, perfluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorooctyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane.

[0027] Perfluorosilanes, upon hydrolysis, release low-molecular-weight alcohols. The resulting reactive silanols can chemically bond with hydroxyl, carboxyl, and oxygen-containing groups in many inorganic and organic substrates, forming self-assembled monomolecular fluorosilicone films on inorganic surfaces. The treated substrates exhibit extremely low surface energy and very poor wettability, resulting in excellent hydrophobic, oleophobic, and antifouling properties.

[0028] Tetraethyl orthosilicate is a colorless liquid with a slight odor. It has a melting point of -77°C (hydrophobic / oleophobic) and a boiling point of 165.5°C. It is slightly soluble in water, but soluble in ethanol and ether. It is used in heat-resistant coatings, chemically resistant coatings, and as an intermediate in organic synthesis. Tetraethyl orthosilicate is also one of the substrates for manufacturing nanoscale silica, typically using an ethanol solution, with the particle properties controlled by adjusting the solution's pH. Adding a certain amount of tetraethyl orthosilicate during the modification of superhydrophobic materials can prepare superhydrophobic / superoleophobic materials.

[0029] The ethylene-tetrafluoroethylene copolymer, commonly known as polyvinylidene fluoride (PVC), is also known as F-40. It has low surface energy, good hydrophobicity, a long-term operating temperature range of -80 to 220 degrees Celsius, excellent chemical corrosion resistance (resistant to all chemicals), the lowest coefficient of friction among plastics, and good electrical properties; its electrical insulation is unaffected by temperature. It exhibits good creep resistance and compressive strength, high tensile strength, and an elongation of 100-300%. It also has good dielectric properties and excellent radiation resistance. Adding an appropriate amount of ethylene-tetrafluoroethylene copolymer to epoxy powder coatings can improve the coating's corrosion resistance, hydrophobicity, abrasion resistance, and flexibility.

[0030] The polyamide resin mentioned is commonly known as nylon. It is non-toxic, lightweight, and possesses excellent mechanical strength, heat resistance, abrasion resistance, chemical resistance, excellent toughness, flexibility, oil resistance, water resistance, mildew resistance, and self-lubricating properties. Adding an appropriate amount of polyamide resin to an epoxy curing system can improve the system's flexibility, impact resistance, abrasion resistance, and chemical corrosion resistance.

[0031] The aluminum tripolyphosphate is a pollution-free and environmentally friendly white anti-rust pigment that is widely used in various anti-rust coatings. It has excellent acid resistance, water resistance, fire resistance, and heavy corrosion resistance.

[0032] The inorganic pigments include titanium dioxide, iron oxide pigments, ceramic pigments, carbon black, etc. Their main functions are coloring and corrosion prevention.

[0033] The leveling agent mentioned is T-988 from Shanghai Sosun Chemical Co., Ltd. It is an acrylic leveling agent adsorbed by silica, a white free-flowing powder with an active ingredient content of >60% and >99%. When applied to powder coatings, it reduces the surface tension of the coating film, eliminates fisheyes and pinholes, and significantly improves the gloss and image quality of the coating film. It can enhance the wetting of the substrate and reduce skinning. It does not contain silicone and does not affect the adhesion of the coating film.

[0034] The wetting accelerator mentioned is BLC701 from Nanhai Chemical, a white powder with a solid content of 99% and a softening point of 95-125℃. In powder coatings, it can reduce melt viscosity and increase molten fluidity; it can also make the surface tension of the coating uniform, alleviating the formation of Bénard vortices and orange peel; it can reduce the interfacial tension between the molten coating and the substrate and fillers, increasing the wettability of the substrate and fillers, reducing pinholes, and improving leveling.

[0035] The benzoin mentioned is Fenghua Jiqi High-Tech's benzoin GK-300, chemically known as benzoyl, a white powder with a purity of 99.7% and a melting point of 133-137℃. Adding an appropriate amount of benzoin to powder coatings can accelerate the vaporization and discharge of trace amounts of moisture and solvents during the curing process, thus avoiding defects such as pinholes, shrinkage cavities, and bubbles on the coating surface.

[0036] The curing accelerator 2-methylimidazole is a white crystalline powder with a melting point of 145-146℃. In epoxy curing systems, it can be used alone as a curing agent for epoxy resins, or as an accelerator with other curing agents such as dicyandiamide and phenolic resins, to lower the curing temperature and shorten the curing time of the epoxy system, and to achieve more complete curing and better performance.

[0037] The special functional additive No. 1 and edge covering agent T-80 (Shanghai Suoshi), a white powder, can effectively improve the "black edge" phenomenon of the coating and prevent sagging.

[0038] Special functional additive No. 1 is a solid lubricant. Graphite or molybdenum disulfide can improve the lubricity, extreme pressure and friction resistance of epoxy-cured coatings.

[0039] The superhydrophobic / oleophobic carbon nanotubes were prepared in-house according to the method provided in this invention. They are multi-walled carbon nanotubes modified with fluorosilane. The carbon nanotubes are hydroxyl-containing multi-walled carbon nanotubes with a diameter of 2–50 nm, a length of 1–30 μm, and a hydroxyl content of 5–8%. The fluorosilane is a long-chain perfluorosilane with a carbon chain length greater than 5 and a triethoxy end group. After modification with fluorosilane, long-chain perfluoroalkyl groups can be grafted onto the surface of the hydroxyl-containing carbon nanotubes, significantly reducing the surface energy of the nanotubes and preventing aggregation. During the preparation process, tetraethyl orthosilicate and ammonia are added to the solution, forming nano-silica nanoparticles that can overlap or entangle with the carbon nanotubes, improving the strength of the nanotube coating and increasing the surface roughness, thereby obtaining a nanoporous rough surface. This plays a crucial role in achieving superhydrophobicity and the bouncing of dew droplets during condensation. Research has found that adding a certain amount of tetraethyl orthosilicate during the modification of carbon nanotubes results in modified carbon nanotubes with superhydrophobic / oleophobic properties. The carbon nanotubes used in this invention possess excellent thermal and electrical conductivity. The superhydrophobic coating obtained using the method described in this invention exhibits good electrical and thermal conductivity, with a rapid nucleation rate and high droplet bouncing speed during condensation, facilitating rapid desorption from the surface. This effectively reduces the amount and size of residual droplets on the surface, which is significant for maintaining surface dryness and improving heat exchange efficiency. It shows promising application prospects in fields such as air conditioning heat exchangers, water collection, seawater desalination, and condensation heat transfer.

[0040] The superhydrophobic / oleophobic nano silica powder is self-made and prepared according to the preparation method provided in this invention. It is a nano silica powder with perfluorosilane surface modification.

[0041] Adding a certain amount of tetraethyl orthosilicate during the modification of nano-silica results in modified nano-silica particles with superhydrophobic / oleophobic properties. Adding an appropriate amount to epoxy powder coatings can create a micron-nano micro-rough structure on the surface of the cured epoxy, similar to the surface of a lotus leaf, exhibiting superhydrophobic / oleophobic, corrosion-resistant, wear-resistant, and self-cleaning functions.

[0042] The superhydrophobic hollow glass microspheres are self-made according to the preparation method provided in this invention. Hollow glass microspheres are tiny, hollow spherical powders. The particle size can be arbitrarily selected between 30-100 micrometers as needed, and the density is 0.1-0.7 g / ml. They have the advantages of being lightweight yet bulky, having low thermal conductivity, high compressive strength, and good dispersibility, flowability, and stability. In addition, they also possess excellent properties such as insulation, self-lubrication, sound insulation, water resistance, fire resistance, corrosion resistance, radiation protection, and non-toxicity. The hollow glass microspheres are surface-modified with perfluorosilane, giving them superhydrophobic properties. They form a superhydrophobic rough structure on the surface of the cured epoxy powder coating, enhancing the coating's anti-icing and self-cleaning properties. Example

[0043] This invention patent provides a method for preparing a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating. In this embodiment, the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, by mass fraction, comprises the following components: 10 parts phenolic epoxy resin, 26 parts bisphenol A epoxy resin, 10 parts phenolic hydroxyl resin curing agent, 1 part superhydrophobic / oleophobic carbon nanotubes, 5 parts ethylene-tetrafluoroethylene copolymer, 3 parts polyamide resin, 10 parts superhydrophobic / oleophobic nano-silica powder, 8 parts superhydrophobic hollow glass microspheres, 5 parts aluminum tripolyphosphate, 5 parts inorganic pigment, 0.8 parts leveling agent, 1.2 parts wetting accelerator, 0.5 parts benzoin, 0.5 parts curing accelerator, 0.8 parts special functional additive No. 1, and 1.5 parts special functional additive No. 2.

[0044] In this embodiment, the preparation of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating according to the above proportions includes the following steps: S1. Preparation of superhydrophobic / oleophobic carbon nanotubes: The raw materials for preparing superhydrophobic / oleophobic carbon nanotubes include the following components by mass percentage: 88-95 parts anhydrous ethanol, 1-2 parts ammonia, 3-5 parts deionized water, 0.5-1.5 parts multi-walled carbon nanotubes, 0.5-1 parts tetraethyl orthosilicate, and 1-2 parts fluorosilane. The mass percentage of anhydrous ethanol is any value between 88-95, the mass percentage of ammonia is any value between 1-2, the mass percentage of deionized water is any value between 3-5, the mass percentage of multi-walled carbon nanotubes is any value between 0.5-1.5, the mass percentage of tetraethyl orthosilicate is any value between 0.5-1, and the mass percentage of fluorosilane is any value between 1-2.

[0045] S1 specifically includes: S11. Under 35℃ water bath conditions, anhydrous ethanol, ammonia, deionized water and multi-walled carbon nanotubes were added to a beaker in proportion and ultrasonically dispersed for 0.5h. Under medium speed stirring, tetraethyl orthosilicate was added dropwise to the solution and reacted for 1h. Finally, fluorosilane was added dropwise to the solution and stirred for 24h to obtain a superhydrophobic coating solution. S12. Place the above superhydrophobic coating solution in an oven at 80°C. After the solvent has completely evaporated, take out the remaining low surface energy modified carbon nanotubes, grind them with a mortar and pestle, and sieve them to obtain superhydrophobic / oleophobic carbon nanotube powder.

[0046] S2. Preparation of superhydrophobic / oleophobic nano-silica powder: The raw materials for preparing superhydrophobic / oleophobic nano-silica powder, by mass percentage, include the following components: 62-78 parts anhydrous ethanol, 3-5 parts ammonia, 15-25 parts silica sol, 2-4 parts tetraethyl orthosilicate, and 2-4 parts fluorosilane. The mass percentages of anhydrous ethanol are any values ​​within the range of 62-78, ammonia is any value within the range of 3-5, silica sol is any value within the range of 15-25, tetraethyl orthosilicate is any value within the range of 2-4, and fluorosilane is any value within the range of 2-4.

[0047] S2 specifically includes: S21. Weigh the anhydrous ethanol according to the proportion and add it to the dispersion tank. Add ammonia water under medium-low speed stirring and stir for 10 min. Slowly add silica sol dropwise. After the addition is complete, switch to high speed stirring for 10 min. Then, slowly add tetraethyl orthosilicate and fluorosilane dropwise under medium-low speed stirring. Seal the solution and stir at 1500 r / min for 24 h to obtain the modified nano silica coating. S22. Place the above modified nano-silica coating in an oven at 80°C. After the compatibilizer has completely evaporated, take out the remaining low surface energy modified SiO2 powder, grind it with a mortar and pestle, and sieve it to obtain superhydrophobic / oleophobic nano-silica powder.

[0048] S3. Preparation of superhydrophobic hollow glass microspheres: The raw materials for preparing superhydrophobic hollow glass microspheres, by mass percentage, include the following components: 71-80 parts anhydrous ethanol, 4-6 parts deionized water, 1-3 parts fluorosilane, and 15-20 parts hollow glass microspheres. The mass percentage of anhydrous ethanol is any value between 71-80, the mass percentage of deionized water is any value between 4-6, the mass percentage of fluorosilane is any value between 1-3, and the mass percentage of hollow glass microspheres is any value between 15-20.

[0049] S3 specifically includes: adding anhydrous ethanol to a dispersion vessel, adding deionized water while stirring, mixing evenly, adding fluorosilane, stirring evenly, adding hollow glass microspheres, heating to 60℃-70℃, continuing to stir for 4 hours, filtering, washing with water, and drying in an oven at 80-100℃; thus obtaining superhydrophobic hollow glass microspheres.

[0050] S4. Finished Product Preparation: Specifically includes... S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

[0051] Example 2.

[0052] This invention patent provides a method for preparing a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating. In this embodiment, the composition of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, by mass fraction, includes the following components: 23 parts phenolic epoxy resin, 10 parts bisphenol A epoxy resin, 12 parts phenolic hydroxyl resin curing agent, 1.2 parts superhydrophobic / oleophobic carbon nanotubes, 3 parts ethylene-tetrafluoroethylene copolymer, 5 parts polyamide resin, 10 parts superhydrophobic / oleophobic nano silica powder, 6 parts superhydrophobic hollow glass microspheres, 4 parts aluminum tripolyphosphate, 1 part inorganic pigment, 0.8 parts leveling agent, 0.8 parts wetting accelerator, 0.4 parts benzoin, 0.5 parts curing accelerator, 1 part special functional additive No. 1, and 1.6 parts special functional additive No. 2.

[0053] In this embodiment, the preparation of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating according to the above proportions includes the following steps: S1. Preparation of superhydrophobic / oleophobic carbon nanotubes, same as in Example 1.

[0054] S2. The preparation of superhydrophobic / oleophobic nano silica powder is the same as in Example 1.

[0055] S3. Preparation of superhydrophobic hollow glass microspheres, same as in Example 1.

[0056] S4. Finished Product Preparation: Specifically includes... S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

[0057] Example 3 This invention patent provides a method for preparing a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating. In this embodiment, the composition of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, by mass fraction, is as follows: 24 parts phenolic epoxy resin, 23 parts bisphenol A epoxy resin, 13 parts phenolic hydroxyl resin curing agent, 4 parts superhydrophobic / oleophobic carbon nanotubes, 4 parts ethylene-tetrafluoroethylene copolymer, 3 parts polyamide resin, 10 parts superhydrophobic / oleophobic nano silica powder, 5 parts superhydrophobic hollow glass microspheres, 5 parts aluminum tripolyphosphate, 3 parts inorganic pigment, 1 part leveling agent, 0.8 parts wetting accelerator, 0.4 parts benzoin, 0.6 parts curing accelerator, 1 part special functional additive No. 1, and 2 parts special functional additive No. 2.

[0058] In this embodiment, the preparation of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating according to the above proportions includes the following steps: S1. Preparation of superhydrophobic / oleophobic carbon nanotubes, same as in Example 1.

[0059] S2. The preparation of superhydrophobic / oleophobic nano silica powder is the same as in Example 1.

[0060] S3. Preparation of superhydrophobic hollow glass microspheres, same as in Example 1.

[0061] S4. Finished Product Preparation: Specifically includes... S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

[0062] Example 4 This invention patent provides a method for preparing a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating. In this embodiment, the composition of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, by mass fraction, includes the following components: 25 parts phenolic epoxy resin, 22 parts bisphenol A epoxy resin, 13 parts phenolic hydroxyl resin curing agent, 1.2 parts superhydrophobic / oleophobic carbon nanotubes, 3 parts ethylene-tetrafluoroethylene copolymer, 4 parts polyamide resin, 5 parts superhydrophobic / oleophobic nano silica powder, 8 parts superhydrophobic hollow glass microspheres, 3 parts aluminum tripolyphosphate, 4 parts inorganic pigment, 1.2 parts leveling agent, 1 part wetting accelerator, 0.4 parts benzoin, 0.5 parts curing accelerator, 1 part special functional additive No. 1, and 1.5 parts special functional additive No. 2.

[0063] In this embodiment, the preparation of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating according to the above proportions includes the following steps: S1. Preparation of superhydrophobic / oleophobic carbon nanotubes, same as in Example 1.

[0064] S2. The preparation of superhydrophobic / oleophobic nano silica powder is the same as in Example 1.

[0065] S3. Preparation of superhydrophobic hollow glass microspheres, same as in Example 1.

[0066] S4. Finished Product Preparation: Specifically includes... S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

[0067] Example 5 This invention patent provides a method for preparing a superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating. In this embodiment, the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating comprises, by mass fraction, the following components: 30 parts phenolic epoxy resin, 30 parts bisphenol A epoxy resin, 15 parts phenolic hydroxyl resin curing agent, 4 parts superhydrophobic / oleophobic carbon nanotubes, 2 parts ethylene-tetrafluoroethylene copolymer, 2 parts polyamide resin, 8 parts superhydrophobic / oleophobic nano silica powder, 8 parts superhydrophobic hollow glass microspheres, 5 parts aluminum tripolyphosphate, 3 parts inorganic pigment, 1 part leveling agent, 1.2 parts wetting accelerator, 0.3 parts benzoin, 0.7 parts curing accelerator, 1.5 parts special functional additive No. 1, and 3 parts special functional additive No. 2.

[0068] In this embodiment, the preparation of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating according to the above proportions includes the following steps: S1. Preparation of superhydrophobic / oleophobic carbon nanotubes, same as in Example 1.

[0069] S2. The preparation of superhydrophobic / oleophobic nano silica powder is the same as in Example 1.

[0070] S3. Preparation of superhydrophobic hollow glass microspheres, same as in Example 1.

[0071] S4. Finished Product Preparation: Specifically includes... S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

[0072] In the above embodiments, The method of using the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating provided by this invention: Construction conditions: Powder coating, electrostatic spraying 40-70KV, coating thickness 350um.

[0073] Baking conditions: Curing at 180℃ for 5 minutes or at 230℃ for 1.5 minutes (hydrophobic / oleophobic). The contact angles of oil droplets and water droplets on the coating surface can reach 160° and 161°, respectively, and the roll-off angles are 2° and 1°, respectively.

[0074] The superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating provided by this invention has the following basic properties after testing: Curing time: 180℃ / 5min; 230℃ / 1.5min; Gelation time: 180℃ / 1.5min; 230℃ / 0.5min; Non-volatile content: Hydrophobic / Oleophobic ≥ 99.4% Particle size distribution: ≤3.0% on 150µm sieve; ≤0.2% on 250µm sieve.

[0075] Density: 1.3-1.5 g / cm³ 3 ; Magnetic material content: ≤0.002%; The performance indicators of the superhydrophobic / oleophobic epoxy anti-corrosion and wear-resistant powder coating are as follows: Appearance: Smooth, uniform color, free of bubbles, cracks, and shrinkage cavities; Adhesion: Grade 0; Resistant to 1.5J impact (-30℃): No pinholes or leaks; Impact resistance (front / back): 50cm; Flexibility: 1mm; Anti-3 O Bending: No cracks; Chemical corrosion resistance: Pass; Cathode stripping at 48h and 65℃: 2mm; Cathode stripping 28d: 3mm; hydrophobic / oleophobic; Cross-sectional porosity: 1; Bonding porosity: Grade 1-2; Abrasion resistance (sand test): 5 L / µm; Salt spray resistance (5% NaCl, 4000h): 2mm; Water contact angle: 161° o ; Oil contact angle: 160° o ; Water roll angle: 1 o ; Oil roll-off angle: 2o .

[0076] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0077] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating, characterized in that, By weight percentage, the product comprises the following components: 10-30 parts phenolic epoxy resin, 10-30 parts bisphenol A epoxy resin, 10-15 parts phenolic hydroxyl resin curing agent, 1-4 parts superhydrophobic / oleophobic carbon nanotubes, 2-5 parts ethylene-tetrafluoroethylene copolymer, 2-5 parts polyamide resin, 5-10 parts superhydrophobic / oleophobic nano silica powder, 5-8 parts superhydrophobic hollow glass microspheres, 3-5 parts aluminum tripolyphosphate, 1-5 parts inorganic pigment, 0.8-1.2 parts leveling agent, 0.8-1.2 parts wetting accelerator, 0.3-0.5 parts benzoin, 0.5-0.7 parts curing accelerator, 0.8-1.5 parts special functional additive No. 1, and 1.5-3.0 parts special functional additive No.

2.

2. The superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating as described in claim 1, characterized in that, The inorganic pigments include one or more of titanium dioxide, iron oxide, ceramic pigments, and carbon black; The leveling agent is an acrylic leveling agent adsorbed by silica; The curing accelerator is 2-methylimidazole; The special functional additive No. 1 is edge covering agent T-80; The special functional additive No. 2 is a solid lubricant containing graphite or molybdenum disulfide.

3. The preparation method of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating as described in any one of claims 1-2, characterized in that, Includes the following steps: S1, Preparation of superhydrophobic / oleophobic carbon nanotubes; The raw materials for preparing superhydrophobic / oleophobic carbon nanotubes include the following components by mass percentage: Anhydrous ethanol 88-95 parts, ammonia 1-2 parts, deionized water 3-5 parts, multi-walled carbon nanotubes 0.5-1.5 parts, tetraethyl orthosilicate 0.5-1 part, fluorosilane 1-2 parts; S2, Preparation of superhydrophobic / oleophobic nano silica powder; The raw materials for preparing superhydrophobic / oleophobic nano-silica powder include the following components by mass percentage: Anhydrous ethanol 62-78 parts, ammonia water 3-5 parts, silica sol 15-25 parts, tetraethyl orthosilicate 2-4 parts, and fluorosilane 2-4 parts; S3. Preparation of superhydrophobic hollow glass microspheres; The raw materials for preparing superhydrophobic hollow glass microspheres include the following components by mass percentage: 71-80 parts anhydrous ethanol, 4-6 parts deionized water, 1-3 parts fluorosilane, and 15-20 parts hollow glass microspheres. 4.S4, Finished Product Preparation: Specifically includes S41. Premixing: Weigh out the following ingredients in the correct proportions and add them sequentially into the mixer: phenolic epoxy resin, bisphenol A epoxy resin, phenolic hydroxyl resin curing agent, superhydrophobic / oleophobic carbon nanotubes, ethylene-tetrafluoroethylene copolymer, polyamide resin, superhydrophobic / oleophobic nano silica powder, aluminum tripolyphosphate, inorganic pigments, and various additives. Mix at high speed for 5 minutes until the mixture is homogeneous. S42. Melt extrusion: Inject the uniformly mixed material into a twin-screw extruder, rotate it 500-1200 rpm, and melt extrude it within the set temperature range (95-115℃). S43. Crushing and grinding: The extruded material is pressed into tablets by a tablet press, cooled by a cooling roller or cooling belt, then crushed by a pulverizer, finely crushed and classified by an air classifier, and then sieved through a rotary screen to a particle size of 120 mesh. Finally, superhydrophobic hollow glass microspheres are added and stirred to mix evenly to obtain the finished powder coating.

5. The preparation method of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating as described in claim 3, characterized in that, In S1, the preparation of superhydrophobic / oleophobic carbon nanotubes specifically includes: S11. Under a 35℃ water bath, anhydrous ethanol, ammonia, deionized water, and multi-walled carbon nanotubes were added to a beaker and ultrasonically dispersed for 0.5 h. Under medium-speed stirring, tetraethyl orthosilicate was added dropwise to the solution and reacted for 1 h. Finally, fluorosilane was added dropwise to the solution and stirred for 24 h to obtain a superhydrophobic coating solution. S12. Place the above superhydrophobic coating solution in an oven at 80°C. After the solvent has completely evaporated, take out the remaining low surface energy modified carbon nanotubes, grind them with a mortar and pestle, and sieve them to obtain superhydrophobic / oleophobic carbon nanotube powder.

6. The preparation method of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating as described in claim 3, Its characteristic lies in the preparation of superhydrophobic / oleophobic nano-silica powder in S2, specifically including: S21. Weigh the anhydrous ethanol according to the proportion and add it to the dispersion tank. Add ammonia water under medium-low speed stirring and stir for 10 min. Slowly add silica sol dropwise. After the addition is complete, switch to high speed stirring for 10 min. Then, slowly add tetraethyl orthosilicate and fluorosilane dropwise under medium-low speed stirring. Seal the solution and stir at 1500 r / min for 24 h to obtain the modified nano silica coating. S22. Place the above modified nano-silica coating in an oven at 80°C. After the compatibilizer has completely evaporated, take out the remaining low surface energy modified SiO2 powder, grind it with a mortar and pestle, and sieve it to obtain superhydrophobic / oleophobic nano-silica powder.

7. The preparation method of the superhydrophobic and oleophobic epoxy anti-corrosion and wear-resistant powder coating as described in claim 3, characterized in that, in S3, the preparation of superhydrophobic hollow glass microspheres specifically includes: Anhydrous ethanol was added to a dispersion vessel, and deionized water was added while stirring. After mixing evenly, fluorosilane was added and stirred evenly. Hollow glass microspheres were then added, and the temperature was raised to 60℃-70℃. Stirring was continued for 4 hours, and the mixture was filtered, washed with water, and dried in an oven at 80-100℃ to obtain superhydrophobic hollow glass microspheres.

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