Fluorosilicone modified hybrid super-amphiphobic coating as well as preparation method and application thereof

Abstract

The invention discloses a fluorine-silicon modified hybrid super-amphiphobic coating and a preparation method and application thereof.The preparation method of the super-amphiphobic coating comprises the following steps that an ester solvent serves as a reaction medium, fluorine-containing silane serves as a surface modifier, an alkaline substance serves as a hydrolysis accelerant, surface modification treatment is conducted on nano-filler in deionized water, and after a full reaction, the super-amphiphobic coating is obtained. The super-amphiphobic nano filler emulsion is obtained; and compounding the super-hydrophobic and super-oleophobic nano filler emulsion with a water-based resin matrix to obtain the fluorine-silicon modified hybrid super-amphiphobic coating. The coating prepared by the invention has super-hydrophobic and super-oleophobic properties, has a self-cleaning characteristic, excellent weather resistance, ultraviolet aging resistance, high and low temperature resistance and wear resistance, also has good anti-corrosion and anti-fouling characteristics, and is suitable for various industrial fields such as aerospace, electronics and electrics, new energy, buildings, automobiles, chemical engineering and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional coating materials and relates to a super-hydrophobic and super-oleophobic coating, and in particular to a fluorosilicone-modified hybrid super-amphiphobic coating and a preparation method and application thereof. Background Art

[0002] Superamphiphobic coatings are surface coating materials with both superhydrophobic and superoleophobic properties, demonstrating excellent self-cleaning, antifouling, and anti-corrosion properties under extreme conditions. Superamphiphobic coatings achieve these properties through micro-nanostructures and low-surface-energy chemistries, resulting in strong repellency to water, oil, and other organic liquids. Their unique self-cleaning properties hold broad application prospects in numerous industrial sectors, including shipbuilding, marine engineering, aerospace, electronics and electrical engineering, new energy, construction, automotive, home appliances, and the chemical industry. The development and application of these materials will generate immeasurable value for both life and industry.

[0003] Although superhydrophobic-superoleophobic coatings have excellent performance and are widely used, the preparation of superhydrophobic-oleophobic coatings is also quite complicated. The construction of superhydrophobic-oleophobic coatings requires the interaction of a rough surface structure and a low surface energy material. In addition, the existing methods for manufacturing superhydrophobic-oleophobic materials have some limitations, including complex reaction conditions, time-consuming and expensive steps, and are not applicable to a variety of substrates. It also limits large-scale production and cannot meet the needs of industrialization.

[0004] Chinese patent CN202210801843.6 discloses a super-amphiphobic and super-weather-resistant organosilicon protective coating and its preparation method. The raw material components of the protective coating are composed of organosilicon resin, fluorocarbon alcohol, polydopamine biomimetic modified nanoparticles, catalyst, organosilicon leveling agent, dispersant, organosilicon defoamer, and organic solvent. This invention uses fluorocarbon alcohol to partially modify the organosilicon resin through a dealcoholization condensation reaction, and then introduces high-bond-energy fluorocarbon segments, giving the resin matrix an extremely low surface energy. The highly active phenolic hydroxyl groups contained on the surface of the polydopamine biomimetic modified nanoparticles can form stable covalent bonds with the modified organosilicon resin matrix and the surface layers of metal and concrete substrates, significantly improving the weather resistance and hydrophobicity of the protective coating while effectively enhancing the bonding strength between the protective coating and the metal and concrete substrates. However, the preparation method of this protective coating has disadvantages such as the catalyst containing heavy metals, which is not conducive to high-end applications.

[0005] Chinese patent CN202210829868.7 discloses a super-hydrophobic and super-oleophobic antibacterial and anti-corrosion coating, its preparation method and application. The super-hydrophobic and super-oleophobic SiO2@POS / N+ antibacterial and anti-corrosion coating is coated on the metal surface by the sol-gel method and the spraying method, thereby achieving the purpose of metal protection. However, the coating has insufficient adhesion and needs to rely on spray coating.

[0006] Therefore, developing super-hydrophobic and super-oleophobic particulate materials with stable properties remains a difficulty in the existing technology. Summary of the Invention

[0007] In order to solve the problems of poor super-amphiphobic performance, difficulty in industrialization, complex construction process and high cost of super-amphiphobic materials in the prior art, the purpose of the present invention is to provide a fluorosilicone modified hybrid super-amphiphobic coating and its preparation method and application. The production process is simple, environmentally friendly, energy-saving and consumption-reducing. The obtained super-amphiphobic coating achieves good super-hydrophobicity and super-oleophobicity, and has excellent comprehensive protective performance of wear resistance, oil resistance, and acid and alkali corrosion resistance.

[0008] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0009] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0010] S1. Nanofiller modification

[0011] The nanofiller is surface-modified in deionized water using an ester solvent as a reaction medium, a fluorinated silane as a surface modifier, and an alkaline substance as a hydrolysis accelerator. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C and the reaction time is 5-12 hours.

[0012] The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L;

[0013] The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate;

[0014] The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane;

[0015] S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 3 to 5 hours to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

[0016] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0017] S1. Nanofiller modification treatment, including the following sub-steps:

[0018] S1.1. Place the nanofiller in a high-temperature furnace and heat it under an inert atmosphere. The inert gas is N2 or Ar with a purity of ≥99.999% and an inert gas flow rate of 50-100 mL / min. Slowly increase the temperature to 200-700°C at a rate of 2-10°C / min and hold for 1-4 hours.

[0019] S1.2. Using an ester solvent as a reaction medium, a fluorinated silane as a surface modifier, and an alkaline substance as a hydrolysis accelerator, the nanofiller is surface-modified in deionized water. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C, and the reaction time is 5-12 hours.

[0020] The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L;

[0021] The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate;

[0022] The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane;

[0023] S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 3 to 5 hours to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

[0024] Furthermore, in the above step S1, the hydrolysis accelerator is a mixture of one or more of ammonia water, triethylamine, tripropylamine, dimethylamine, diethanolamine, 1,2-propylenediamine, 4-dimethylaminopyridine, N-phenyl-1-naphthylamine, and hexamethyldisilazane.

[0025] Furthermore, in the above step S2, the water-based resin matrix is at least one of a water-based organosilicon-modified resin, a water-based fluorocarbon resin, and a water-based fluorosilicone resin.

[0026] Furthermore, in the above step S1, the mass ratio of the nanofiller, the ester solvent, the surface modifier, the hydrolysis accelerator, and the deionized water is (1-5): (40-80): (1-6): (2-6): (3-15).

[0027] Furthermore, in the above step S2, the mass ratio of the super-hydrophobic and super-oleophobic nano-filler emulsion to the aqueous resin matrix is 1:(0.1-0.8).

[0028] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0029] S1. Nanofiller modification

[0030] The nanofiller is surface-modified in deionized water using an ester solvent as a reaction medium, a mixture of a fluorinated silane and an organic coupling agent as a surface modifier, and an alkaline substance as a hydrolysis accelerator. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C, and the reaction time is 5-12 hours.

[0031] The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L;

[0032] The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate;

[0033] The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane;

[0034] The organic coupling agent is a mixture of one or more of methyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, methyl orthosilicate, ethyl orthosilicate, 1,2-bis(triethoxysilyl)ethane, vinyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, glycidoxypropyl caged polysilsesquioxane, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and tetraethyl titanate;

[0035] S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 30 to 100 minutes to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

[0036] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0037] S1. Nanofiller modification

[0038] S1.1. Place the nanofiller in a high-temperature furnace and heat it under an inert atmosphere. The inert gas is N2 or Ar with a purity of ≥99.999% and an inert gas flow rate of 50-100 mL / min. Slowly increase the temperature to 200-700°C at a rate of 2-10°C / min and hold for 1-4 hours.

[0039] S1.2. Surface modification of the nanofiller in deionized water using an ester solvent as the reaction medium, a mixture of a fluorinated silane and an organic coupling agent as the surface modifier, and an alkaline substance as the hydrolysis accelerator. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C, and the reaction time is 5-12 hours.

[0040] The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L;

[0041] The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate;

[0042] The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane;

[0043] The organic coupling agent is a mixture of one or more of methyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, methyl orthosilicate, ethyl orthosilicate, 1,2-bis(triethoxysilyl)ethane, vinyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, glycidoxypropyl caged polysilsesquioxane, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and tetraethyl titanate;

[0044] S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 30 to 100 minutes to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

[0045] Furthermore, in the above step S1, the hydrolysis accelerator is a mixture of one or more of ammonia water, triethylamine, tripropylamine, dimethylamine, diethanolamine, 1,2-propylenediamine, 4-dimethylaminopyridine, N-phenyl-1-naphthylamine, and hexamethyldisilazane.

[0046] Furthermore, in the above step S2, the water-based resin matrix is at least one of a water-based organosilicon-modified resin, a water-based fluorocarbon resin, a water-based fluorosilicone resin, and a water-based organosilicon-modified polyurethane resin.

[0047] Furthermore, in the above-mentioned step S1, the mass ratio of the nanofiller, the ester solvent, the surface modifier, the hydrolysis accelerator, and the deionized water is (1-5): (40-80): (1-6): (2-6): (3-15), wherein the mass ratio of the fluorinated silane to the organic coupling agent in the mixture is 1: (1-2).

[0048] Furthermore, in the above step S2, the mass ratio of the super-hydrophobic and super-oleophobic nano-filler emulsion to the aqueous resin matrix is 1:(0.2-0.8).

[0049] A fluorine-silicon modified hybrid super-amphiphobic coating is prepared by the above-mentioned preparation method of the fluorine-silicon modified hybrid super-amphiphobic coating.

[0050] Another object of the present invention is to provide an application of the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating, comprising the following steps: applying the fluorine-silicon modified hybrid super-amphiphobic coating to the surface of the substrate by wire rod coating or spraying, and controlling the coating thickness to 50 to 200 μm, and curing at room temperature and pressure for 24 to 36 hours.

[0051] Furthermore, the above-mentioned substrate includes but is not limited to metal, glass, ceramic, plastic, wood, and concrete.

[0052] The above-mentioned metal substrates include but are not limited to ship surfaces, automobile shells, and mechanical equipment; the glass substrates include but are not limited to building curtain walls, automobile glass, and touch screens.

[0053] Due to the adoption of the above technical solution, the present invention has the following advantages:

[0054] The invention discloses a method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating, which comprises the following steps: surface fluorine-silicon modification treatment is performed on a nanofiller to form an emulsion of the nanofiller, wherein the super-hydrophobic and super-oleophobic nanofiller emulsion has excellent compatibility with an aqueous resin, and the modified super-hydrophobic and super-oleophobic nanofiller emulsion and the aqueous resin are organic-inorganic hybridized according to a mass ratio to prepare a coating having super-hydrophobic and super-oleophobic properties, and having self-cleaning properties and excellent weather resistance, ultraviolet aging resistance, high and low temperature resistance and wear resistance, as well as good anti-corrosion and anti-fouling properties; the method is simple and easy, and no "three wastes" are discharged during the production process, which reduces production costs and is conducive to large-scale industrial production; the super-amphiphobic coating of the invention is applied to different substrate surfaces by wire rod coating or spraying to form a coating with a static water contact angle greater than 160° and an oil contact angle greater than 150°, and is suitable for many industrial fields such as aerospace, electronics and electrical, new energy, construction, automobiles, and chemicals, and has broad market application prospects.

[0055] The present invention discloses a method for preparing a fluorosilicone-modified hybrid super-amphiphobic coating, which comprises the following steps: subjecting nanoparticles to a high-temperature heat treatment to remove surface impurities, exposing more hydroxyl groups, improving the efficiency of fluorosilane grafting, promoting dehydration condensation of surface hydroxyl groups, reducing the surface hydroxyl density of the nanoparticles, forming a more stable silicon-oxygen bond, improving temperature resistance and chemical stability, and then modifying and combining the nanoparticles with a surface modifier, i.e., a fluorosilane or a mixture of a fluorosilane and an organic coupling agent. The surface modifier is reacted with the hydroxyl groups on the surface of the nanoparticles after the high-temperature treatment to introduce low surface energy groups to form a dense fluorinated layer, significantly reducing the surface energy. At the same time, the fluorinated layer can block erosion by oxygen and water molecules, thereby enhancing thermal stability and chemical inertness. Through chemical-physical synergy, the super-hydrophobicity, super-oleophobicity, high-temperature resistance, and corrosion resistance of the nanofiller are improved, so that the prepared super-amphiphobic coating is widely used in the anti-corrosion and anti-fouling treatment of automobiles, ships, and electronic appliances, as well as the anti-corrosion protection of chemical machinery and equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 is a scanning electron microscope image of the super-hydrophobic and super-oleophobic coating in Example 1 of the present invention;

[0057] Figure 2 yes Figure 1 Water contact angle and sliding angle diagram of the super-hydrophobic and super-oleophobic coating surface; where (a) is the contact angle; (b) is the sliding angle;

[0058] Figure 3 yes Figure 1 Oil contact angle and sliding angle diagram of the superhydrophobic and superoleophobic coating surface; where (a) is the contact angle; (b) is the sliding angle;

[0059] Figure 4 1 is a surface morphology characterization diagram of the super-hydrophobic and super-oleophobic coating in Example 1 of the present invention; wherein, (a) is a 2 μm morphology diagram; (b) is a 10 μm morphology diagram;

[0060] Figure 5 1 is an elemental analysis diagram of the super-hydrophobic and super-oleophobic coating in Example 1 of the present invention;

[0061] Figure 6 3 is a transmittance curve of the super-hydrophobic and super-oleophobic coating in Example 1 of the present invention. DETAILED DESCRIPTION

[0062] The technical solution of the present invention is further described in detail below through the drawings and embodiments.

[0063] This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0064] In the following examples, the particle size of the nanofiller is 10-100 nm, and the specific surface area is 280-350 m 2 / g, and the apparent density is 30-60g / L.

[0065] The preparation method of the fluorine-silicon modified hybrid super-amphiphobic coating of the present invention comprises the following steps: when the nanofiller is subjected to high-temperature heat treatment in an inert atmosphere, preferably, the heating temperature of nano-silicon dioxide is 200-400°C, the heating temperature of nano-titanium dioxide is 300-500°C, the heating temperature of nano-alumina is 400-600°C, the heating temperature of nano-zirconia is 500-700°C, and the heating temperature of nano-zinc oxide is 300-450°C.

[0066] Example 1

[0067] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0068] First, 10 g of fumed nano-silica with a particle size of 5 to 60 nm and 400 g of ethyl acetate were added to a three-necked flask, followed by the addition of 25 g of deionized water, 30 g of aqueous ammonia, and 5 g of perfluorooctylethyltrimethoxysilane. The flask was placed in an oil bath and heated to 40°C. The mixture was stirred and reacted for 5 h. The flask was then taken out and subjected to ultrasonic dispersion for 3 h to obtain a super-amphiphobic nano-filler emulsion. The super-amphiphobic nano-filler emulsion was stored as a suspension.

[0069] Then, 5g of the super-amphiphobic nanofiller emulsion was in-situ compounded with 2g of a water-based organosilicon-modified acrylic resin and dispersed at high speed at 45°C for 30min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0070] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 100 μm, and it was cured at room temperature and pressure for 24 hours to obtain a super-hydrophobic and super-oleophobic coating, and the coating was subjected to the following tests.

[0071] (1) Observation of the morphology of super-hydrophobic and super-oleophobic coatings, such as Figure 1 As shown in the figure, the superhydrophobic and superoleophobic coating presents a uniform, non-agglomerated spherical particle morphology.

[0072] (2) Use a static hydrophobic angle measuring instrument to measure the contact angle and rolling angle of the super-hydrophobic and super-oleophobic coating surface to water and oil respectively; Figure 2 As shown in Figure 2, the water contact angle of the superhydrophobic and superoleophobic coating is 160.2° and the sliding angle is 2.4°; Figure 3 As shown, the oil contact angle is 152.6° and the sliding angle is 3.5°.

[0073] (3) Figure 4 These are the surface morphologies of the super-hydrophobic and super-oleophobic coatings of the present invention at different magnifications.

[0074] (4) Figure 5 This is the element analysis-site diagram of the super-hydrophobic and super-oleophobic coating of the present invention. The content of each element in the super-hydrophobic and super-oleophobic coating is shown in Table 1.

[0075] Table 1

[0076] element wt% C 61.33 N 0.52 F 16.00 Si 22.15 Total 100.00

[0077] (5) The super-hydrophobic and super-oleophobic coating was subjected to a salt spray resistance test. The experimental time was 2400 h. The comparison results before and after the salt spray resistance test are shown in Table 2, indicating that the super-hydrophobic and super-oleophobic coating has good anti-corrosion performance.

[0078] Table 2

[0079] Water contact angle Water rolling angle Oil contact angle Oil rolling angle Before salt spray test 160.2° 2.4° 152.6° 3.5° After salt spray test 150.0° 3.3° 143.5° 5.6°

[0080] (6) The light transmittance of the super-hydrophobic and super-oleophobic coating of the present invention is 83.65%, and the light transmittance of the blank control example (i.e., the coating without adding the super-hydrophobic and super-oleophobic nanofiller emulsion) is 84.40%.

[0081] Example 2

[0082] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0083] First, 8 g of fumed nano-silica with a particle size of 20 to 100 nm and 350 g of ethyl acetate were added to a three-necked flask, followed by the addition of 20 g of deionized water, 10 g of hexamethyldisilazane, and 17 g of perfluorodecylethyltrimethoxysilane. The flask was placed in an oil bath and heated to 45°C. The mixture was stirred and reacted for 5 h. The flask was then taken out and subjected to ultrasonic dispersion for 3 h to obtain a super-amphiphobic nanofiller. The super-amphiphobic nanofiller emulsion was stored in the form of a suspension.

[0084] Then, 5g of super-amphiphobic nanofiller was in-situ compounded with 1g of water-based fluorocarbon resin and dispersed at high speed at 45°C for 30min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0085] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 100 μm, and it was cured at room temperature and pressure for 24 hours to obtain a super-hydrophobic and super-oleophobic coating.

[0086] Example 3

[0087] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0088] First, 15g of nano-titanium dioxide with a particle size of 20-100nm and 300g of ethyl acetate were added to a three-necked flask, followed by the addition of 40g of deionized water, 15g of ammonia water, and 15g of perfluorodecylethyltrimethoxysilane. The flask was placed in an oil bath and heated to 50°C. The mixture was stirred and reacted for 6h. The flask was taken out and subjected to ultrasonic dispersion treatment for 3.5h to obtain a super-amphiphobic nanofiller. The super-amphiphobic nanofiller emulsion was stored in the form of a suspension.

[0089] Then, 5g of super-amphiphobic nanofiller was in-situ compounded with 1g of water-based fluorosilicone resin and dispersed at high speed at 50°C for 30min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0090] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 80 μm, and it was cured at room temperature and pressure for 28 hours to obtain a super-hydrophobic and super-oleophobic coating.

[0091] Example 4

[0092] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0093] First, 10 g of nano-titanium dioxide with a particle size of 20 to 80 nm, 5 g of nano-zinc oxide with a particle size of 20 to 100 nm, and 300 g of ethyl acetate were added to a three-necked flask, and then 42 g of deionized water, 15 g of hexamethyldisilazane, 10 g of perfluorodecylethyltrimethoxysilane, and 7 g of methyltriethoxysilane were added in sequence. The mixture was placed in an oil bath and heated to 55° C. The mixture was stirred and reacted for 6 h. The mixture was taken out and ultrasonically dispersed for 3.5 h to obtain a super-amphiphobic nanofiller. The super-amphiphobic nanofiller emulsion was stored in the form of a suspension.

[0094] Then, 5 g of super-amphiphobic nanofiller was in situ compounded with 1.5 g of water-based fluorocarbon resin and dispersed at high speed at 50°C for 50 min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0095] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 120 μm, and it was cured at room temperature and pressure for 28 hours to obtain a super-hydrophobic and super-oleophobic coating.

[0096] Example 5

[0097] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0098] First, 8 g of fumed nano-silica with a particle size of 20 to 100 nm, 5 g of nano-alumina with a particle size of 30 to 100 nm, and 250 g of n-butyl acetate were added to a three-necked flask, followed by the addition of 60 g of deionized water, 20 g of ammonia water, and 15 g of perfluorobutylethyltriethoxysilane. The flask was placed in an oil bath and heated to 60° C. The mixture was stirred and reacted for 4 hours. The flask was then taken out and subjected to ultrasonic dispersion treatment for 3 hours to obtain a super-amphiphobic nano-filler. The super-amphiphobic nano-filler emulsion was stored in the form of a suspension.

[0099] Then, 6 g of super-amphiphobic nanofiller was in-situ compounded with 0.5 g of water-based organosilicon-modified acrylic resin and 1.0 g of water-based fluorocarbon resin, and high-speed dispersed at 55°C for 30 min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0100] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 150 μm, and it was cured at room temperature and pressure for 30 hours to obtain a super-hydrophobic and super-oleophobic coating.

[0101] Example 6

[0102] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0103] First, 10 g of nano-zirconium oxide with a particle size of 20 to 100 nm, 5 g of nano-titanium dioxide with a particle size of 20 to 100 nm, and 300 g of n-butyl acetate were added to a three-necked flask, and then 40 g of deionized water, 20 g of ammonia water, and 10 g of perfluorodecylethyltrimethoxysilane were added in sequence. The mixture was placed in an oil bath and heated to 65° C., stirred for reaction for 3 hours, and then taken out and ultrasonically dispersed for 4 hours to obtain a super-amphiphobic nanofiller. The super-amphiphobic nanofiller emulsion was stored in the form of a suspension.

[0104] The above-mentioned nano-zirconia and nano-titanium dioxide are all pre-treated nanoparticles. The pretreatment steps are as follows: placing the nano-zirconia in a high-temperature furnace, passing inert gas N2 with a purity of ≥99.999% at a flow rate of 50 mL / min, slowly heating to 700°C at a rate of 2°C / min, and keeping the temperature for 2 hours;

[0105] Place nano-titanium dioxide in a high-temperature furnace, introduce inert gas N2 with a purity of ≥99.999% at a flow rate of 50 mL / min, slowly heat to 500°C at a rate of 2°C / min, and keep warm for 2 hours;

[0106] Then, 5g of super-amphiphobic nanofiller was in-situ compounded with 1.2g of water-based organosilicon-modified acrylic resin and dispersed at high speed at 55°C for 40min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0107] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 180 μm, and it was cured at room temperature and pressure for 30 hours to obtain a super-hydrophobic and super-oleophobic coating.

[0108] Example 7

[0109] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0110] First, 12g of nano-alumina with a particle size of 20-100nm and 300g of n-butyl acetate were added to a three-necked flask, followed by the addition of 35g of deionized water, 12g of ammonia water, and 8g of perfluorooctylethyltriethoxysilane. The flask was placed in an oil bath and heated to 55°C. The mixture was stirred and reacted for 5h. The flask was then taken out and subjected to ultrasonic dispersion for 3h to obtain a super-amphiphobic nanofiller. The super-amphiphobic nanofiller emulsion was stored in the form of a suspension.

[0111] The nano-alumina is prepared by pre-treating the nano-particles. The pre-treatment steps are as follows: placing the nano-alumina in a high-temperature furnace, introducing inert gas Ar with a purity of ≥99.999% at a flow rate of 100 mL / min, slowly heating to 500°C at a rate of 5°C / min, and keeping the temperature for 3 hours;

[0112] Then, 5g of super-amphiphobic nanofiller was in-situ compounded with 1.2g of water-based organosilicon-modified acrylic resin and dispersed at high speed at 50°C for 80min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0113] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 200 μm, and it was cured at room temperature and pressure for 32 hours to obtain a super-hydrophobic and super-oleophobic coating.

[0114] Example 8

[0115] A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating comprises the following steps:

[0116] First, 5 g of fumed nano-silica with a particle size of 20 to 70 nm, 5 g of nano-titanium dioxide with a particle size of 20 to 100 nm, 5 g of nano-zinc oxide with a particle size of 20 to 100 nm, 150 g of ethyl acetate, and 100 g of dimethyl carbonate were added to a three-necked flask, and then 55 g of deionized water, 10 g of hexamethyldisilazane, and 15 g of perfluorodecylethyltrimethoxysilane were added in sequence. The mixture was placed in an oil bath and heated to 60° C., stirred and reacted for 5 h, and then taken out and ultrasonically dispersed for 3 h to obtain a super-amphiphobic nano-filler. The super-amphiphobic nano-filler emulsion was stored in the form of a suspension.

[0117] Then, 5g of super-amphiphobic nanofiller was in-situ compounded with 1.6g of waterborne organosilicon-modified polyurethane resin and dispersed at high speed at 60°C for 40min to prepare a white emulsion-like fluorosilicone-modified hybrid super-amphiphobic coating.

[0118] Finally, the above-mentioned fluorine-silicon modified hybrid super-amphiphobic coating was sprayed on the surface of the metal substrate, the coating thickness was controlled at 200 μm, and it was cured at room temperature and pressure for 36 hours to obtain a super-hydrophobic and super-oleophobic coating.

[0119] The contact angles of the super-hydrophobic and super-oleophobic coatings in Examples 1 to 8 were tested using a static hydrophobic angle measuring instrument. The test results are shown in Table 3.

[0120] Table 3

[0121] Water contact angle Water rolling angle Oil contact angle Oil rolling angle Example 1 160.2° 2.4° 152.6° 3.5° Example 2 165.1° 2.0° 155.2° 3.4° Example 3 161.8° 2.2° 150.9° 4.2° Example 4 169.9° 1.7° 156.3° 3.2° Example 5 162.6° 2.1° 150.8° 4.2° Example 6 170.5° 1.6° 157.0° 3.1° Example 7 168.2° 1.8° 155.9° 3.3° Example 8 169.4° 1.7° 153.6° 3.8°

[0122] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating, characterized in that: It includes the following steps: S1. Nanofiller modification The nanofiller is surface-modified in deionized water using an ester solvent as a reaction medium, a fluorinated silane as a surface modifier, and an alkaline substance as a hydrolysis accelerator. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C and the reaction time is 5-12 hours. The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L; The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate; The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane; S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 3 to 5 hours to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

2. A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating, characterized in that: It includes the following steps: S1. Nanofiller modification treatment, including the following sub-steps: S1.

1. Place the nanofiller in a high-temperature furnace and heat it under an inert atmosphere. The inert gas is N2 or Ar with a purity of ≥99.999% and an inert gas flow rate of 50-100 mL / min. Slowly increase the temperature to 200-700°C at a rate of 2-10°C / min and hold for 1-4 hours. S1.

2. Using an ester solvent as a reaction medium, a fluorinated silane as a surface modifier, and an alkaline substance as a hydrolysis accelerator, the nanofiller is surface-modified in deionized water. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C, and the reaction time is 5-12 hours. The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L; The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate; The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane; S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 3 to 5 hours to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

3. A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating, characterized in that: It includes the following steps: S1. Nanofiller modification The nanofiller is surface-modified in deionized water using an ester solvent as a reaction medium, a mixture of a fluorinated silane and an organic coupling agent as a surface modifier, and an alkaline substance as a hydrolysis accelerator. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C, and the reaction time is 5-12 hours. The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L; The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate; The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane; The organic coupling agent is a mixture of one or more of methyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, methyl orthosilicate, ethyl orthosilicate, 1,2-bis(triethoxysilyl)ethane, vinyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, glycidoxypropyl caged polysilsesquioxane, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and tetraethyl titanate; S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 30 to 100 minutes to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

4. A method for preparing a fluorine-silicon modified hybrid super-amphiphobic coating, characterized in that: It includes the following steps: S1. Nanofiller modification S1.

1. Place the nanofiller in a high-temperature furnace and heat it under an inert atmosphere. The inert gas is N2 or Ar with a purity of ≥99.999% and an inert gas flow rate of 50-100 mL / min. Slowly increase the temperature to 200-700°C at a rate of 2-10°C / min and hold for 1-4 hours. S1.

2. Surface modification of the nanofiller in deionized water using an ester solvent as the reaction medium, a mixture of a fluorinated silane and an organic coupling agent as the surface modifier, and an alkaline substance as the hydrolysis accelerator. After sufficient reaction, a super-amphiphobic nanofiller emulsion is obtained. The reaction temperature of the entire modification process is 40-70°C, and the reaction time is 5-12 hours. The nano filler is a mixture of one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, and nano zinc oxide; the particle size of the nano filler is 10 to 100 nm, and the specific surface area is 280 to 350 m 2 / g, apparent density is 30~60g / L; The ester solvent is a mixture of one or more of ethyl acetate, n-butyl acetate, and dimethyl carbonate; The fluorine-containing silane is a mixture of one or more of perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorodecylethyltrimethoxysilane, perfluorodecylethyltriethoxysilane, perfluorobutylethyltrimethoxysilane, perfluorobutylethyltriethoxysilane, trifluoromethylethyltrimethoxysilane, and trifluoromethylethylmethyldimethoxysilane; The organic coupling agent is a mixture of one or more of methyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, methyl orthosilicate, ethyl orthosilicate, 1,2-bis(triethoxysilyl)ethane, vinyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, glycidoxypropyl caged polysilsesquioxane, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and tetraethyl titanate; S2. Compounding the super-hydrophobic and super-oleophobic nanofiller emulsion obtained in step S1 with an aqueous resin matrix, stirring and mixing at a temperature of 45 to 60° C. for 30 to 100 minutes to obtain a fluorosilicone-modified hybrid super-amphiphobic coating.

5. according to the preparation method of the fluorine-silicon modified hybrid super-amphiphobic coating described in claim 1,2,3 or 4, it is characterized in that: It also includes any one or more of the following features: (1) In step S1, the hydrolysis accelerator is a mixture of one or more of ammonia water, triethylamine, tripropylamine, dimethylamine, diethanolamine, 1,2-propylenediamine, 4-dimethylaminopyridine, N-phenyl-1-naphthylamine, and hexamethyldisilazane. (2) In step S2, the water-based resin matrix is at least one of a water-based organosilicon-modified resin, a water-based fluorocarbon resin, a water-based fluorosilicone resin, and a water-based organosilicon-modified polyurethane resin.

6. according to the preparation method of the fluorine-silicon modified hybrid super-amphiphobic coating described in claim 1,2,3 or 4, it is characterized in that: In step S1, the mass ratio of the nanofiller, the ester solvent, the surface modifier, the hydrolysis accelerator, and the deionized water is (1-5): (40-80): (1-6): (2-6): (3-15), wherein the mass ratio of the fluorinated silane to the organic coupling agent in the mixture is 1: (1-2).

7. according to the preparation method of the fluorine-silicon modified hybrid super-amphiphobic coating described in claim 1,2,3 or 4, it is characterized in that: In the step S2, the mass ratio of the super-hydrophobic and super-oleophobic nano-filler emulsion to the aqueous resin matrix is 1:(0.2-0.8).

8. A fluorine-silicon modified hybrid super-amphiphobic coating, characterized by: The invention is prepared by the preparation method of the fluorine-silicon modified hybrid super-amphiphobic coating according to any one of claims 1 to 7.

9. An application of the fluorine-silicon modified hybrid super-amphiphobic coating according to claim 8, characterized in that: It includes the following steps: The fluorine-silicon modified hybrid super-amphiphobic coating is applied to the substrate surface by wire rod coating or spraying, the coating thickness is controlled at 50 to 200 μm, and it is cured at room temperature and pressure for 24 to 36 hours.

10. The use of the fluorine-silicon modified hybrid super-amphiphobic coating according to claim 9, characterized in that: The substrate includes but is not limited to metal, glass, ceramic, plastic, wood, concrete.

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