High-insulation wear-resistant super-hydrophobic protective coating and preparation method thereof

Abstract

The invention belongs to the technical field of coatings, and particularly relates to a high-insulation wear-resistant super-hydrophobic protective coating and a preparation method thereof. The coating comprises the following raw materials in parts by weight: 100 parts of matrix resin, 20-35 parts of liquid rubber modified inorganic particles, 0.5-2 parts of a bird repellent, 0.2-1.5 parts of an anti-ultraviolet agent, 0.1-1 part of an antioxidant and 15-35 parts of a diluent. The coating disclosed by the invention has excellent hydrophobic wear resistance, adhesive force, salt fog resistance and cold and heat resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and in particular relates to a highly insulating, wear-resistant, super-hydrophobic protective coating and a preparation method thereof. Background Art

[0002] Bird repellent paint is a specially formulated paint that can effectively repel birds and prevent them from nesting or staying in a specific area. The paint is harmless to birds, but it can make birds feel uncomfortable through its special smell, color or touch, thereby playing a repellent effect. Applying bird repellent paint on power equipment can effectively prevent birds from nesting and roosting, reduce the risk of equipment failures such as short circuits and flashovers caused by bird activities, and improve the safety and stability of the power system.

[0003] CN112680102A provides an AC / DC filter bird-proof insulating coating, coating and preparation method thereof, which realizes insulation of all charged bodies of the filter tower by spraying the insulating coating on the AC filter tower, and can withstand the voltage difference when the bird is short-circuited. At the same time, the addition of calcium tartrate can effectively improve the hydrophobicity of the insulating glue layer, and the insulating coating finally obtained has a strong curing degree and good quality. In the refining stage of the mill, the insulating coating is added with granular fulvic acid to assist in rolling, so that the insulating coating has strong adhesion, firmly adheres to the capacitor paint film, does not affect the adhesion of the paint film, effectively ensures the insulation effect and does not fall off, but the addition of granular fulvic acid to assist in rolling is actually a physical force, and cannot increase the adhesion of the coating well.

[0004] CN107312450A provides a bird-proofing and bird-repelling coating, which is composed of water-based silicone resin, silicon dioxide, solvent, acid-base buffer, flavoring agent and inorganic reflective filler and other ingredients, and has the advantages of fast drying, convenient construction, good adhesion, 5) good weather resistance, light retention and color retention. However, it uses water-based silicone resin as the base of the coating and has the defect of poor water resistance. Summary of the invention

[0005] The room temperature in the present invention refers to 18-25°C.

[0006] The first aspect of the present invention provides a highly insulating, wear-resistant and super-hydrophobic protective coating. The raw materials of the coating include, by weight: 100 parts of a base resin, 20-35 parts of liquid rubber-modified inorganic particles, 0.5-2 parts of a bird repellent, 0.2-1.5 parts of an anti-ultraviolet agent, 0.1-1 parts of an antioxidant, and 15-35 parts of a diluent.

[0007] As a preferred technical solution of the present invention, the raw materials of the coating include, by weight: 100 parts of base resin, 25-30 parts of liquid rubber modified inorganic particles, 0.6-0.8 parts of anti-ultraviolet agent, 1-1.5 parts of bird repellent, 0.3-0.5 parts of antioxidant, and 20-25 parts of diluent.

[0008] As a preferred technical solution of the present invention, the base resin is selected from a combination of silicone resin and acrylic resin.

[0009] As a preferred technical solution of the present invention, the weight ratio of the silicone resin to the acrylic resin is (60-80):(20-40), preferably (65-75):(25-35).

[0010] The organosilicon resin in the present invention can be obtained commercially, for example, the N-9801A organosilicon resin produced by Changzhou Jianuo Organosilicon Co., Ltd.

[0011] As a preferred technical solution of the present invention, the preparation method of the acrylic resin comprises:

[0012] S1: adding solvent A to a container equipped with a stirring device, a condensing reflux device, a heating and heat preservation device, and a dripping device, and heating to 80-90° C., and then dripping a mixture A of methyl methacrylate, butyl acrylate, styrene, trimethylaminopropyl methacrylamide chloride, and initiator A to carry out a first reaction;

[0013] After S2, a mixture B of solvent B and initiator B is added dropwise to carry out a second reaction.

[0014] The solvent A and solvent B in the present invention are only used to distinguish the solvents added in different steps. Similarly, the initiator A and initiator B are only used to distinguish the initiators added in different steps, and do not constitute a limitation to the present invention.

[0015] As a preferred technical solution of the present invention, the solvent A and the solvent B are independently selected from C3-C7 monohydric alcohols, such as isopropanol, n-butanol, etc., preferably n-butanol.

[0016] As a preferred technical solution of the present invention, the initiator A and the initiator B are independently selected from azo initiators; wherein the specific type of the azo initiator is not particularly limited, for example, it is one of azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptanenitrile. In the present invention, azobisisobutyronitrile is used as an example.

[0017] As a preferred technical solution of the present invention, the mass ratio of the solvent A to methyl methacrylate is 1:(0.5-1), preferably 1:(0.6-0.8).

[0018] As a preferred technical solution in the present invention, the weight ratio of methyl methacrylate, butyl acrylate, styrene and trimethylaminopropyl methacrylamide chloride is 1: (0.5-1.5): (0.3-0.8): (0.3-0.8), preferably 1: (0.8-1.2): (0.5-0.6): (0.5-0.6).

[0019] As a preferred technical solution in the present invention, the weight ratio of methyl methacrylate to initiator A is 1:(0.2-0.3).

[0020] As a preferred technical solution of the present invention, the weight ratio of the solvent B to the initiator B is 1:(0.08-0.2), preferably 1:(0.1-0.15).

[0021] As a preferred technical solution in the present invention, the weight ratio of the mixture A to the mixture B is (6-15):1, preferably (8-10):1.

[0022] As a preferred technical solution of the present invention, the mixture A and the mixture B are dripped independently within 0.5 hours.

[0023] As a preferred technical solution of the present invention, the conditions of the first reaction include: temperature of 80-90° C. and time of 1-1.5 h.

[0024] As a preferred technical solution of the present invention, the conditions of the second reaction include: temperature of 80-90°C and time of 3-4h.

[0025] As a more preferred technical solution of the present invention, the preparation method of the acrylic resin comprises:

[0026] S1: Add n-butanol (with a mass ratio of 1:(0.6-0.8) to methyl methacrylate) into a container equipped with a stirring device, a condensing reflux device, a heating and heat preservation device, and a dripping device, and heat it to 80-90°C, then drip a mixture A of methyl methacrylate, butyl acrylate, styrene, trimethylaminopropyl methacrylamide chloride and azobisisobutyronitrile in a weight ratio of 1:(0.8-1.2):(0.5-0.6):(0.5-0.6):(0.2-0.3), control the dripping of the mixture A to be completed within 0.5h, and continue the heat preservation reaction for 1-1.5h;

[0027] S2 continues to drip a mixture B of n-butanol and azobisisobutyronitrile in a weight ratio of 1:(0.1-0.15) (with a weight ratio of 1:(8-10) to mixture A), and controls the dripping of mixture B to be completed within 0.5h. Continue to keep the temperature for 3-4h, cool down, and discharge to obtain acrylic resin.

[0028] The use of the acrylic resin in the present invention can better increase the salt spray resistance of the coating, presumably because the trimethylaminopropyl methacrylamide chloride in the present invention can make the coating system have anti-electrolyte properties, further improving the salt spray resistance of the coating.

[0029] As a preferred technical solution of the present invention, the preparation method of the liquid rubber modified inorganic particles comprises:

[0030] (1) mixing inorganic particles with a sodium hydroxide aqueous solution, and then drying the solid phase to obtain pretreated inorganic particles;

[0031] (2) hydrolyzing the ethanol aqueous solution and the vinyl silane coupling agent, then adding the pretreated inorganic particles in step (1) to perform a first modification, then filtering, washing the filter cake, and drying to obtain coupling agent-modified inorganic particles;

[0032] (3) The initiator, liquid rubber and the coupling agent-modified inorganic particles in step (2) are mixed and then subjected to a second modification to obtain liquid rubber-modified inorganic particles.

[0033] As a preferred technical solution of the present invention, the average particle size of the inorganic particles is 200-2000 mesh, preferably 600-1500 mesh.

[0034] As a preferred technical solution of the present invention, the inorganic particles are selected from at least one of hydrotalcite, silicon dioxide, titanium dioxide and organic montmorillonite.

[0035] As a more preferred technical solution of the present invention, the inorganic particles are selected from hydrotalcite and / or organic montmorillonite.

[0036] In the present invention, it is found that the inorganic particles used in the present invention, hydrotalcite and / or organic montmorillonite, can better increase the hydrophobicity and wear resistance of the coating. It is speculated that this is because the gas layered structure can effectively prevent the entry and transmission of gas in the system, and at the same time its layered structure can withstand the load applied to the coating surface and reduce the adhesive wear of the polymer matrix.

[0037] As a more preferred technical solution of the present invention, the inorganic particles are selected from hydrotalcite and organic montmorillonite.

[0038] As a more preferred technical solution of the present invention, the weight ratio of the hydrotalcite to the organic montmorillonite is 1:(0.1-1), for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, preferably 1:(0.5-0.6).

[0039] In the present invention, specific hydrotalcite and organic montmorillonite are used as inorganic particles, and by controlling the ratio of hydrotalcite to organic montmorillonite, the wear resistance of the coating formed by the coating can be further increased, and the salt spray resistance of the coating can be better increased. It is speculated that this is because both hydrotalcite and organic montmorillonite have a layered structure, and both can form interlacing or peeling when modified by liquid rubber, and further form interlacing or peeling when acting with the matrix resin, and have better structural strength, and the degree of interlacing or peeling formed by hydrotalcite and organic montmorillonite is different. This different degree of interlacing or peeling is similar to the layered peeling of "off-peak", so that when the coating is subjected to external force, the adhesive wear of the resin matrix can be better reduced.

[0040] As a preferred technical solution of the present invention, the organic montmorillonite is an organic montmorillonite modified with hydroxyl-containing organic ammonium.

[0041] The organic montmorillonite modified with hydroxyl-containing organic ammonium in the present invention can be obtained commercially, preferably purchased from Zhejiang Fenghong New Materials Co., Ltd., with model DK32B and an average particle size of 1000 meshes.

[0042] As a preferred technical solution of the present invention, the hydrotalcite is magnesium-aluminum hydrotalcite.

[0043] The magnesium aluminum hydrotalcite in the present invention can be obtained commercially, preferably purchased from Hefei Anyuhe New Material Technology Co., Ltd., model DK32B, model Anyuhe D200, and the average particle size is 800 mesh.

[0044] In the present invention, the concentration of the sodium hydroxide aqueous solution is not particularly limited. As a preferred technical solution of the present invention, the concentration of the sodium hydroxide aqueous solution is 0.2-0.5 mol / L.

[0045] As a preferred technical solution of the present invention, in step (1), the weight ratio of the inorganic particles to the sodium hydroxide aqueous solution is 1:(10-30), preferably 1:(15-20).

[0046] The mixing in step (1) of the present invention only needs to allow the inorganic particles and the sodium hydroxide aqueous solution to be fully mixed. As a preferred technical solution of the present invention, the mixing conditions include: a temperature of 65-80° C. and a time of 2-3 hours.

[0047] The solid phase in step (1) of the present invention refers to the solid phase in the mixed material, and the method for obtaining the solid phase can be a conventional method in the art, such as filtration.

[0048] The drying in step (1) of the present invention can be a conventional drying method in the art. Preferably, in step (1), the drying conditions include: a temperature of 100-120° C. and a time of 10-48 hours.

[0049] As a most preferred embodiment of the present invention, the specific steps in step (1) include: mixing inorganic particles in a weight ratio of 1:(15-20) with a sodium hydroxide aqueous solution with a concentration of 0.2-0.5 mol / L at a temperature of 65-80°C for 2-3 hours, then filtering to obtain a solid phase, and then drying the solid phase at a temperature of 100-120°C for 10-48 hours to obtain pretreated inorganic particles.

[0050] In the present invention, the ethanol aqueous solution refers to a mixed liquid of ethanol and water. As a preferred technical solution of the present invention, in the ethanol aqueous solution, the volume ratio of ethanol to water is (10-15):1.

[0051] As a preferred technical solution of the present invention, the vinyl silane coupling agent is selected from any one of vinyl trimethoxy silane, vinyl triethoxy silane, methyl vinyl diethoxy silane, and vinyl triisopropoxy silane, preferably vinyl triethoxy silane.

[0052] As a preferred technical solution of the present invention, the weight ratio of the ethanol aqueous solution to the vinyl silane coupling agent is (200-300):1.

[0053] As a preferred technical solution of the present invention, the weight ratio of the vinyl silane coupling agent to the inorganic particles is 1:(1-2), preferably 1:(1.2-1.5).

[0054] As a preferred technical solution of the present invention, in step (2), the hydrolysis conditions include: the temperature is room temperature, and the time is 3-10 minutes.

[0055] As a preferred technical solution of the present invention, in step (2), the conditions for the first modification include: temperature of 60-70° C. and time of 3-4 hours.

[0056] As a preferred technical solution of the present invention, in step (2), the filter cake is washed by alternately washing with water and ethanol for 4-6 times.

[0057] As a preferred technical solution of the present invention, in step (2), the drying conditions include: temperature of 100-120° C. and time of 10-48 hours.

[0058] As a more preferred technical solution of the present invention, the specific steps in step (2) include: hydrolyzing an ethanol aqueous solution (the volume ratio of ethanol to water is (10-15):1) and vinyl triethoxysilane (the weight ratio of vinyl triethoxysilane to inorganic particles is 1: (1.2-1.5)) in a weight ratio of (200-300):1 at room temperature for 3-10 minutes, then adding the pretreated inorganic particles in step (1) for a first modification at a temperature of 60-70°C for 3-4 hours, then filtering, washing the filter cake with water and ethanol alternately for 4-6 times, and drying at 100-120°C for 10-48 hours to obtain coupling agent modified inorganic particles.

[0059] As a preferred technical solution of the present invention, the liquid rubber is selected from at least one of liquid polybutadiene rubber, liquid silicone rubber and liquid fluororubber, and is preferably liquid polybutadiene rubber.

[0060] As a more preferred technical solution of the present invention, the vinyl content of the liquid polybutadiene rubber is 20-35wt%.

[0061] As a more preferred technical solution of the present invention, the number average molecular weight of the liquid polybutadiene rubber is 2000-3000 g / mol.

[0062] The present invention has been studied and found that the use of liquid rubber-modified inorganic particles, especially liquid polybutadiene rubber-modified inorganic particles, can better increase the adhesion, wear resistance, salt spray resistance, and heat and cold resistance of the coating. Although the mechanism is not yet clear, it is speculated that this is because the liquid rubber-modified inorganic particles form a specific core-shell structure. At the same time, the liquid polybutadiene rubber as the shell has double bonds, which can better interact with the matrix resin and improve the crosslinking degree of the coating. In addition, the liquid polybutadiene rubber is flexible and can better increase the flexibility of the coating.

[0063] The liquid polybutadiene rubber in the present invention can be obtained from the market, and its preferred model is liquid polybutadiene Ricon 130 (vinyl content of 30 wt%, number average molecular weight of 2500 g / mol).

[0064] As a preferred technical solution of the present invention, the initiator is selected from peroxide initiators, preferably at least one selected from dibenzoyl peroxide, dicumyl peroxide and cumene hydroperoxide.

[0065] As a preferred technical solution of the present invention, the weight ratio of the initiator, the liquid rubber and the coupling agent-modified inorganic particles in step (2) is (0.1-1):(50-100):1000, preferably (0.5-0.6):(80-85):1000.

[0066] The mixing in step (3) of the present invention only needs to make the initiator, liquid rubber and the coupling agent-modified inorganic particles in step (2) uniformly mixed. Preferably, the mixing conditions in step (3) include: the temperature is room temperature and the time is 20-40 minutes.

[0067] As a preferred technical solution of the present invention, in step (3), the conditions for the second modification include: temperature of 130-150° C. and time of 40-60 minutes.

[0068] As a more preferred technical solution of the present invention, the specific steps in step (3) include: mixing a peroxide initiator and liquid polybutadiene rubber in a weight ratio of (0.5-0.6): (80-85): 1000 with the coupling agent-modified inorganic particles in step (2) at room temperature for 20-40 minutes, and then performing a second modification at 130-150° C. for 40-60 minutes to obtain liquid rubber-modified inorganic particles.

[0069] The anti-ultraviolet agent in the present invention can be any anti-ultraviolet agent in the art, for example, at least one of phenyl o-hydroxybenzoate, resorcinol monobenzoate, 2,4-dihydroxybenzophenone, and 2-(2'-hydroxy-3',5'-di-tert-phenyl)-5-chlorobenzotriazole.

[0070] The antioxidant in the present invention can be any antioxidant in the art, for example, at least one of antioxidant 1010, antioxidant 3114, antioxidant 264, antioxidant 1076 and antioxidant 168.

[0071] The bird repellent in the present invention may be any bird repellent in the art, such as at least one of ethyl phenylacetate, o-aminoacetophenone, veratrylamine, methiocarb, caffeine, chlorpyrifos and trihalothrin.

[0072] As a preferred technical solution of the present invention, the diluent is selected from at least one of ketone solvents and alcohol solvents, preferably selected from at least one of methanol, ethanol and acetone, further preferably a combination of ethanol and acetone, preferably a weight ratio of ethanol to acetone of 1: (1-2).

[0073] The second aspect of the present invention provides a method for preparing the high-insulation, wear-resistant and super-hydrophobic protective coating according to the first aspect of the present invention, the preparation method comprising: mixing a base resin, liquid rubber-modified inorganic particles, a bird repellent, an anti-ultraviolet agent, an antioxidant and a diluent.

[0074] As a preferred technical solution of the present invention, the mixing conditions include: the temperature is room temperature, the rotation speed is 2000-3000r / min, and the time is 30-50 minutes; the mixing can be carried out in a high-speed mixer.

[0075] The coating of the present invention can be used for preventing bird damage to distribution network equipment.

[0076] Compared with the prior art, the present invention has at least the following beneficial effects:

[0077] 1. The coating in the present invention uses resin as a matrix and can be used when the equipment is powered and operating normally. It has high insulation and strong corrosion resistance. The high insulation, wear-resistant and super-hydrophobic protective coating in the present invention can form a protective coating on the surface of the tower to isolate pollutants and line obstacles in the environment, such as ice and snow, rain, daily debris, bird droppings, bird bodies, bird nests, etc., to ensure the safe operation of the equipment.

[0078] 2. The coating of the present invention has excellent adhesion and can be stably adhered to the electrical equipment.

[0079] 3. The coating of the present invention has excellent hydrophobicity, wear resistance, salt spray resistance and heat and cold resistance, and can effectively prevent power equipment from being eroded and corroded by chemicals such as water and salt, thereby reducing the cost and time of maintenance and replacement of equipment. DETAILED DESCRIPTION

[0080] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0081] Example 1

[0082] Preparation of acrylic resin A:

[0083] S1: Add n-butanol (the mass ratio of n-butanol to methyl methacrylate is 1:0.55) to a container equipped with a stirring device, a condensing reflux device, a heating and heat preservation device, and a dripping device, and heat it to 85°C, then drip a mixture A of methyl methacrylate, butyl acrylate, styrene, trimethylaminopropyl methacrylamide chloride, and azobisisobutyronitrile in a weight ratio of 1:1:0.52:0.52:0.23, and control the dripping of the mixture A to be completed within 0.5h, and continue the heat preservation reaction for 1.5h;

[0084] S2 continues to drop a mixture B of n-butanol and azobisisobutyronitrile in a weight ratio of 1:0.12 (the weight ratio of mixture B to mixture A is 1:8.5), controls the addition of mixture B to be completed within 0.5h, continues to keep warm and react for 3.5h, cools down, and discharges to obtain acrylic resin A.

[0085] Preparation of liquid rubber modified inorganic particles A:

[0086] (1) Inorganic particles with a weight ratio of 1:18 and a sodium hydroxide aqueous solution with a concentration of 0.3 mol / L were mixed at a temperature of 72° C. for 2.5 hours, and then filtered to obtain a solid phase, and then the solid phase was dried at a temperature of 115° C. for 12 hours to obtain pretreated inorganic particles, wherein the inorganic particles are magnesium aluminum hydrotalcite (purchased from Hefei Anyuhe New Material Technology Co., Ltd., model DK32B, model Anyuhe D200, average particle size of 800 mesh) and hydroxy organic ammonium modified organic montmorillonite (purchased from Zhejiang Fenghong New Materials Co., Ltd., model DK32B, average particle size of 1000 mesh), and the weight ratio is 1:0.55;

[0087] (2) hydrolyzing an ethanol aqueous solution (the volume ratio of ethanol to water is 12:1) and vinyl triethoxysilane (the weight ratio of vinyl triethoxysilane to inorganic particles is 1:1.3) in a weight ratio of 265:1 at room temperature for 5 minutes, then adding the pretreated inorganic particles in step (1) for a first modification at a temperature of 65°C for 3.5 hours, then filtering, washing the filter cake with water and ethanol alternately for 5 times, and drying at 115°C for 12 hours to obtain coupling agent-modified inorganic particles;

[0088] (3) Dibenzoyl peroxide and liquid polybutadiene rubber in a weight ratio of 0.52:82:1000 are mixed with the coupling agent-modified inorganic particles in step (2) at room temperature for 30 minutes, and then subjected to a second modification at 145° C. for 40 minutes to obtain liquid rubber-modified inorganic particles A; wherein the model of the liquid polybutadiene rubber is liquid polybutadiene Ricon 130 (vinyl content of 30 wt %, number average molecular weight of 2500 g / mol).

[0089] Preparation of coating raw materials:

[0090] Prepare, by weight, 70 parts of silicone resin (N-9801A silicone resin purchased from Changzhou Jianuo Silicone Co., Ltd.), 30 parts of acrylic resin A, 28 parts of liquid rubber modified inorganic particles A, 1.5 parts of caffeine, 0.7 parts of 2,4-dihydroxybenzophenone, 0.45 parts of antioxidant 1010, 10 parts of ethanol, and 13 parts of acetone.

[0091] Preparation of coating: The above coating raw materials were added into a high-speed mixer and mixed for 45 minutes at room temperature and a rotation speed of 2500 r / min to obtain the coating.

[0092] Example 2

[0093] Preparation of acrylic resin B:

[0094] S1: Add n-butanol (the mass ratio of n-butanol to methyl methacrylate is 1:0.8) to a container equipped with a stirring device, a condensing reflux device, a heating and heat preservation device, and a dripping device, and heat it to 90°C, then drip a mixture A of methyl methacrylate, butyl acrylate, styrene, trimethylaminopropyl methacrylamide chloride, and azobisisobutyronitrile in a weight ratio of 1:0.8:0.6:0.5:0.3, control the dripping of the mixture A to be completed within 0.5h, and continue the heat preservation reaction for 1h;

[0095] S2 continues to drip a mixture B of n-butanol and azobisisobutyronitrile in a weight ratio of 1:0.15 (the weight ratio of mixture B to mixture A is 1:10), controls the dripping of mixture B to be completed within 0.5h, continues the heat preservation reaction for 3h, cools down, and discharges the material to obtain acrylic resin B.

[0096] Preparation of liquid rubber modified inorganic particles B:

[0097] (1) Inorganic particles with a weight ratio of 1:15 and a sodium hydroxide aqueous solution with a concentration of 0.5 mol / L were mixed at a temperature of 65°C for 2 hours, and then filtered to obtain a solid phase, and then the solid phase was dried at a temperature of 120°C for 10 hours to obtain pretreated inorganic particles, wherein the inorganic particles are magnesium aluminum hydrotalcite (purchased from Hefei Anyuhe New Material Technology Co., Ltd., model DK32B, model Anyuhe D200, average particle size of 800 mesh) and hydroxy organic ammonium modified organic montmorillonite (purchased from Zhejiang Fenghong New Materials Co., Ltd., model DK32B, average particle size of 1000 mesh), and the weight ratio is 1:6;

[0098] (2) hydrolyzing an ethanol aqueous solution (the volume ratio of ethanol to water is 15:1) and vinyl triethoxysilane (the weight ratio of vinyl triethoxysilane to inorganic particles is 1:1.2) in a weight ratio of 300:1 at room temperature for 10 minutes, then adding the pretreated inorganic particles in step (1) for a first modification at a temperature of 65°C for 4 hours, then filtering, washing the filter cake with water and ethanol alternately for 5 times, and drying at 115°C for 12 hours to obtain coupling agent-modified inorganic particles;

[0099] (3) Dibenzoyl peroxide and liquid polybutadiene rubber in a weight ratio of 0.5:85:1000 are mixed with the coupling agent-modified inorganic particles in step (2) at room temperature for 40 minutes, and then subjected to a second modification at 150° C. for 40 minutes to obtain liquid rubber-modified inorganic particles B; wherein the model of the liquid polybutadiene rubber is liquid polybutadiene Ricon 130 (vinyl content of 30 wt %, number average molecular weight of 2500 g / mol).

[0100] Preparation of coating raw materials:

[0101] Prepare, by weight, 75 parts of silicone resin (N-9801A silicone resin purchased from Changzhou Jianuo Silicone Co., Ltd.), 30 parts of acrylic resin B, 30 parts of liquid rubber modified inorganic particles B, 1.5 parts of caffeine, 0.8 parts of 2,4-dihydroxybenzophenone, 0.3 parts of antioxidant 1010, 10 parts of ethanol, and 15 parts of acetone.

[0102] Preparation of coating: The above coating raw materials were added into a high-speed mixer and mixed for 50 minutes at room temperature and a rotation speed of 2300 r / min to obtain the coating.

[0103] Example 3

[0104] Preparation of coating raw materials:

[0105] Prepare, by weight, 65 parts of silicone resin (N-9801A silicone resin purchased from Changzhou Jianuo Silicone Co., Ltd.), 35 parts of acrylic resin A (same as in Example 1), 30 parts of liquid rubber modified inorganic particles B (same as in Example 2), 1.2 parts of caffeine, 0.7 parts of 2,4-dihydroxybenzophenone, 0.45 parts of antioxidant 1010, 10 parts of ethanol, and 14 parts of acetone.

[0106] Preparation of coating: The above coating raw materials were added into a high-speed mixer and mixed for 50 minutes at room temperature and a rotation speed of 2500 r / min to obtain the coating.

[0107] Example 4

[0108] The method of Example 1 was followed, except that the inorganic particles were magnesium aluminum hydrotalcite (purchased from Hefei Anyuhe New Material Technology Co., Ltd., model DK32B, model Anyuhe D200, average particle size 800 mesh), and finally a coating was prepared.

[0109] Example 5

[0110] The method of Example 1 was followed, except that the inorganic particles were organic montmorillonite modified with hydroxy organic ammonium (purchased from Zhejiang Fenghong New Materials Co., Ltd., model DK32B, average particle size 1000 mesh), and finally a coating was prepared.

[0111] Example 6

[0112] The method of Example 1 was followed, except that the inorganic particles were silicon oxide (purchased from Baiyi Mineral Products Processing Plant in Lingshou County, with an average particle size of 10 μm), and finally a coating was prepared.

[0113] Example 7

[0114] The coating was finally prepared according to the method of Example 1, except that trimethylaminopropyl methacrylamide chloride was not added when preparing the acrylic resin.

[0115] Comparative Example 1

[0116] The method of Example 1 is followed, except that: coupling agent-modified inorganic particles are used to replace the liquid rubber-modified inorganic particles A; the coupling agent-modified inorganic particles are the coupling agent-modified inorganic particles prepared in step (2) of Example 1, and finally a coating is prepared.

[0117] Performance Testing

[0118] Use a brush to evenly apply the coating on a polytetrafluoroethylene plate (coating amount is 0.2 g / cm2), leave it at 40±2°C until the solvent evaporates completely, and then leave it at room temperature for 3 days to obtain a coating sample.

[0119] 1. Test the wear of the coating sample according to ASTM D4060-19 standard (wheel model CS-10, load 250g, speed 60rpm, wear number 50 revolutions).

[0120] 2. Hydrophobicity test: Use a water drop angle tester to test the hydrophobicity of the coating sample.

[0121] 3. Adhesion test: Refer to GB / T 1720-2020 to test the adhesion of the coating sample.

[0122] 4. Salt spray resistance test: Refer to GB / T 10125-2021 standard to test the salt spray resistance of the coating sample, and record the stable existence time of the paint film sample in neutral salt spray (the coating has no abnormal phenomena such as cracking, discoloration, loss of gloss, peeling, etc.).

[0123] 5. Resistance to cold and heat: Place the coating sample in a -30°C environment for 3 hours, then at room temperature for 1 hour, then at 55°C for 5 hours, then at room temperature for 1 hour. Repeat the above steps 50 times. If the coating has no abnormal phenomena such as cracking, discoloration, loss of gloss, peeling, etc., it is qualified; otherwise, it is unqualified.

[0124] The test results are shown in Table 1:

[0125] Table 1

[0126]

[0127]

[0128] It can be seen from the above test results that the coating of the present invention has excellent hydrophobic wear resistance, adhesion, salt spray resistance, and cold and heat resistance.

[0129] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A highly insulating, wear-resistant, super-hydrophobic protective coating, characterized in that: The raw materials of the coating include, by weight: 100 parts of base resin, 20-35 parts of liquid rubber modified inorganic particles, 0.5-2 parts of bird repellent, 0.2-1.5 parts of anti-ultraviolet agent, 0.1-1 parts of antioxidant, and 15-35 parts of diluent.

2. The coating according to claim 1, characterized in that The base resin is selected from a combination of silicone resin and acrylic resin.

3. The coating according to claim 2, characterized in that The weight ratio of the silicone resin to the acrylic resin is (60-80):(20-40).

4. The coating according to claim 2, characterized in that The preparation method of the acrylic resin comprises: S1: adding solvent A to a container equipped with a stirring device, a condensing reflux device, a heating and heat preservation device, and a dripping device, and heating to 80-90° C., and then dripping a mixture A of methyl methacrylate, butyl acrylate, styrene, trimethylaminopropyl methacrylamide chloride, and initiator A to carry out a first reaction; After S2, a mixture B of solvent B and initiator B is added dropwise to carry out a second reaction.

5. The coating according to claim 4, characterized in that The solvent A and the solvent B are each independently selected from C3-C7 monohydric alcohols; the initiator A and the initiator B are each independently selected from azo initiators; the weight ratio of methyl methacrylate, butyl acrylate, styrene and trimethylaminopropyl methacrylamide chloride is 1: (0.5-1.5): (0.3-0.8): (0.3-0.8); the conditions of the first reaction include: temperature of 80-90°C and time of 1-1.5h; the conditions of the second reaction include: temperature of 80-90°C and time of 3-4h.

6. The coating according to claim 1, characterized in that The preparation method of the liquid rubber modified inorganic particles comprises: (1) mixing inorganic particles with a sodium hydroxide aqueous solution, and then drying the solid phase to obtain pretreated inorganic particles; (2) hydrolyzing the ethanol aqueous solution and the vinyl silane coupling agent, then adding the pretreated inorganic particles in step (1) to perform a first modification, then filtering, washing the filter cake, and drying to obtain coupling agent-modified inorganic particles; (3) The initiator, liquid rubber and the coupling agent-modified inorganic particles in step (2) are mixed and then subjected to a second modification to obtain liquid rubber-modified inorganic particles.

7. The coating according to claim 6, characterized in that The inorganic particles are selected from at least one of hydrotalcite, silicon dioxide, titanium dioxide and organic montmorillonite; in step (2), the conditions for hydrolysis include: temperature is room temperature, and time is 3-10 minutes; in step (2), the conditions for the first modification include: temperature is 60-70°C, and time is 3-4 hours.

8. The coating according to claim 6, characterized in that The liquid rubber is selected from at least one of liquid polybutadiene rubber, liquid silicone rubber and liquid fluororubber; the weight ratio of the initiator, the liquid rubber and the coupling agent modified inorganic particles in step (2) is (0.1-1): (50-100): 1000; the conditions for the second modification include: temperature of 130-150°C and time of 40-60 minutes.

9. The coating according to claim 1, characterized in that The diluent is selected from at least one of a ketone solvent and an alcohol solvent.

10. A method for preparing the highly insulating, wear-resistant, super-hydrophobic protective coating according to any one of claims 1 to 9, characterized in that: The preparation method comprises: mixing base resin, liquid rubber modified inorganic particles, bird repellent, anti-ultraviolet agent, antioxidant and diluent.

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