A powder coating, its preparation method and application

Abstract

This invention relates to a powder coating, its preparation method, and its application, belonging to the field of powder coating technology. It comprises the following raw materials: 40-50 parts of bisphenol A type epoxy resin, 20-25 parts of modified phenolic resin, 10-15 parts of phenolic epoxy resin, 8-10 parts of curing agent, 3-5 parts of leveling agent, 1-2 parts of pigment, 4-6 parts of filler, and 5-7 parts of dispersant. In this invention, a corrosion-resistant and wear-resistant composite is obtained by combining linear amino polysiloxane with a wear-resistant composite material; the corrosion-resistant and wear-resistant composite is combined with 3,4-difluoromaleic anhydride to obtain a reinforcing material; the reinforcing material is combined with vinylated phenolic resin to obtain a modified phenolic resin; the bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, curing agent, leveling agent, pigment, filler, and dispersant are mixed, extruded, granulated, and sieved to obtain the powder coating; the overall corrosion resistance, wear resistance, and mechanical properties of the powder coating are improved.

Description

Technical Field

[0001] This invention belongs to the field of powder coating technology, specifically relating to a powder coating, its preparation method, and its application. Background Technology

[0002] Powder coatings are solid powdered synthetic resin coatings composed of solid resins, pigments, fillers, and additives. Compared to traditional solvent-based coatings, powder coatings offer advantages such as solvent-free evaporation, low pollution, high utilization rate, and versatility, making them widely used in automotive manufacturing, building decoration, home appliances, pipeline corrosion protection, and many other fields. However, in chemical production environments, especially under extreme climatic conditions, highly corrosive media, and high-intensity friction and wear, higher requirements are placed on the corrosion resistance and wear resistance of coatings. Pipelines, storage tanks, and reactors in chemical plants are frequently exposed to various corrosive substances, which can easily lead to equipment damage and shortened service life. Furthermore, many mechanical devices, such as agitators and valves, often face high-intensity friction and wear, easily resulting in peeling, scratches, and other problems, ultimately losing their protective function and affecting the normal operation of the equipment. Therefore, there is an urgent need to develop powder coatings with better corrosion resistance and wear resistance.

[0003] In existing technologies, powder coatings are mostly made by mixing resin with nanomaterials. However, because nanomaterials have poor dispersibility in resin and are prone to agglomeration, as well as poor compatibility with resin, the adhesion and corrosion resistance of the powder coating film are poor, which greatly shortens the service life of the powder coating and fails to provide good protection. Furthermore, adding a large amount of wear-resistant fillers (such as silicon carbide, nano-silica, etc.) to the resin, although increasing the hardness of the powder coating, will reduce its toughness, resulting in a decrease in its mechanical properties and further affecting the final quality of the product. Summary of the Invention

[0004] The purpose of this invention is to provide a powder coating, its preparation method, and its application. A corrosion-resistant and wear-resistant composite material is obtained by combining linear amino polysiloxane with a wear-resistant composite material; the corrosion-resistant and wear-resistant composite material is then combined with 3,4-difluoromaleic anhydride to obtain a reinforcing material; the reinforcing material is then combined with vinylated phenolic resin to obtain a modified phenolic resin; bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, curing agent, leveling agent, pigment, filler, and dispersant are mixed, and the mixture is extruded, granulated, ground, and sieved to finally obtain the powder coating. The modified phenolic resin significantly improves the corrosion resistance, wear resistance, thermal stability, hardness, and mechanical properties of the powder coating, thereby enhancing its overall performance and extending its service life.

[0005] The technical problem this invention aims to solve is as follows: In the prior art, most powder coatings are made by mixing resin with nanomaterials. However, due to the poor dispersibility of nanomaterials in resin, they are prone to agglomeration and have poor compatibility with resin. This results in poor adhesion and corrosion resistance of the powder coating after film formation, greatly shortening the service life of the powder coating and failing to provide good protection. Furthermore, adding a large amount of wear-resistant fillers (such as silicon carbide, nano-silica, etc.) to the resin, although increasing the hardness of the powder coating, will reduce its toughness, leading to a decrease in its mechanical properties and further affecting the final quality of the product.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A powder coating comprises the following raw materials in parts by weight: 40-50 parts of bisphenol A type epoxy resin, 20-25 parts of modified phenolic resin, 10-15 parts of phenolic epoxy resin, 8-10 parts of curing agent, 3-5 parts of leveling agent, 1-2 parts of pigment, 4-6 parts of filler and 5-7 parts of dispersant;

[0008] The preparation method of the modified phenolic resin includes the following steps:

[0009] S1: A corrosion-resistant and wear-resistant composite material is obtained by combining linear amino polysiloxane with wear-resistant composite material;

[0010] S2: The anti-corrosion and wear-resistant composite is combined with 3,4-difluoromaleic anhydride to obtain a reinforced material;

[0011] S3: Combine the reinforcing material with vinylated phenolic resin to obtain modified phenolic resin.

[0012] Furthermore, step S1 specifically includes:

[0013] Linear aminopolysiloxane and wear-resistant composite material are mixed, deionized water is added, and the mixture is stirred in a constant temperature water bath at 75-85℃ for 0.5-1.5h. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with ethanol and deionized water, and finally vacuum dried at 55-65℃ to obtain the anti-corrosion and wear-resistant composite material.

[0014] In the above reaction process, the linear amino polysiloxane has amino groups, and the graphene oxide in the wear-resistant composite material has carboxyl groups. The amino groups in the linear amino polysiloxane can combine with the carboxyl groups in the wear-resistant composite material, thus combining the linear amino polysiloxane with the wear-resistant composite material to finally obtain the anti-corrosion and wear-resistant composite material.

[0015] Furthermore, the mass ratio of the linear amino polysiloxane, the wear-resistant composite material, and the deionized water is 1.4-1.6:0.8-1.2:280-320.

[0016] Furthermore, the preparation method of the linear amino polysiloxane includes the following steps:

[0017] Pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane were added to deionized water and reacted at 25-35℃ for 10-20 min. Then N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and deionized water were added and the reaction was continued for 40-50 min. The temperature was then raised to 70-80℃ and the mixture was stirred and refluxed for 3-5 h. After the reaction was completed, the reaction was continued under reduced pressure for 8-10 h to finally obtain linear amino polysiloxane.

[0018] In the above reaction process, pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane combine through hydrolysis and condensation reactions to finally obtain linear amino polysiloxane.

[0019] Furthermore, the mass ratio of the pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane, and deionized water is 5.8-6.2:5.8-6.2:0.5-0.7.

[0020] Furthermore, the temperature under the pressure reduction conditions is 70-80℃ and the pressure is −0.005MPa.

[0021] Furthermore, the preparation method of the wear-resistant composite material includes the following steps:

[0022] Ammonium molybdate tetrahydrate was added to anhydrous ethanol and deionized water, and then stirred for 10-20 min to obtain a precursor solution. The composite material was dispersed in ethanol and mixed evenly to obtain a dispersion. The dispersion was added to the precursor solution and stirred in a water bath at 75-85℃ for 8-10 h. After cooling to room temperature, it was filtered, washed with deionized water, and finally vacuum dried at 50-60℃ to obtain the wear-resistant composite material.

[0023] In the above reaction process, molybdenum disulfide nanoparticles are loaded onto the surface of the composite material through the sol-gel method, thereby combining the molybdenum disulfide nanoparticles with the composite material, and finally obtaining a wear-resistant composite material.

[0024] Furthermore, the mass ratio of the ammonium molybdate tetrahydrate, anhydrous ethanol, and deionized water is 0.8-1.2:10-15:40-50.

[0025] Furthermore, the mass ratio of the composite material to ethanol is 0.4-0.6:90-110.

[0026] Furthermore, the mass ratio of the dispersion to the precursor solution is 1:1.

[0027] Furthermore, the method for preparing the composite material includes the following steps:

[0028] Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water were mixed evenly to obtain a mixed solution. Graphene oxide was added to the mixed solution and stirred evenly. The mixture was then heated to 75-85℃, and sodium hydroxide solution was added to adjust the pH of the system to 10-10.5. The mixture was stirred for 2-3 hours and aged at 75-85℃ for 14-16 hours. The mixture was then filtered through a filter membrane, washed with deionized water, and finally dried at 75-85℃ to obtain the composite material.

[0029] In the above reaction process, magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride and deionized water are mixed to form a layered double hydroxide. Graphene oxide and the layered double hydroxide are combined by in-situ co-precipitation method to combine graphene oxide and the layered double hydroxide, and finally the composite material is obtained.

[0030] Furthermore, the mass ratio of magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water is 0.8-1.2:0.8-1.2:0.4-0.6:1.8-2.2:140-160.

[0031] Furthermore, the mass ratio of the graphene oxide to the mixed solution is 1.4-1.6:3.4-3.6.

[0032] Furthermore, the filter membrane is a 0.45 μm polyethersulfone membrane.

[0033] Furthermore, step S2 specifically includes:

[0034] The anti-corrosion and wear-resistant composite from step S1 is mixed with 3,4-difluoromaleic anhydride, and then N,N-dimethylformamide is added. The mixture is then reacted at 70-80℃ for 2-4 hours, the temperature is increased to 90-100℃, and the reaction continues for 13-15 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with ethanol and deionized water, and finally vacuum dried at 55-65℃ to obtain the reinforced material.

[0035] In the above reaction process, the graphene oxide in the corrosion-resistant and wear-resistant composite has hydroxyl groups and epoxy groups, and the 3,4-difluoromaleic anhydride has anhydride groups. The hydroxyl and epoxy groups in the corrosion-resistant and wear-resistant composite can react and combine with the anhydride groups on the 3,4-difluoromaleic anhydride, thus combining the 3,4-difluoromaleic anhydride with the corrosion-resistant and wear-resistant composite to finally obtain the reinforced material.

[0036] Furthermore, the mass ratio of the corrosion-resistant and wear-resistant composite, 3,4-difluoromaleic anhydride, and N,N-dimethylformamide is 0.1-0.2:1.8-2:30-40.

[0037] Furthermore, step S3 specifically includes:

[0038] The reinforcing material from step S2 is mixed with the vinyl phenolic resin, and then benzoyl peroxide is added. The mixture is then reacted at 75-85°C for 3.5-4.5 hours. After the reaction is complete, the mixture is cooled to room temperature, filtered, washed with ether, and finally dried under vacuum at 20-30°C to obtain the modified phenolic resin.

[0039] In the above reaction process, the 3,4-difluoromaleic anhydride in the reinforcing material has carbon-carbon double bonds, and the vinyl phenolic resin also has carbon-carbon double bonds. The carbon-carbon double bonds in the reinforcing material can combine with the carbon-carbon double bonds on the vinyl phenolic resin through free radical polymerization reaction, thus combining the reinforcing material with the vinyl phenolic resin to finally obtain the modified phenolic resin.

[0040] Furthermore, the mass ratio of the reinforcing material, vinyl phenolic resin, and benzoyl peroxide is 0.8-1.2:1.8-2.2:0.02-0.04.

[0041] Furthermore, the preparation method of the vinylated phenolic resin includes the following steps:

[0042] Boron-modified phenolic resin was heated to 75-85℃, and then a silane coupling agent and p-toluenesulfonic acid were added. The mixture was then reacted at 80-90℃ for 2.5-3.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with ethanol, and finally dried under vacuum at 35-45℃ to obtain vinylated phenolic resin.

[0043] In the above reaction process, the boron-modified phenolic resin contains hydroxymethyl groups, and the silane coupling agent contains methoxy groups. The methoxy groups in the silane coupling agent can combine with the hydroxymethyl groups in the boron-modified phenolic resin, grafting the silane coupling agent onto the boron-modified phenolic resin, and finally obtaining the vinylated phenolic resin.

[0044] Furthermore, the mass ratio of the boron-modified phenolic resin, silane coupling agent, and p-toluenesulfonic acid is 0.8-1.2:0.1-0.2:0.01-0.03.

[0045] Furthermore, the silane coupling agent is 3-methacryloyloxypropyltrimethoxysilane.

[0046] Furthermore, the preparation method of the boron-modified phenolic resin includes the following steps:

[0047] Phenol and formaldehyde solutions were mixed, oxalic acid was added, and the pH of the solution was adjusted to 3. The mixture was reacted at 70°C for 1 hour. Boric acid was then added, the temperature was raised to 95°C, and the reaction was continued for 1 hour. Sodium hydroxide solution was added, and the pH of the system was adjusted to 7. The mixture was then added to deionized water and stirred for 10 minutes. The mixture was allowed to stand and separate into layers. The upper water layer was removed, leaving the lower resin layer. The resin layer was then dehydrated under vacuum at 145°C to obtain boron-modified phenolic resin.

[0048] Furthermore, the mass ratio of phenol, formaldehyde solution, oxalic acid, boric acid, and deionized water is 1.2:1:0.01:0.05:100.

[0049] A method for preparing a powder coating includes the following steps:

[0050] Weigh out the raw materials by weight, mix bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, curing agent, leveling agent, pigment, filler and dispersant, and stir at 1000-2000 rpm for 3-5 minutes to obtain a mixture. Add the mixture to a twin-screw extruder for extrusion granulation, then grind and pass through a 100-140 mesh sieve to finally obtain a powder coating.

[0051] Furthermore, the curing agent is at least one of diethylaminopropylamine, tetraethylenepentamine, and cyclohexanone peroxide.

[0052] Furthermore, the leveling agent is at least one of BYK-307 leveling agent, BYK-358N leveling agent, and polydimethylsiloxane.

[0053] Furthermore, the pigment is titanium dioxide or silica.

[0054] Furthermore, the filler is at least one of sodium bentonite, calcium carbonate, and barium sulfate.

[0055] Furthermore, the dispersant is dispersant 5040 or polyethylene wax.

[0056] Furthermore, the operating temperature of the twin-screw extruder is 110-120℃, and the main machine speed is 200-400rpm.

[0057] The beneficial effects of this invention are:

[0058] (1) In the technical solution of this invention, a corrosion-resistant and wear-resistant composite material is obtained by combining linear amino polysiloxane with wear-resistant composite material; the linear amino polysiloxane is prepared by combining pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane; the three silanes form linear amino polysiloxane through hydrolysis and condensation reaction. Pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane have fluorine atoms, which can improve the corrosion resistance of powder coating. N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane has amino groups, which can provide reaction sites for subsequent reactions. The linear amino polysiloxane formed by combining the three silanes can effectively improve the corrosion resistance and thermal stability of powder coating; the bonding force between the linear amino polysiloxane and the wear-resistant composite material is good. The wear-resistant composite material is prepared by combining graphene oxide with layers of... The process involves combining layered double hydroxides with molybdenum disulfide nanoparticles. This effective combination of molybdenum disulfide nanoparticles, graphene oxide, and layered double hydroxides achieves a synergistic effect, significantly improving the wear resistance, hardness, and mechanical properties of powder coatings. It also enhances the corrosion resistance and thermal stability of the powder coatings. Furthermore, the wear-resistant composite material provides reaction sites for subsequent reactions, further improving the wear resistance and corrosion resistance of the powder coatings. Combining the anti-corrosion and wear-resistant composite with 3,4-difluoromaleic anhydride yields a reinforcing material. 3,4-difluoromaleic anhydride not only exhibits good bonding with the anti-corrosion and wear-resistant composite but also provides reaction sites for subsequent reactions. Simultaneously, it increases the dispersibility of the anti-corrosion and wear-resistant composite in the resin, enhancing the compatibility between the anti-corrosion and wear-resistant composite and the resin, further improving the corrosion resistance, wear resistance, thermal stability, and mechanical properties of the powder coating.

[0059] (2) In the technical solution of the present invention, a modified phenolic resin is obtained by combining the reinforcing material with the vinylated phenolic resin; the vinylated phenolic resin is prepared by modifying the boron-modified phenolic resin with 3-methacryloyloxypropyltrimethoxysilane; the vinylated phenolic resin not only increases the bonding force between the boron-modified phenolic resin and the reinforcing material, but also improves the dispersion performance of the reinforcing material, prevents its agglomeration, and enhances its compatibility with the boron-modified phenolic resin. Combining the reinforcing material with the vinylated phenolic resin effectively improves the corrosion resistance, wear resistance, thermal stability and mechanical properties of the powder coating; the bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, curing agent, leveling agent, pigment, filler and dispersant are mixed, extruded and granulated, ground and sieved, and finally the powder coating is obtained. The modified phenolic resin effectively improves the overall performance of the powder coating.

[0060] (3) In the technical solution of the present invention, a modified phenolic resin is obtained by combining linear amino polysiloxane with wear-resistant composite material, then with 3,4-difluoromaleic anhydride, and finally with vinyl phenolic resin; bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, curing agent, leveling agent, pigment, filler and dispersant are mixed, extruded and granulated, ground and sieved, and finally powder coating is obtained; the overall corrosion resistance, wear resistance, thermal stability, hardness and mechanical properties of the powder coating are improved, and the service life of the powder coating is extended, and the overall comprehensive performance is good. Detailed Implementation

[0061] 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.

[0062] The specific parameters of the raw materials used in this invention are as follows:

[0063] Graphene oxide, No. S25040, provided by Shanghai Yuanye Biotechnology Co., Ltd.; 3,4-difluoromaleic anhydride, CAS No. 669-78-3, provided by Jinan Hongshengdi New Materials Co., Ltd.; Titanium dioxide (rutile titanium dioxide), particle size / mesh: 1000 mesh, provided by Hebei Kuoyou Chemical Technology Co., Ltd.; Silica, 1500 mesh, provided by Lingshou Zhuolei Building Materials Co., Ltd.; Sodium bentonite, 325 mesh, provided by Lingshou Yongshun Mineral Products Processing Co., Ltd. The following materials are provided by the manufacturer: Calcium carbonate, 800 mesh, provided by Shijiazhuang Shiye Mineral Products Co., Ltd.; Barium sulfate, 325 mesh, provided by Tianjin Hongqiao District Tianbao Haotong Stone Processing Plant; Polyethylene wax, provided by Henan Tianchou Chemical Products Co., Ltd.; Bisphenol A type epoxy resin, CAS No.: 25085-99-8, Product No.: R149551, provided by Shanghai Yi'en Chemical Technology Co., Ltd.; Phenolic epoxy resin, Model: F51, provided by Wuxi Jiunai Anticorrosion Materials Co., Ltd.

[0064] The preparation method of boron-modified phenolic resin includes the following steps:

[0065] Phenol, formaldehyde solution, oxalic acid, boric acid, and deionized water were mixed in a mass ratio of 1.2:1:0.01:0.05:100. Oxalic acid was then added and the pH of the solution was adjusted to 3. The mixture was reacted at 70°C for 1 hour. Boric acid was then added, the temperature was raised to 95°C, and the reaction was continued for 1 hour. A 1 mol / L sodium hydroxide solution was added and the pH of the system was adjusted to 7. Then, deionized water was added and the mixture was stirred for 10 minutes. The mixture was allowed to stand and separate into layers. The upper water layer was removed, leaving the lower resin layer. The resin layer was then dehydrated under vacuum at 145°C and a vacuum pressure of -0.08 MPa to obtain boron-modified phenolic resin.

[0066] Example 1

[0067] The specific steps for preparing modified phenolic resin are as follows:

[0068] S1: The linear amino polysiloxane, wear-resistant composite material, and deionized water were mixed in a mass ratio of 1.4:0.8:280. Then, deionized water was added, and the mixture was stirred in a constant temperature water bath at 75°C for 0.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 4% of the mass of the above deionized water, and each time the mass of deionized water was 6% of the mass of the above deionized water). Finally, the mixture was vacuum dried at 55°C for 12 h to obtain the anti-corrosion and wear-resistant composite material.

[0069] The preparation method of linear amino polysiloxane includes the following steps:

[0070] According to the mass ratio of pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane, and deionized water of 5.8:5.8:0.5, pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane were added to deionized water and reacted at 25°C for 10 min. Then, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane mass was 85% of the mass of pentafluorophenyltriethoxysilane) and deionized water (deionized water mass was 50% of the above deionized water mass) were added, and the reaction was continued for 40 min. Then, the temperature was raised to 70°C, and the mixture was stirred and refluxed for 3 h. After the reaction was completed, the reaction was continued for 8 h under reduced pressure conditions. The temperature of the reduced pressure conditions was 70°C and the pressure was −0.005 MPa. Finally, linear amino polysiloxane was obtained.

[0071] The preparation method of wear-resistant composite materials includes the following steps:

[0072] According to the mass ratio of ammonium molybdate tetrahydrate, anhydrous ethanol, and deionized water of 0.8:10:40, ammonium molybdate tetrahydrate was added to anhydrous ethanol and deionized water, and then stirred at 100 rpm for 20 min to obtain a precursor solution. According to the mass ratio of composite material to ethanol of 0.4:90, the composite material was dispersed in ethanol and mixed evenly to obtain a dispersion. According to the mass ratio of dispersion to precursor solution of 1:1, the dispersion was added to the precursor solution, and then stirred in a water bath at 75℃ for 8 h. After cooling to room temperature, it was filtered, washed three times with deionized water (each time the mass of deionized water was 40% of the above deionized water mass), and finally vacuum dried at 50℃ for 24 h to obtain the wear-resistant composite material.

[0073] The preparation method of composite materials includes the following steps:

[0074] The magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water were mixed evenly in a mass ratio of 0.8:0.8:0.4:1.8:140 to obtain a mixed solution. Graphene oxide was added to the mixed solution in a mass ratio of 1.4:3.4, and the mixture was stirred evenly. The solution was then heated to 75°C, and a 1 mol / L sodium hydroxide solution was added to adjust the pH to 10. The mixture was stirred for 2 hours and aged at 75°C for 14 hours. The final product was filtered through a 0.45 μm polyethersulfone membrane, washed with deionized water (10% of the total deionized water mass), and finally dried at 75°C for 10 hours to obtain the composite material.

[0075] S2: According to the mass ratio of the anti-corrosion and wear-resistant composite, 3,4-difluoromaleic anhydride, and N,N-dimethylformamide of 0.1:1.8:30, the anti-corrosion and wear-resistant composite and 3,4-difluoromaleic anhydride from step S1 were mixed, and then N,N-dimethylformamide was added. The mixture was then reacted at 70°C for 2 hours, the temperature was increased to 90°C, and the reaction was continued for 13 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 30% of the mass of N,N-dimethylformamide, and each time the mass of deionized water was 50% of the mass of N,N-dimethylformamide). Finally, the mixture was vacuum dried at 55°C for 12 hours to obtain the reinforced material.

[0076] S3: According to the mass ratio of reinforcing material, vinyl phenolic resin, and benzoyl peroxide of 0.8:1.8:0.02, the reinforcing material and vinyl phenolic resin from step S2 are mixed, and then benzoyl peroxide is added. The mixture is then reacted at 75°C for 3.5 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and washed three times with diethyl ether (each time the mass of diethyl ether is 10 times the mass of the reinforcing material). Finally, the mixture is vacuum dried at 20°C for 24 hours to obtain the modified phenolic resin.

[0077] The preparation method of vinylated phenolic resin includes the following steps:

[0078] The boron-modified phenolic resin, 3-methacryloxypropyltrimethoxysilane, and p-toluenesulfonic acid were mixed in a mass ratio of 0.8:0.1:0.01. The boron-modified phenolic resin was heated to 75°C, and then 3-methacryloxypropyltrimethoxysilane and p-toluenesulfonic acid were added. The mixture was then reacted at 80°C for 2.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times with ethanol (each time the mass of ethanol was 10 times the mass of 3-methacryloxypropyltrimethoxysilane). Finally, the mixture was vacuum dried at 35°C for 12 h to obtain the vinylated phenolic resin.

[0079] A powder coating comprises the following raw materials in parts by weight: 40 parts of bisphenol A type epoxy resin, 20 parts of modified phenolic resin, 10 parts of phenolic epoxy resin, 8 parts of diethylaminopropylamine, 3 parts of BYK-307 leveling agent, 1 part of titanium dioxide, 4 parts of sodium bentonite, and 5 parts of polyethylene wax.

[0080] The preparation method includes the following steps:

[0081] Weigh out the raw materials by weight, and mix bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, diethylaminopropylamine, BYK-307 leveling agent, titanium dioxide, sodium bentonite and polyethylene wax. Stir at 1000 rpm for 5 minutes to obtain a mixture. Add the mixture to a twin-screw extruder for extrusion granulation. The working temperature of the twin-screw extruder is 110℃ and the main motor speed is 200 rpm. Then grind and pass through a 100-mesh sieve to finally obtain powder coating.

[0082] Example 2

[0083] The specific steps for preparing modified phenolic resin are as follows:

[0084] S1: The linear amino polysiloxane, wear-resistant composite material, and deionized water were mixed in a mass ratio of 1.5:1:300. Then, deionized water was added, and the mixture was stirred in a constant temperature water bath at 80°C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 4% of the mass of the above deionized water, and each time the mass of deionized water was 6% of the mass of the above deionized water). Finally, the mixture was vacuum dried at 60°C for 12 hours to obtain the anti-corrosion and wear-resistant composite material.

[0085] The preparation method of linear amino polysiloxane includes the following steps:

[0086] The pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane, and deionized water were added to deionized water at a mass ratio of 6:6:0.6 and reacted at 30°C for 15 min. Then, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (85% of the mass of pentafluorophenyltriethoxysilane) and deionized water (50% of the mass of the above deionized water) were added and the reaction was continued for 45 min. The temperature was then increased to 75°C and the mixture was stirred and refluxed for 4 h. After the reaction was completed, the reaction was continued for 9 h under reduced pressure at a temperature of 75°C and a pressure of −0.005 MPa. Finally, linear amino polysiloxane was obtained.

[0087] The preparation method of wear-resistant composite materials includes the following steps:

[0088] According to the mass ratio of ammonium molybdate tetrahydrate, anhydrous ethanol, and deionized water of 1:12:45, ammonium molybdate tetrahydrate was added to anhydrous ethanol and deionized water, and then stirred at 160 rpm for 15 min to obtain a precursor solution. According to the mass ratio of composite material to ethanol of 0.5:100, the composite material was dispersed in ethanol and mixed evenly to obtain a dispersion. According to the mass ratio of dispersion to precursor solution of 1:1, the dispersion was added to the precursor solution, and then stirred in a water bath at 80℃ for 9 h. After cooling to room temperature, it was filtered, washed three times with deionized water (each time the mass of deionized water was 40% of the above deionized water mass), and finally vacuum dried at 55℃ for 24 h to obtain the wear-resistant composite material.

[0089] The preparation method of composite materials includes the following steps:

[0090] Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water were mixed evenly in a mass ratio of 1:1:0.5:2:150 to obtain a mixed solution. Graphene oxide was added to the mixed solution in a mass ratio of 1.5:3.5 and stirred evenly. The mixture was then heated to 80°C, and a 1 mol / L sodium hydroxide solution was added to adjust the pH to 10.3. The mixture was stirred for 2.5 hours and aged at 80°C for 15 hours. The final product was filtered through a 0.45 μm polyethersulfone membrane, washed with deionized water (10% of the total deionized water mass), and finally dried at 80°C for 11 hours to obtain the composite material.

[0091] S2: According to the mass ratio of the anti-corrosion and wear-resistant composite, 3,4-difluoromaleic anhydride, and N,N-dimethylformamide of 0.15:1.9:35, the anti-corrosion and wear-resistant composite and 3,4-difluoromaleic anhydride from step S1 were mixed, and then N,N-dimethylformamide was added. The mixture was then reacted at 75°C for 3 hours, the temperature was increased to 95°C, and the reaction was continued for 14 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 30% of the mass of N,N-dimethylformamide, and each time the mass of deionized water was 50% of the mass of N,N-dimethylformamide). Finally, the mixture was vacuum dried at 60°C for 12 hours to obtain the reinforced material.

[0092] S3: According to the mass ratio of reinforcing material, vinyl phenolic resin, and benzoyl peroxide of 1:2:0.03, the reinforcing material and vinyl phenolic resin from step S2 are mixed, and then benzoyl peroxide is added. The mixture is then reacted at 80°C for 4 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and washed three times with diethyl ether (each time the mass of diethyl ether is 10 times the mass of the reinforcing material). Finally, the mixture is vacuum dried at 25°C for 24 hours to obtain the modified phenolic resin.

[0093] The preparation method of vinylated phenolic resin includes the following steps:

[0094] The boron-modified phenolic resin, 3-methacryloxypropyltrimethoxysilane, and p-toluenesulfonic acid were mixed in a mass ratio of 1:0.15:0.02. The boron-modified phenolic resin was heated to 80°C, and then 3-methacryloxypropyltrimethoxysilane and p-toluenesulfonic acid were added. The mixture was then reacted at 85°C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times with ethanol (each time the mass of ethanol was 10 times the mass of 3-methacryloxypropyltrimethoxysilane). Finally, the mixture was vacuum dried at 40°C for 12 hours to obtain the vinylated phenolic resin.

[0095] A powder coating comprises the following raw materials in parts by weight: 45 parts of bisphenol A type epoxy resin, 22 parts of modified phenolic resin, 13 parts of phenolic epoxy resin, 9 parts of tetraethylenepentamine, 4 parts of BYK-358N leveling agent, 1.5 parts of silica, 5 parts of calcium carbonate, and 6 parts of dispersant 5040.

[0096] The preparation method includes the following steps:

[0097] Weigh out the raw materials by weight, and mix bisphenol A epoxy resin, modified phenolic resin, phenolic epoxy resin, tetraethylenepentamine, BYK-358N leveling agent, silica, calcium carbonate and dispersant 5040. Stir at 1500 rpm for 4 minutes to obtain a mixture. Add the mixture to a twin-screw extruder for extrusion granulation. The working temperature of the twin-screw extruder is 115℃ and the main extruder speed is 300 rpm. Then grind and pass through a 120-mesh sieve to finally obtain a powder coating.

[0098] Example 3

[0099] The specific steps for preparing modified phenolic resin are as follows:

[0100] S1: The linear amino polysiloxane, wear-resistant composite material, and deionized water were mixed in a mass ratio of 1.6:1.2:320. Then, deionized water was added, and the mixture was stirred in a constant temperature water bath at 85°C for 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 4% of the mass of the deionized water, and each time the mass of deionized water was 6% of the mass of the deionized water). Finally, the mixture was vacuum dried at 65°C for 12 hours to obtain the anti-corrosion and wear-resistant composite material.

[0101] The preparation method of linear amino polysiloxane includes the following steps:

[0102] According to the mass ratio of pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane, and deionized water of 6.2:6.2:0.7, pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane were added to deionized water and reacted at 35°C for 20 min. Then, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane mass was 85% of the mass of pentafluorophenyltriethoxysilane) and deionized water (deionized water mass was 50% of the mass of the above deionized water) were added, and the reaction was continued for 50 min. Then, the temperature was raised to 80°C and the mixture was stirred and refluxed for 5 h. After the reaction was completed, the reaction was continued for 10 h under reduced pressure conditions. The temperature of the reduced pressure conditions was 80°C and the pressure was −0.005 MPa. Finally, linear amino polysiloxane was obtained.

[0103] The preparation method of wear-resistant composite materials includes the following steps:

[0104] According to the mass ratio of ammonium molybdate tetrahydrate, anhydrous ethanol, and deionized water of 1.2:15:50, ammonium molybdate tetrahydrate was added to anhydrous ethanol and deionized water, and then stirred at 200 rpm for 10 min to obtain a precursor solution. According to the mass ratio of composite material to ethanol of 0.6:110, the composite material was dispersed in ethanol and mixed evenly to obtain a dispersion. According to the mass ratio of dispersion to precursor solution of 1:1, the dispersion was added to the precursor solution, and then stirred in a water bath at 85℃ for 10 h. After cooling to room temperature, it was filtered, washed three times with deionized water (each time the mass of deionized water was 40% of the above deionized water mass), and finally vacuum dried at 60℃ for 24 h to obtain the wear-resistant composite material.

[0105] The preparation method of composite materials includes the following steps:

[0106] Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water were mixed evenly in a mass ratio of 1.2:1.2:0.6:2.2:160 to obtain a mixed solution. Graphene oxide was added to the mixed solution in a mass ratio of 1.6:3.6, and the mixture was stirred evenly. The solution was then heated to 85°C, and a 1 mol / L sodium hydroxide solution was added to adjust the pH to 10.5. The mixture was stirred for 3 hours and aged at 85°C for 16 hours. The final product was filtered through a 0.45 μm polyethersulfone membrane, washed with deionized water (10% of the total deionized water mass), and finally dried at 85°C for 12 hours to obtain the composite material.

[0107] S2: According to the mass ratio of the anti-corrosion and wear-resistant composite, 3,4-difluoromaleic anhydride, and N,N-dimethylformamide of 0.2:2:40, the anti-corrosion and wear-resistant composite and 3,4-difluoromaleic anhydride from step S1 were mixed, and then N,N-dimethylformamide was added. The mixture was then reacted at 80°C for 4 hours, the temperature was increased to 100°C, and the reaction was continued for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 30% of the mass of N,N-dimethylformamide, and each time the mass of deionized water was 50% of the mass of N,N-dimethylformamide). Finally, the mixture was vacuum dried at 65°C for 12 hours to obtain the reinforced material.

[0108] S3: According to the mass ratio of reinforcing material, vinyl phenolic resin, and benzoyl peroxide of 1.2:2.2:0.04, the reinforcing material and vinyl phenolic resin from step S2 were mixed, and then benzoyl peroxide was added. The mixture was then reacted at 85°C for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times with diethyl ether (each time the mass of diethyl ether was 10 times the mass of the reinforcing material). Finally, the mixture was vacuum dried at 30°C for 24 h to obtain the modified phenolic resin.

[0109] The preparation method of vinylated phenolic resin includes the following steps:

[0110] The boron-modified phenolic resin, 3-methacryloxypropyltrimethoxysilane, and p-toluenesulfonic acid were mixed in a mass ratio of 1.2:0.2:0.03. The boron-modified phenolic resin was heated to 85°C, and then 3-methacryloxypropyltrimethoxysilane and p-toluenesulfonic acid were added. The mixture was then reacted at 90°C for 3.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times with ethanol (each time the mass of ethanol was 10 times the mass of 3-methacryloxypropyltrimethoxysilane). Finally, the mixture was vacuum dried at 45°C for 12 h to obtain the vinylated phenolic resin.

[0111] A powder coating comprises the following raw materials in parts by weight: 50 parts of bisphenol A type epoxy resin, 25 parts of modified phenolic resin, 15 parts of phenolic epoxy resin, 10 parts of cyclohexanone peroxide, 5 parts of polydimethylsiloxane, 2 parts of titanium dioxide, 6 parts of barium sulfate, and 7 parts of polyethylene wax.

[0112] The preparation method includes the following steps:

[0113] Weigh out the raw materials by weight, mix bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, cyclohexanone peroxide, polydimethylsiloxane, titanium dioxide, barium sulfate and polyethylene wax, and stir at 2000 rpm for 3 minutes to obtain a mixture. Add the mixture to a twin-screw extruder for extrusion granulation. The working temperature of the twin-screw extruder is 120℃ and the main motor speed is 400 rpm. Then grind and pass through a 140-mesh sieve to finally obtain powder coating.

[0114] Comparative Example 1

[0115] The difference between this comparative example and Example 3 is that, in the preparation of the modified phenolic resin, the linear amino polysiloxane in step S1 is obtained by combining pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane, while the remaining steps and raw materials are the same as in Example 3.

[0116] The preparation method of linear amino polysiloxane includes the following steps:

[0117] According to the mass ratio of pentafluorophenyltriethoxysilane to deionized water of 6.2:0.7, pentafluorophenyltriethoxysilane was added to deionized water and reacted at 35°C for 20 min. Then, trimethoxy(pentafluorophenyl)silane (the mass of trimethoxy(pentafluorophenyl)silane was 85% of the mass of pentafluorophenyltriethoxysilane) and deionized water (the mass of deionized water was 50% of the mass of the above deionized water) were added, and the reaction was continued for 50 min. Then, the temperature was raised to 80°C and the mixture was stirred and refluxed for 5 h. After the reaction was completed, the reaction was continued for 10 h under reduced pressure conditions. The temperature of the reduced pressure conditions was 80°C and the pressure was −0.005 MPa. Finally, linear amino polysiloxane was obtained.

[0118] Comparative Example 2

[0119] The difference between this comparative example and Example 3 is that, in the preparation of the modified phenolic resin, the linear amino polysiloxane in step S1 is obtained by combining pentafluorophenyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, while the remaining steps and raw materials are the same as in Example 3.

[0120] The preparation method of linear amino polysiloxane includes the following steps:

[0121] According to the mass ratio of pentafluorophenyltriethoxysilane to deionized water of 6.2:0.7, pentafluorophenyltriethoxysilane was added to deionized water and reacted at 35°C for 20 min. Then, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane mass was 85% of the mass of pentafluorophenyltriethoxysilane) and deionized water (deionized water mass was 50% of the mass of the above deionized water) were added, and the reaction was continued for 50 min. Then, the temperature was raised to 80°C and the mixture was stirred and refluxed for 5 h. After the reaction was completed, the reaction was continued for 10 h under reduced pressure conditions. The temperature under reduced pressure conditions was 80°C and the pressure was −0.005 MPa. Finally, linear amino polysiloxane was obtained.

[0122] Comparative Example 3

[0123] The difference between this comparative example and Example 3 is that, in the preparation of the modified phenolic resin, the linear amino polysiloxane in step S1 is obtained by combining trimethoxy(pentafluorophenyl)silane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, while the remaining steps and raw materials are the same as in Example 3.

[0124] The preparation method of linear amino polysiloxane includes the following steps:

[0125] Trimethoxy(pentafluorophenyl)silane and deionized water were added to deionized water at a mass ratio of 6.2:0.7, and reacted at 35°C for 20 min. Then, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (85% of the mass of trimethoxy(pentafluorophenyl)silane) and deionized water (50% of the mass of the above deionized water) were added, and the reaction was continued for 50 min. The temperature was then raised to 80°C, and the mixture was stirred and refluxed for 5 h. After the reaction was completed, the reaction was continued for 10 h under reduced pressure at 80°C and -0.005 MPa, finally yielding linear amino polysiloxane.

[0126] Comparative Example 4

[0127] The difference between this comparative example and Example 3 is that, in the preparation of the modified phenolic resin, the wear-resistant composite material in step S1 is prepared by graphene oxide loaded with molybdenum disulfide nanoparticles, while the remaining steps and raw materials are the same as in Example 3.

[0128] The preparation method of wear-resistant composite materials includes the following steps:

[0129] Ammonium molybdate tetrahydrate, anhydrous ethanol, and deionized water were added to anhydrous ethanol and deionized water at a mass ratio of 1.2:15:50, and stirred at 200 rpm for 10 min to obtain a precursor solution. Graphene oxide was dispersed in ethanol at a mass ratio of 0.6:110 and mixed thoroughly to obtain a dispersion. The dispersion was added to the precursor solution at a mass ratio of 1:1, and then stirred in a water bath at 85°C for 10 h. After cooling to room temperature, the mixture was filtered, washed three times with deionized water (each time the deionized water mass was 40% of the total deionized water mass), and finally vacuum dried at 60°C for 24 h to obtain the wear-resistant composite material.

[0130] Comparative Example 5

[0131] The difference between this comparative example and Example 3 is that the wear-resistant composite material in step S1 is prepared by layered double hydroxide loaded with molybdenum disulfide nanoparticles, while the remaining steps and raw materials are the same as in Example 3.

[0132] The preparation method of wear-resistant composite materials includes the following steps:

[0133] According to the mass ratio of ammonium molybdate tetrahydrate, anhydrous ethanol, and deionized water of 1.2:15:50, ammonium molybdate tetrahydrate was added to anhydrous ethanol and deionized water, and then stirred at 200 rpm for 10 min to obtain a precursor solution. According to the mass ratio of layered double hydroxide to ethanol of 0.6:110, the layered double hydroxide was dispersed in ethanol and mixed evenly to obtain a dispersion. According to the mass ratio of dispersion to precursor solution of 1:1, the dispersion was added to the precursor solution, and then stirred in a water bath at 85℃ for 10 h. After cooling to room temperature, it was filtered, washed three times with deionized water (each time the mass of deionized water was 40% of the above deionized water mass), and finally vacuum dried at 60℃ for 24 h to obtain the wear-resistant composite material.

[0134] The preparation method of layered double hydroxides includes the following steps:

[0135] The magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water were mixed evenly in a mass ratio of 1.2:1.2:0.6:2.2:160, and stirred at room temperature for 3 hours. After filtration, the mixture was washed with deionized water (the mass of deionized water was 10% of the mass of the above deionized water), and finally dried at 85°C for 12 hours to obtain a layered double hydroxide.

[0136] Comparative Example 6

[0137] The difference between this comparative example and Example 3 is that, in the preparation of the modified phenolic resin, the wear-resistant composite material in step S1 is composed of a mixture of graphene oxide, layered double hydroxide and molybdenum disulfide nanoparticles, while the remaining steps and raw materials are the same as in Example 3.

[0138] S1: The linear amino polysiloxane, wear-resistant composite material, and deionized water were mixed in a mass ratio of 1.6:1.2:320. Then, deionized water was added, and the mixture was stirred in a constant temperature water bath at 85°C for 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 4% of the mass of the above deionized water, and each time the mass of deionized water was 6% of the mass of the above deionized water). Finally, the mixture was vacuum dried at 65°C for 12 hours to obtain the anti-corrosion and wear-resistant composite material. The wear-resistant composite material was composed of graphene oxide, layered double hydroxide, and molybdenum disulfide nanoparticles in a mass ratio of 1:1:1.

[0139] Comparative Example 7

[0140] The difference between this comparative example and Example 3 is that, in the preparation of the modified phenolic resin, the 3,4-difluoromaleic anhydride in step S2 is replaced by maleic anhydride by mass, while the remaining steps and raw materials are the same as in Example 3.

[0141] S2: According to the mass ratio of the anti-corrosion and wear-resistant composite, maleic anhydride, and N,N-dimethylformamide of 0.2:2:40, the anti-corrosion and wear-resistant composite and maleic anhydride from step S1 were mixed, and then N,N-dimethylformamide was added. The mixture was then reacted at 80°C for 4 hours, the temperature was increased to 100°C, and the reaction was continued for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 30% of the mass of N,N-dimethylformamide, and each time the mass of deionized water was 50% of the mass of N,N-dimethylformamide). Finally, the mixture was vacuum dried at 65°C for 12 hours to obtain the reinforced material.

[0142] Comparative Example 8

[0143] The difference between this comparative example and Example 3 is that, in the preparation of the modified phenolic resin, the vinyl phenolic resin in step S3 is replaced by boron-modified phenolic resin by an equal mass, while the remaining steps and raw materials are the same as in Example 3.

[0144] S3: According to the mass ratio of reinforcing material, boron-modified phenolic resin, and benzoyl peroxide of 1.2:2.2:0.04, the reinforcing material and boron-modified phenolic resin from step S2 are mixed, and then benzoyl peroxide is added. The mixture is then reacted at 85°C for 4.5 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and washed three times with diethyl ether (each time the mass of diethyl ether is 10 times the mass of the reinforcing material). Finally, the mixture is vacuum dried at 30°C for 24 hours to obtain the modified phenolic resin.

[0145] Comparative Example 9

[0146] The difference between this comparative example and Example 3 is that, in preparing the modified phenolic resin, the anti-corrosion and wear-resistant composite in step S1 is directly combined with the vinyl phenolic resin in step S3, and the original step S2 is deleted. The remaining steps and raw materials are the same as in Example 3.

[0147] S1: The linear amino polysiloxane, wear-resistant composite material, and deionized water were mixed in a mass ratio of 1.6:1.2:320. Then, deionized water was added, and the mixture was stirred in a constant temperature water bath at 85°C for 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times each with ethanol and deionized water (each time the mass of ethanol was 4% of the mass of the deionized water, and each time the mass of deionized water was 6% of the mass of the deionized water). Finally, the mixture was vacuum dried at 65°C for 12 hours to obtain the anti-corrosion and wear-resistant composite material.

[0148] The preparation method of linear amino polysiloxane includes the following steps:

[0149] According to the mass ratio of pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane, and deionized water of 6.2:6.2:0.7, pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane were added to deionized water and reacted at 35°C for 20 min. Then, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane mass was 85% of the mass of pentafluorophenyltriethoxysilane) and deionized water (deionized water mass was 50% of the mass of the above deionized water) were added, and the reaction was continued for 50 min. Then, the temperature was raised to 80°C and the mixture was stirred and refluxed for 5 h. After the reaction was completed, the reaction was continued for 10 h under reduced pressure conditions. The temperature of the reduced pressure conditions was 80°C and the pressure was −0.005 MPa. Finally, linear amino polysiloxane was obtained.

[0150] The preparation method of wear-resistant composite materials includes the following steps:

[0151] According to the mass ratio of ammonium molybdate tetrahydrate, anhydrous ethanol, and deionized water of 1.2:15:50, ammonium molybdate tetrahydrate was added to anhydrous ethanol and deionized water, and then stirred at 200 rpm for 10 min to obtain a precursor solution. According to the mass ratio of composite material to ethanol of 0.6:110, the composite material was dispersed in ethanol and mixed evenly to obtain a dispersion. According to the mass ratio of dispersion to precursor solution of 1:1, the dispersion was added to the precursor solution, and then stirred in a water bath at 85℃ for 10 h. After cooling to room temperature, it was filtered, washed three times with deionized water (each time the mass of deionized water was 40% of the above deionized water mass), and finally vacuum dried at 60℃ for 24 h to obtain the wear-resistant composite material.

[0152] The preparation method of composite materials includes the following steps:

[0153] Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water were mixed evenly in a mass ratio of 1.2:1.2:0.6:2.2:160 to obtain a mixed solution. Graphene oxide was added to the mixed solution in a mass ratio of 1.6:3.6, and the mixture was stirred evenly. The solution was then heated to 85°C, and a 1 mol / L sodium hydroxide solution was added to adjust the pH to 10.5. The mixture was stirred for 3 hours and aged at 85°C for 16 hours. The final product was filtered through a 0.45 μm polyethersulfone membrane, washed with deionized water (10% of the total deionized water mass), and finally dried at 85°C for 12 hours to obtain the composite material.

[0154] S2: The anti-corrosion and wear-resistant compound, vinyl phenolic resin, and benzoyl peroxide were mixed in a mass ratio of 1.2:2.2:0.04. Then, benzoyl peroxide was added and the mixture was reacted at 85°C for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times with ether (each time the mass of ether was 10 times the mass of the anti-corrosion and wear-resistant compound). Finally, the mixture was vacuum dried at 30°C for 24 h to obtain the modified phenolic resin.

[0155] The preparation method of vinylated phenolic resin includes the following steps:

[0156] The boron-modified phenolic resin, 3-methacryloxypropyltrimethoxysilane, and p-toluenesulfonic acid were mixed in a mass ratio of 1.2:0.2:0.03. The boron-modified phenolic resin was heated to 85°C, and then 3-methacryloxypropyltrimethoxysilane and p-toluenesulfonic acid were added. The mixture was then reacted at 90°C for 3.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed three times with ethanol (each time the mass of ethanol was 10 times the mass of 3-methacryloxypropyltrimethoxysilane). Finally, the mixture was vacuum dried at 45°C for 12 h to obtain the vinylated phenolic resin.

[0157] The powder coatings prepared in Examples 1-3 and Comparative Examples 1-9 were tested for corrosion resistance, wear resistance, hardness and mechanical properties. The powder coatings prepared in Examples 1-3 and Comparative Examples 1-9 were sprayed onto the surface-treated tinplate substrate using electrostatic spraying technology. The spraying thickness was 70 μm. The coatings were then baked and cured at 200°C for 20 min to form a coating.

[0158] Salt spray resistance test: The salt spray resistance test is conducted according to GB / T 1771-2001. After the test, observe whether there are any abnormal phenomena such as blistering, peeling or discoloration on the coating surface. Acid resistance test: Immerse 2 / 3 of each coating in a 4.5% sulfuric acid solution at 25℃. Remove the coating every 24 hours, wash the coating sample with water, and wipe the surface with absorbent paper. Check the coating surface for discoloration, loss of gloss, small bubbles, spots, peeling, etc. Alkali resistance test: Immerse 2 / 3 of each coating in a 4.5% sodium hydroxide solution at 25℃. Remove the coating every 24 hours, wash the coating sample with water, and wipe the surface with absorbent paper. Check the coating surface for discoloration, loss of gloss, small bubbles, spots, peeling, etc.

[0159] Wear resistance test: The coating samples prepared in Examples 1-3 and Comparative Examples 1-9 were fixed on a rotating platform with the outer surface of the sample facing upward. Two grinding wheels were lowered under a certain load so that they just contacted the surface of the sample. The rotation speed was set to 60 r / min, and CS-10 grinding wheels were used. The test time was 1 hour, and the weight loss (mg) of each sample after wear was recorded. The lower the weight loss, the better the wear resistance of the coating.

[0160] Hardness test: Pencil hardness was determined according to GB / T 6739-2006, the pencil test method for coating hardness; Mechanical property test: Impact strength of the coating was tested according to GB / T 1732-1993, and the mechanical properties were characterized by impact strength. The test results are shown in Table 1 below:

[0161] Table 1 Performance parameters of powder coatings prepared in Examples 1-3 and Comparative Examples 1-9

[0162]

[0163] As shown in Table 1 above, and by comparing Comparative Examples 1-3 and Example 3, the linear amino polysiloxane used in step S1 is prepared by combining pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane, or by combining pentafluorophenyltriethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, or by combining trimethoxy(pentafluorophenyl)silane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane. The powder coating prepared by combining pentafluorophenyltriethoxysilane was worse than that prepared in Example 3. This indicates that the linear amino polysiloxane prepared by combining pentafluorophenyltriethoxysilane, trimethoxy(pentafluorophenyl)silane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane can effectively improve the corrosion resistance and thermal stability of the powder coating, and can provide reaction sites for subsequent reactions, further improving the corrosion resistance, wear resistance, hardness and mechanical properties of the powder coating.

[0164] Comparing Comparative Examples 4-6 and Example 3, it can be seen that the wear-resistant composite material in step S1, which is prepared by loading molybdenum disulfide nanoparticles onto graphene oxide, or by loading molybdenum disulfide nanoparticles onto layered double hydroxide, or by mixing graphene oxide, layered double hydroxide, and molybdenum disulfide nanoparticles, yields worse test results compared to Example 3. This indicates that combining graphene oxide and layered double hydroxide and then loading molybdenum disulfide nanoparticles can better disperse the molybdenum disulfide nanoparticles, prevent their aggregation, and effectively combine graphene oxide, layered double hydroxide, and molybdenum disulfide nanoparticles to achieve a synergistic effect, further improving the corrosion resistance, wear resistance, hardness, and mechanical properties of the powder coating.

[0165] Comparing Comparative Examples 7-9 and Example 3, it can be seen that when the 3,4-difluoromaleic anhydride in step S2 is replaced by maleic anhydride by an equal mass, or the vinylated phenolic resin in step S3 is replaced by boron-modified phenolic resin by an equal mass, or the anti-corrosion and wear-resistant composite in step S1 is directly combined with the vinylated phenolic resin in step S3, the test results of the powder coating are worse than those of Example 3. This indicates that combining 3,4-difluoromaleic anhydride with the anti-corrosion and wear-resistant composite not only has better bonding strength, but also... Anhydrides can enhance the corrosion resistance of powder coatings and increase the compatibility between the anti-corrosion and wear-resistant composite and the resin. Modifying boron-modified phenolic resin with a silane coupling agent can improve the bonding force between the anti-corrosion and wear-resistant composite and the boron-modified phenolic resin, effectively improving the corrosion resistance and wear resistance of the powder coating. Combining the anti-corrosion and wear-resistant composite with vinyl phenolic resin using 3,4-difluoromaleic anhydride increases the dispersibility of the anti-corrosion and wear-resistant composite in the resin, further improving the corrosion resistance, wear resistance, hardness, and mechanical properties of the powder coating.

[0166] As shown in Table 1 above, compared with the powder coatings prepared in Comparative Examples 1-9, the powder coatings prepared in Examples 1-3, through the combination of linear amino polysiloxane with wear-resistant composite material, then with 3,4-difluoromaleic anhydride, and finally with vinylated phenolic resin, obtained modified phenolic resin; the powder coatings prepared in Examples 1-3, through the mixing of bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, curing agent, leveling agent, pigment, filler and dispersant, followed by extrusion granulation, grinding and sieving, met the performance requirements, while the powder coatings prepared in Comparative Examples 1-9 did not meet the performance requirements. This indicates that the powder coatings prepared in this invention not only have better corrosion resistance, wear resistance, thermal stability, hardness and mechanical properties, but also extend the service life of the powder coating, and have good comprehensive performance.

[0167] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0168] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A powder coating, characterized in that, The raw materials include the following parts by weight: 40-50 parts of bisphenol A type epoxy resin, 20-25 parts of modified phenolic resin, 10-15 parts of phenolic epoxy resin, 8-10 parts of curing agent, 3-5 parts of leveling agent, 1-2 parts of pigment, 4-6 parts of filler and 5-7 parts of dispersant; The preparation method of the modified phenolic resin includes the following steps: S1: A corrosion-resistant and wear-resistant composite material is obtained by combining linear amino polysiloxane with wear-resistant composite material; S2: The anti-corrosion and wear-resistant composite is combined with 3,4-difluoromaleic anhydride to obtain a reinforced material; S3: Combine the reinforcing material with vinylated phenolic resin to obtain modified phenolic resin; The preparation method of the linear amino polysiloxane includes the following steps: Pentafluorophenyltriethoxysilane and trimethoxy(pentafluorophenyl)silane were added to deionized water and reacted at 25-35℃ for 10-20 min. Then N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and deionized water were added and the reaction was continued for 40-50 min. The temperature was then raised to 70-80℃ and the mixture was stirred and refluxed for 3-5 h. After the reaction was completed, the reaction was continued under reduced pressure for 8-10 h to finally obtain linear amino polysiloxane. The preparation method of the wear-resistant composite material includes the following steps: Ammonium molybdate tetrahydrate was added to anhydrous ethanol and deionized water, and then stirred for 10-20 min to obtain a precursor solution. The composite material was dispersed in ethanol and mixed evenly to obtain a dispersion. The dispersion was added to the precursor solution and stirred in a water bath at 75-85℃ for 8-10 h. After cooling to room temperature, it was filtered, washed with deionized water, and finally vacuum dried at 50-60℃ to obtain the wear-resistant composite material. The method for preparing the composite material includes the following steps: Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate, sodium chloride, and deionized water were mixed evenly to obtain a mixed solution. Graphene oxide was added to the mixed solution and stirred evenly. The mixture was then heated to 75-85℃, and sodium hydroxide solution was added to adjust the pH of the system to 10-10.

5. The mixture was stirred for 2-3 hours and aged at 75-85℃ for 14-16 hours. The mixture was then filtered through a filter membrane, washed with deionized water, and finally dried at 75-85℃ to obtain the composite material.

2. The powder coating according to claim 1, characterized in that, Step S1 is as follows: Linear aminopolysiloxane and wear-resistant composite material are mixed, deionized water is added, and the mixture is stirred in a constant temperature water bath at 75-85℃ for 0.5-1.5h. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with ethanol and deionized water, and finally vacuum dried at 55-65℃ to obtain the anti-corrosion and wear-resistant composite material.

3. The powder coating according to claim 1, characterized in that, Step S2 is as follows: The anti-corrosion and wear-resistant composite from step S1 is mixed with 3,4-difluoromaleic anhydride, and then N,N-dimethylformamide is added. The mixture is then reacted at 70-80℃ for 2-4 hours, the temperature is increased to 90-100℃, and the reaction continues for 13-15 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with ethanol and deionized water, and finally vacuum dried at 55-65℃ to obtain the reinforced material.

4. The powder coating according to claim 1, characterized in that, Step S3 is as follows: The reinforcing material from step S2 is mixed with the vinyl phenolic resin, and then benzoyl peroxide is added. The mixture is then reacted at 75-85°C for 3.5-4.5 hours. After the reaction is complete, the mixture is cooled to room temperature, filtered, washed with ether, and finally dried under vacuum at 20-30°C to obtain the modified phenolic resin.

5. A powder coating according to claim 4, characterized in that, The preparation method of the vinylated phenolic resin includes the following steps: Boron-modified phenolic resin was heated to 75-85℃, and then a silane coupling agent and p-toluenesulfonic acid were added. The mixture was then reacted at 80-90℃ for 2.5-3.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with ethanol, and finally dried under vacuum at 35-45℃ to obtain vinylated phenolic resin.

6. A method for preparing a powder coating as described in any one of claims 1-5, characterized in that, Includes the following steps: Weigh out the raw materials by weight, mix bisphenol A type epoxy resin, modified phenolic resin, phenolic epoxy resin, curing agent, leveling agent, pigment, filler and dispersant, and stir at 1000-2000 rpm for 3-5 minutes to obtain a mixture. Add the mixture to a twin-screw extruder for extrusion granulation, then grind and pass through a 100-140 mesh sieve to finally obtain a powder coating.

7. The application of a powder coating as described in any one of claims 1-5 in chemical pipelines and chemical equipment.

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