Environment-friendly paint and preparation method thereof

Abstract

The present application belongs to the technical field of paint, and particularly relates to a green and environment-friendly paint and a preparation method thereof. The green and environment-friendly paint prepared by the present application comprises the following raw materials in parts by weight: alcohol acid resin 100-140 parts; diethylene glycol tert-butyl ether 5-15 parts; diethylene glycol butyl ether 10-20 parts; zinc abietate 0.02-0.04 parts; Cu modified MIL-100(Fe) 0.04-0.08 parts; PANI@Ni doped molybdenum sulfide composite material 0.03-0.07 parts; leveling agent 1-2 parts; dispersing agent 0.4-0.6 parts; defoaming agent 0.5-0.7 parts; and drying agent 1-2 parts. The green and environment-friendly paint prepared by the present application has excellent corrosion resistance and other performances by adding Cu modified MIL-100(Fe) and ANI@Ni doped molybdenum sulfide composite material and cooperating with zinc abietate.

Description

Technical Field

[0001] This invention belongs to the field of paint technology. More specifically, it relates to a green and environmentally friendly paint and its preparation method. Background Technology

[0002] Metallic materials are important structural materials, widely used in aerospace, transportation, and everyday infrastructure. However, these metallic materials are often subject to corrosion due to harsh external environments. Coating metal surfaces with a paint film is the most convenient, direct, and economical method of protection. Alkyd resin varnish is an important anti-corrosion coating; however, pure alkyd resin, due to its large number of ester bonds and hydroxyl groups, results in poor corrosion resistance and low hardness. Therefore, incorporating other materials into alkyd resin varnish to improve its performance has become increasingly popular among scholars both domestically and internationally.

[0003] Metal-organic frameworks (MOFs) are porous compounds with variable structures formed by the coordination of metal clusters with polydentate organic ligands containing oxygen and nitrogen. They have attracted widespread attention from scholars in various fields due to their advantages, such as ultra-high specific surface area and tunable framework structure. Because of their high specific surface area, MOFs can increase their contact area with resins, thereby increasing the density of the coating and improving its corrosion resistance.

[0004] CN118931339A discloses a method for preparing a varnish coating using modular nickel oxide nanoparticles as a sealant. This method employs modular nickel oxide nanoparticles as a surface sealant for metal components, followed by a coat of 2-mercaptobenzothiazole-enhanced alkyd resin varnish. The coating prepared by this method exhibits a high corrosion potential, low corrosion current, and high impedance, indicating good corrosion resistance. This coating can be applied to corrosion protection of metal parts in electrical equipment such as air conditioners, electric water heaters, refrigerators, and mechanical equipment such as tractors and cranes.

[0005] CN118620524A discloses a water-resistant and rust-proof fast-drying epoxy alkyd varnish and its preparation process, comprising the following raw materials in parts by weight: 35-45 parts epoxy alkyd resin, 8-12 parts graphene-based modifier, 4-8 parts soybean oil, 5-7 parts compensating agent, 4-6 parts silane coupling agent, 4-6 parts curing agent, 0.2-0.3 parts drier, and 30-35 parts solvent. This invention's fast-drying epoxy alkyd varnish uses epoxy alkyd resin as the base material. By adding soybean oil, silane coupling agent, curing agent, and drier as functional additives, and simultaneously adding the graphene-based modifier and compensating agent, the two work synergistically to improve the product's fast drying, impact resistance, salt spray rust prevention, and water stability.

[0006] CN117264514A discloses a method for preparing an alkyd resin varnish doped with damaged rice-grain-shaped cobalt MOFs. The method involves mixing a drying, long-oil alkyd resin as the main film-forming substance, damaged rice-grain-shaped cobalt MOFs as the dopant, cobalt naphthenate as the drying agent, and n-butanol as the solvent, followed by high-speed stirring to obtain the alkyd resin varnish doped with damaged rice-grain-shaped cobalt MOFs. This varnish exhibits a high corrosion potential, low corrosion current, high impedance, and high hardness. It can be applied to corrosion protection engineering for metal parts of electrical equipment such as air conditioners, electric water heaters, refrigerators, and mechanical equipment such as tractors and cranes.

[0007] CN117050623A discloses a method for preparing an alkyd resin varnish doped with cobalt MOFs in the form of decayed wood rods. The method involves mixing a drying, long-oil alkyd resin and zinc rosinate as the main film-forming substances, cobalt MOFs in the form of decayed wood rods as the dopant, cobalt naphthenate as the drying agent, and n-butanol as the solvent. The mixture is stirred at high speed to obtain the alkyd resin varnish doped with cobalt MOFs in the form of decayed wood rods. This varnish exhibits a high corrosion potential, low corrosion current, high impedance, and high hardness. It can be applied to corrosion protection engineering for metal parts of electrical equipment such as air conditioners, electric water heaters, refrigerators, and mechanical equipment such as tractors and cranes.

[0008] CN116102959A discloses a high-gloss alkyd paint and its preparation method. The high-gloss alkyd paint, by weight percentage, comprises: 40-60 wt% alkyd resin, 10-20 wt% pigment, 10-20 wt% functional filler, 0.5-2 wt% additives, and solvent to make up the balance. When the weight ratio of alkyd resin, pigment, and functional filler is 11:(3-5):(2-6), the adhesion and gloss of the prepared alkyd paint can be improved. When the functional filler is calcium carbonate, diatomaceous earth, or talc, and the weight ratio of calcium carbonate, diatomaceous earth, and talc is 1:(1-2):(0.5-1), the drying time of the alkyd paint can be further reduced.

[0009] Adding additives to paint can improve its performance. Depending on the required performance, the necessary additives can be added to achieve the corresponding properties of the paint. Based on this, the present invention provides a green and environmentally friendly paint with excellent corrosion resistance and other properties. Summary of the Invention

[0010] The technical problem to be solved by this invention is to overcome the defects and deficiencies in the prior art and provide a green and environmentally friendly paint and its preparation method. The green and environmentally friendly paint prepared by this invention comprises, by weight, the following raw materials: 100-140 parts alkyd resin; 5-15 parts diethylene glycol tert-butyl ether; 10-20 parts diethylene glycol butyl ether; 0.02-0.04 parts zinc rosinate; 0.04-0.08 parts Cu-modified MIL-100(Fe); 0.03-0.07 parts PANI@Ni-doped molybdenum sulfide composite material; 1-2 parts leveling agent; 0.4-0.6 parts dispersant; 0.5-0.7 parts defoamer; and 1-2 parts drying agent. The green and environmentally friendly paint prepared by this invention, through the addition of Cu-modified MIL-100(Fe) and PANI@Ni-doped molybdenum sulfide composite material, and in combination with zinc rosinate, gives the environmentally friendly paint excellent corrosion resistance and other properties.

[0011] The purpose of this invention is to provide a green and environmentally friendly paint.

[0012] Another objective of this invention is to provide a method for preparing green and environmentally friendly paint.

[0013] The above-mentioned objective of this invention is achieved through the following technical solution:

[0014] A green and environmentally friendly paint, by weight, comprises the following raw materials:

[0015] 100-140 parts of alkyd resin;

[0016] 5-15 parts of diethylene glycol tert-butyl ether;

[0017] 10-20 parts of diethylene glycol butyl ether;

[0018] Zinc rosinate 0.02–0.04 parts;

[0019] 0.04–0.08 parts of Cu-modified MIL-100(Fe);

[0020] 0.03–0.07 parts of PANI@Ni-doped molybdenum sulfide composite material;

[0021] 1-2 parts leveling agent;

[0022] Dispersant 0.4–0.6 parts;

[0023] Defoamer 0.5-0.7 parts;

[0024] 1-2 parts of drying agent.

[0025] In this invention, a preferred technical solution is provided, wherein the method for preparing Cu-modified MIL-100(Fe) includes the following steps:

[0026] Copper salt, iron salt and pyromellitic acid were added to deionized water and stirred for a certain period of time. Then the mixture was transferred to a hydrothermal reactor for hydrothermal reaction. After cooling to room temperature, the mixture was filtered, washed and dried to obtain Cu-modified MIL-100(Fe).

[0027] Preferably, the copper salt is at least one of copper nitrate, copper chloride, and copper acetate, and the iron salt is at least one of ferric chloride, ferric acetate, and ferric nitrate. The molar ratio of the copper salt, iron salt, and trimesic acid is 0.1-0.3:1.7-1.9:1.

[0028] More preferably, the stirring time is 20-40 min, the hydrothermal reaction is carried out at 140-180℃ for 12-16 h, and the drying is carried out at 80-100℃ for 10-14 h.

[0029] In a further preferred embodiment of the present invention, the preparation method of the PANI@Ni-doped molybdenum sulfide composite material includes the following steps:

[0030] (1) Add nickel salt, molybdate, thiourea and hydroxylamine hydrochloride to deionized water, then transfer to a hydrothermal reactor for hydrothermal reaction, cool to room temperature, filter, wash and dry to obtain Ni-doped molybdenum sulfide nanosheets.

[0031] (2) The Ni-doped molybdenum sulfide nanosheets obtained in step (1) and mercaptoacetic acid are ultrasonically dispersed in deionized water, ultrasonicated for 2-4 hours, stirred for 25-35 hours, filtered, washed, and dried at 60-80℃ for 12-16 hours to obtain carboxylated Ni-doped molybdenum sulfide nanosheets.

[0032] (3) The carboxylated Ni-doped molybdenum sulfide nanosheets obtained in step (2) were ultrasonically dispersed in deionized water to obtain a dispersion. Then, p-phenylenediamine was added to adjust the pH of the dispersion. The mixture was then reacted at 85-95℃ for 6-8h, cooled to room temperature, filtered, and dried at 60-80℃ for 14-18h to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets. The p-phenylenediamine-modified molybdenum sulfide nanosheets were then dispersed in a 0.7-0.9 mol / L hydrochloric acid solution. Aniline was then added and stirred rapidly for 30-50 min. Ammonium persulfate was then added and stirred at 500-1000 rpm for 20-40 min. The mixture was then reacted at 0℃ for 6-12h while maintaining the stirring speed. The mixture was then filtered, washed, and dried under vacuum at 60-80℃ for 8-12h to obtain the PANI@Ni-doped molybdenum sulfide composite material.

[0033] Preferably, in step (1), the nickel salt is one of nickel chloride, nickel nitrate, and nickel acetate, the molybdate is sodium molybdate or potassium molybdate, and the molar ratio of the nickel salt, molybdate, thiourea and hydroxylamine hydrochloride is 0.04-0.08:1:3.5-5.5:1.5-2.5.

[0034] More preferably, in step (1), the hydrothermal reaction is carried out at 180-220°C for 20-28 hours; and the drying is carried out at 60-80°C for 12-16 hours.

[0035] More preferably, in step (2), the mass ratio of the Ni-doped molybdenum sulfide nanosheets to mercaptoacetic acid is 1:4 to 8.

[0036] More preferably, in step (3), the pH is 9 to 11; the mass ratio of the carboxylated Ni-doped molybdenum sulfide nanosheets to p-phenylenediamine is 1:3 to 5; and the mass ratio of the p-phenylenediamine-modified molybdenum sulfide nanosheets, aniline, and ammonium persulfate is 1:10 to 12:12 to 14.

[0037] The preparation method of the green and environmentally friendly paint described above includes the following steps:

[0038] Alkyd resin, diethylene glycol tert-butyl ether, and diethylene glycol butyl ether are stirred and mixed at a speed of 2500–3500 rpm for 5–15 minutes. Then, the remaining raw materials are added, and stirring is continued at a speed of 2000–3000 rpm for 30–50 minutes to obtain a green and environmentally friendly paint.

[0039] The present invention has the following beneficial effects:

[0040] This invention improves the corrosion resistance of paint by adding zinc rosinate. By adding self-made Cu-modified MIL-100(Fe) and PANI@Ni-doped molybdenum sulfide composite material, the contact between the external environment and the metal surface is effectively blocked, thereby effectively improving the corrosion resistance. Moreover, the paint prepared by this invention also has excellent surface drying time, that is, it has good overall performance and wide application. Detailed Implementation

[0041] The present invention will be further illustrated below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field.

[0042] The alkyd resin is alkyd resin 307, the leveling agent is RG-5335, the dispersant is BYK110, the defoamer is F-2561, and the catalyst is cobalt naphthenate.

[0043] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0044] Example 1

[0045] A green and environmentally friendly paint, by weight, comprises the following raw materials:

[0046] 120 parts alkyd resin;

[0047] 10 parts of diethylene glycol tert-butyl ether;

[0048] 15 parts of diethylene glycol butyl ether;

[0049] 0.03 parts of zinc rosinate;

[0050] 0.06 parts of Cu-modified MIL-100(Fe);

[0051] 0.05 parts of PANI@Ni-doped molybdenum sulfide composite material;

[0052] 1.5 parts leveling agent;

[0053] 0.5 parts dispersant;

[0054] 0.6 parts of defoamer;

[0055] 1.6 parts of drying agent.

[0056] The preparation method of Cu-modified MIL-100(Fe) includes the following steps:

[0057] 0.2 mol copper nitrate, 1.8 mol ferric chloride and 1 mol trimesic acid were added to 200 mL of deionized water and stirred for 30 min. Then the mixture was transferred to a hydrothermal reactor and hydrothermally reacted at 160 °C for 14 h. After cooling to room temperature, the mixture was filtered, washed and dried at 90 °C for 12 h to obtain Cu-modified MIL-100(Fe).

[0058] The preparation method of PANI@Ni-doped molybdenum sulfide composite material includes the following steps:

[0059] (1) Add 0.06 mol nickel chloride, 1 mol sodium molybdate, 4.5 mol thiourea and 2 mol hydroxylamine hydrochloride to 250 mL of deionized water, then transfer to a hydrothermal reactor and react at 200 °C for 24 h. Cool to room temperature, filter, wash, and dry at 70 °C for 14 h to obtain Ni-doped molybdenum sulfide nanosheets.

[0060] (2) 10g of Ni-doped molybdenum sulfide nanosheets obtained in step (1) and 60g of mercaptoacetic acid were ultrasonically dispersed in 150mL of deionized water, ultrasonicated for 3h, then stirred for 30h, filtered, washed, and dried at 70℃ for 14h to obtain carboxylated Ni-doped molybdenum sulfide nanosheets.

[0061] (3) 10g of carboxylated Ni-doped molybdenum sulfide nanosheets obtained in step (2) were ultrasonically dispersed in 150mL of deionized water to obtain a dispersion. Then, 40g of p-phenylenediamine was added to adjust the pH of the dispersion to pH=10. The mixture was then reacted at 90℃ for 7h, cooled to room temperature, filtered, and dried at 70℃ for 16h to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets. Then, 10g of p-phenylenediamine-modified molybdenum sulfide nanosheets were dispersed in 100mL of 0.8mol / L hydrochloric acid solution. Then, 110g of aniline was added and stirred rapidly for 40min. Subsequently, 130g of ammonium persulfate was added and stirred at 800rpm for 30min. Under the condition of maintaining the stirring speed, the mixture was reacted at 0℃ for 10h, filtered, washed, and dried under vacuum at 70℃ for 10h to obtain PANI@Ni-doped molybdenum sulfide composite material.

[0062] A method for preparing a green and environmentally friendly paint includes the following steps:

[0063] Alkyd resin, diethylene glycol tert-butyl ether, and diethylene glycol butyl ether are stirred and mixed at a speed of 3000 rpm for 10 minutes. Then, the remaining raw materials are added, and stirring is continued at 2500 rpm for 40 minutes to obtain a green and environmentally friendly paint.

[0064] Example 2

[0065] A green and environmentally friendly paint, by weight, comprises the following raw materials:

[0066] 140 parts of alkyd resin;

[0067] 5 parts of diethylene glycol tert-butyl ether;

[0068] 20 parts of diethylene glycol butyl ether;

[0069] 0.02 parts of zinc rosinate;

[0070] 0.08 parts of Cu-modified MIL-100(Fe);

[0071] 0.03 parts of PANI@Ni-doped molybdenum sulfide composite material;

[0072] 2 parts leveling agent;

[0073] 0.4 parts dispersant;

[0074] 0.7 parts of defoamer;

[0075] One part of drying agent.

[0076] The preparation method of Cu-modified MIL-100(Fe) includes the following steps:

[0077] 0.3 mol copper chloride, 1.7 mol ferric acetate and 1 mol trimesic acid were added to 200 mL of deionized water and stirred for 40 min. Then the mixture was transferred to a hydrothermal reactor and hydrothermally reacted at 180 °C for 12 h. After cooling to room temperature, the mixture was filtered, washed, and dried at 100 °C for 10 h to obtain Cu-modified MIL-100(Fe).

[0078] The preparation method of PANI@Ni-doped molybdenum sulfide composite material is the same as in Example 1.

[0079] The preparation method of a green and environmentally friendly paint is the same as that of Example 1.

[0080] Example 3

[0081] A green and environmentally friendly paint, by weight, comprises the following raw materials:

[0082] 100 parts alkyd resin;

[0083] 15 parts of diethylene glycol tert-butyl ether;

[0084] 10 parts of diethylene glycol butyl ether;

[0085] 0.04 parts of zinc rosinate;

[0086] 0.04 parts of Cu-modified MIL-100(Fe);

[0087] 0.07 parts of PANI@Ni-doped molybdenum sulfide composite material;

[0088] 1 part leveling agent;

[0089] 0.6 parts dispersant;

[0090] 0.5 parts of defoamer;

[0091] Two parts of drying agent.

[0092] The preparation method of Cu-modified MIL-100(Fe) includes the following steps:

[0093] 0.1 mol copper acetate, 1.9 mol ferric nitrate, and 1 mol trimellitic acid were added to 200 mL of deionized water and stirred for 20 min. The mixture was then transferred to a hydrothermal reactor and hydrothermally reacted at 140 °C for 16 h. After cooling to room temperature, the mixture was filtered, washed, and dried at 80 °C for 14 h to obtain Cu-modified MIL-100(Fe). The copper salt was at least one selected from copper nitrate, copper chloride, and copper acetate; the iron salt was at least one selected from ferric chloride, ferric acetate, and ferric nitrate; and the molar ratio of the copper salt, iron salt, and trimellitic acid was 0.1:1.9:1.

[0094] The preparation method of PANI@Ni-doped molybdenum sulfide composite material is the same as that in Example 1.

[0095] The preparation method of a green and environmentally friendly paint is the same as that of Example 1.

[0096] Compare with Example 1

[0097] Comparative Example 1 is basically the same as Example 1, except that an equal amount of MIL-100(Fe) is used to replace Cu-modified MIL-100(Fe). The preparation method of MIL-100(Fe) includes the following steps:

[0098] 2 mol of ferric chloride and 1 mol of trimesic acid were added to 200 mL of deionized water and stirred for 30 min. Then the mixture was transferred to a hydrothermal reactor and hydrothermally reacted at 160 °C for 14 h. After cooling to room temperature, the mixture was filtered, washed, and dried at 90 °C for 12 h to obtain MIL-100(Fe).

[0099] Compare with Example 2

[0100] Comparative Example 2 is basically the same as Example 1. The difference is that step (1) in the preparation method of molybdenum sulfide composite material is: 1.06 mol sodium molybdate, 4.5 mol thiourea and 2 mol hydroxylamine hydrochloride are added to 250 mL of deionized water, then transferred to a hydrothermal reactor, and hydrothermally reacted at 200 °C for 24 h. After cooling to room temperature, the mixture is filtered, washed, and dried at 70 °C for 14 h to obtain molybdenum sulfide nanosheets.

[0101] Compare with Example 3

[0102] Comparative Example 3 is basically the same as Example 1, except that the preparation method of the PANI@Ni-doped molybdenum sulfide composite material includes the following steps:

[0103] (1) Add 0.06 mol nickel chloride, 1 mol sodium molybdate, 4.5 mol thiourea and 2 mol hydroxylamine hydrochloride to 250 mL of deionized water, then transfer to a hydrothermal reactor and react at 200 °C for 24 h. Cool to room temperature, filter, wash, and dry at 70 °C for 14 h to obtain Ni-doped molybdenum sulfide nanosheets.

[0104] (2) 10g of Ni-doped molybdenum sulfide nanosheets obtained in step (1) were ultrasonically dispersed in 150mL of deionized water to obtain a dispersion. Then, 40g of p-phenylenediamine was added to adjust the pH of the dispersion to pH=10. The mixture was then reacted at 90℃ for 7h, cooled to room temperature, filtered, and dried at 70℃ for 16h to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets. Then, 10g of p-phenylenediamine-modified molybdenum sulfide nanosheets were dispersed in 100mL of 0.8mol / L hydrochloric acid solution. Then, 110g of aniline was added and stirred rapidly for 40min. Subsequently, 130g of ammonium persulfate was added and stirred at 800rpm for 30min. Under the condition of maintaining the stirring speed, the mixture was reacted at 0℃ for 10h, filtered, washed, and dried under vacuum at 70℃ for 10h to obtain PANI@Ni-doped molybdenum sulfide composite material.

[0105] Compare with Example 4

[0106] Comparative Example 4 is basically the same as Example 1, except that an equal amount of Ni-doped molybdenum sulfide composite material is used instead of PANI@Ni-doped molybdenum sulfide composite material. The preparation method of the Ni-doped molybdenum sulfide composite material includes the following steps:

[0107] (1) Add 0.06 mol nickel chloride, 1 mol sodium molybdate, 4.5 mol thiourea and 2 mol hydroxylamine hydrochloride to 250 mL of deionized water, then transfer to a hydrothermal reactor and react at 200 °C for 24 h. Cool to room temperature, filter, wash, and dry at 70 °C for 14 h to obtain Ni-doped molybdenum sulfide nanosheets.

[0108] (2) 10g of Ni-doped molybdenum sulfide nanosheets obtained in step (1) and 60g of mercaptoacetic acid were ultrasonically dispersed into 150mL of deionized water, ultrasonicated for 3h, stirred for 30h, filtered, washed, and dried at 70℃ for 14h to obtain carboxylated Ni-doped molybdenum sulfide nanosheets.

[0109] Compare with Example 5

[0110] Comparative Example 5 is basically the same as Example 1, except that it does not contain Cu-modified MIL-100(Fe), and the zinc rosinate content is 0.08 parts.

[0111] Compare with Example 6

[0112] Comparative Example 6 is basically the same as Example 1, except that it does not contain Cu-modified MIL-100(Fe), and the amount of PANI@Ni-doped molybdenum sulfide composite material is 0.11 parts.

[0113] The properties of the paints prepared in Examples 1-3 and Comparative Examples 1-6 were tested.

[0114] The surface drying time and actual drying time were tested according to the GB / T 1728-1979 method.

[0115] Salt spray tests were conducted according to the method in GB / T 1771-2007.

[0116] The test results are shown in Table 1:

[0117] Table 1

[0118] Surface drying time h Practical time h Salt spray test Example 1 3.9 15.8 173h Example 2 4.4 16.9 168h Example 3 4.2 16.4 171h Compare with Example 1 4.7 17.6 163h Compare with Example 2 4.5 17.2 166h Compare with Example 3 5.2 18.3 158h Compare with Example 4 5.4 18.6 152h Compare with Example 5 5.8 19.1 144h Compare with Example 6 5.7 18.8 146h

[0119] The hardness of Examples 1-3 was tested using GB / T 1730-2007B method, and the specific test results are shown in Table 2.

[0120] Table 2

[0121] Example 1 Example 2 Example 3 hardness 0.42 0.45 0.44

[0122] As shown in Table 1, by comparing Example 1 with Comparative Examples 1-6, the green and environmentally friendly paint prepared by this invention exhibits excellent corrosion resistance, and also demonstrates excellent surface drying time and complete drying time. As shown in Table 2, the environmentally friendly paint prepared by this invention also possesses excellent hardness. In summary, the green and environmentally friendly paint prepared by this invention exhibits good overall performance and has wide applications.

[0123] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A green and environmentally friendly paint, characterized in that: By weight, it includes the following ingredients: 100-140 parts of alkyd resin; 5-15 parts of diethylene glycol tert-butyl ether; 10-20 parts of diethylene glycol butyl ether; Zinc rosinate 0.02–0.04 parts; Cu-modified MIL-100(Fe) 0.04–0.08 parts; 0.03–0.07 parts of PANI@Ni-doped molybdenum sulfide composite material; 1-2 parts leveling agent; Dispersant 0.4–0.6 parts; Defoamer 0.5-0.7 parts; 1-2 parts of drying agent; The preparation method of the PANI@Ni-doped molybdenum sulfide composite material includes the following steps: (1) Add nickel salt, molybdate, thiourea and hydroxylamine hydrochloride to deionized water, then transfer to a hydrothermal reactor for hydrothermal reaction, cool to room temperature, filter, wash and dry to obtain Ni-doped molybdenum sulfide nanosheets; the molar ratio of nickel salt, molybdate, thiourea and hydroxylamine hydrochloride is 0.04~0.08:1:3.5~5.5:1.5~2.5; (2) The Ni-doped molybdenum sulfide nanosheets obtained in step (1) and mercaptoacetic acid are ultrasonically dispersed in deionized water, ultrasonicated for 2-4 hours, stirred for 25-35 hours, filtered, washed, and dried at 60-80℃ for 12-16 hours to obtain carboxylated Ni-doped molybdenum sulfide nanosheets; the mass ratio of the Ni-doped molybdenum sulfide nanosheets to mercaptoacetic acid is 1:4-8. (3) The carboxylated Ni-doped molybdenum sulfide nanosheets obtained in step (2) were ultrasonically dispersed in deionized water to obtain a dispersion. Then, p-phenylenediamine was added to adjust the pH of the dispersion. The mixture was then reacted at 85–95 °C for 6–8 h, cooled to room temperature, filtered, and dried at 60–80 °C for 14–18 h to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets. The p-phenylenediamine-modified molybdenum sulfide nanosheets were then dispersed in a 0.7–0.9 mol / L hydrochloric acid solution. Aniline was then added and the mixture was stirred rapidly for 30–50 min. Ammonium persulfate was then added, and the mixture was stirred at 500–1000 rpm for 20–40 min. While maintaining the stirring speed, the mixture was reacted at 0°C for 6–12 h. After filtration and washing, the mixture was vacuum dried at 60–80°C for 8–12 h to obtain the PANI@Ni-doped molybdenum sulfide composite material. The mass ratio of the carboxylated Ni-doped molybdenum sulfide nanosheets to p-phenylenediamine was 1:3–5. The mass ratio of the p-phenylenediamine-modified molybdenum sulfide nanosheets, aniline, and ammonium persulfate was 1:10–12:12–14.

2. The green and environmentally friendly paint according to claim 1, characterized in that: The method for preparing Cu-modified MIL-100(Fe) includes the following steps: Copper salt, iron salt and pyromellitic acid were added to deionized water and stirred for a certain period of time. Then the mixture was transferred to a hydrothermal reactor for hydrothermal reaction. After cooling to room temperature, the mixture was filtered, washed and dried to obtain Cu-modified MIL-100(Fe).

3. The green and environmentally friendly paint according to claim 2, characterized in that: The copper salt is at least one of copper nitrate, copper chloride, and copper acetate, and the iron salt is at least one of ferric chloride, ferric acetate, and ferric nitrate. The molar ratio of the copper salt, iron salt, and trimesic acid is 0.1-0.3:1.7-1.9:

1.

4. The green and environmentally friendly paint according to claim 2, characterized in that: The stirring time is 20-40 min, the hydrothermal reaction is carried out at 140-180℃ for 12-16 h, and the drying is carried out at 80-100℃ for 10-14 h.

5. The green and environmentally friendly paint according to claim 1, characterized in that: In step (1), the nickel salt is one of nickel chloride, nickel nitrate, and nickel acetate, and the molybdate is sodium molybdate or potassium molybdate.

6. The green and environmentally friendly paint according to claim 1, characterized in that: In step (1), the hydrothermal reaction is carried out at 180-220°C for 20-28 hours; the drying is carried out at 60-80°C for 12-16 hours.

7. The green and environmentally friendly paint according to claim 1, characterized in that: In step (3), the pH is 9 to 11.

8. A method for preparing a green and environmentally friendly paint according to any one of claims 1-7, characterized in that: The preparation method includes the following steps: Alkyd resin, diethylene glycol tert-butyl ether, and diethylene glycol butyl ether are stirred and mixed at a speed of 2500–3500 rpm for 5–15 minutes. Then, the remaining raw materials are added, and stirring is continued at a speed of 2000–3000 rpm for 30–50 minutes to obtain a green and environmentally friendly paint.