Green environment-friendly paint and preparation method thereof

Abstract

The invention belongs to the technical field of paint, and particularly relates to green and environment-friendly paint and a preparation method thereof. The green environment-friendly paint prepared by the invention comprises the following raw materials in parts by weight: 100-140 parts of alkyd resin; 5 to 15 parts of diethylene glycol tert-butyl ether; 10 to 20 parts of diethylene glycol butyl ether; 0.02 to 0.04 part of zinc abietate; 0.04 to 0.08 part of Cu modified MIL-100 (Fe); 0.03 to 0.07 part of a PANI (at) Ni doped molybdenum sulfide composite material; 1-2 parts of a leveling agent; 0.4 to 0.6 part of a dispersant; 0.5 to 0.7 part of a defoaming agent; and 1-2 parts of a drier. According to the environment-friendly paint prepared by the invention, the Cu-modified MIL-100 (Fe) and ANI-Ni doped molybdenum sulfide composite material is added, and zinc abietate is matched, so that the environment-friendly paint has excellent corrosion resistance and other properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of paints. More specifically, it relates to a green and environment-friendly paint and a preparation method thereof. Background Art

[0002] Metal materials are an important type of structural materials, widely used in fields such as aerospace, transportation, and daily infrastructure. However, these metal materials are often corroded due to the influence of the harsh external environment. Coating a paint film on the metal surface is the most convenient, direct, and economical protection method. Alkyd resin varnish is an important anti-corrosion coating, but a single alkyd resin has poor corrosion resistance and low hardness due to the presence of a large number of ester bonds and hydroxyl groups. Therefore, incorporating some other materials into alkyd resin varnish to improve its performance has been favored by scholars at home and abroad.

[0003] Metal-organic framework compounds refer to porous compounds with variable structures formed by the coordination of metal clusters and multi-dentate organic ligands containing oxygen, nitrogen, etc. They have attracted extensive attention from scholars in various fields due to a series of advantages such as an ultra-high specific surface area and adjustable framework structure. Due to the relatively high specific surface area of metal-organic framework compounds, the contact surface with the resin can be increased, and the denseness of the coating can be enhanced, thereby improving the anti-corrosion performance of the coating.

[0004] CN118931339A discloses a preparation method of a varnish coating using block-shaped nickel oxide nanoparticles as a sealant. In this coating preparation method, block-shaped nickel oxide nanoparticles are used as the sealant on the surface of the metal component substrate, and then a layer of alkyd resin varnish enhanced with 2-mercaptobenzothiazole is coated. The coating prepared by this method has a relatively high corrosion potential, a relatively low corrosion current, and a relatively large impedance, indicating that the coating has good anti-corrosion performance. This coating can be applied to the anti-corrosion projects of the metal parts surfaces of electrical equipment such as air conditioners, electric water heaters, air conditioners, and refrigerators, as well as mechanical equipment such as tractors and cranes.

[0005] CN118620524A discloses a fast-drying epoxy alkyd varnish with water resistance and rust prevention and its preparation process, including the following raw materials in parts by weight: 35 - 45 parts of epoxy alkyd resin, 8 - 12 parts of a reinforcing modifier based on flaky graphene, 4 - 8 parts of soybean oil, 5 - 7 parts of a supplementary compatibility agent, 4 - 6 parts of a silane coupling agent, 4 - 6 parts of a curing agent, 0.2 - 0.3 parts of a drier, and 30 - 35 parts of a solvent. The fast-drying epoxy alkyd varnish of the present invention uses epoxy alkyd resin as the base material, and by adding soybean oil, silane coupling agent, curing agent, and drier as functional auxiliaries, and at the same time adding the reinforcing modifier based on flaky graphene and the supplementary compatibility agent to coordinate and cooperate with each other, the fast-drying property and impact resistance of the product are coordinately improved, and the salt spray resistance, water resistance, and stability of the product are significantly improved.

[0006] CN117264514A discloses a preparation method of alkyd resin varnish doped with broken rice grain-shaped cobalt MOFs. Using dry long-oil alkyd resin as the main film-forming substance, broken rice grain-shaped cobalt MOFs doping as the dopant, cobalt naphthenate as the drier, and n-butanol as the solvent, and mixing them, then stirring at high speed to obtain the alkyd resin varnish doped with broken rice grain-shaped cobalt MOFs. This varnish has a relatively high corrosion potential, a relatively low corrosion current, a relatively large impedance, and a relatively high hardness. This varnish can be applied to the anti-corrosion projects of metal parts of electrical equipment such as air conditioners, electric water heaters, air conditioners, refrigerators, etc., and mechanical equipment such as tractors and cranes.

[0007] CN117050623A discloses a preparation method of alkyd resin varnish doped with rotten wooden rod-shaped cobalt MOFs. Using dry long-oil alkyd resin and zinc rosinate as the main film-forming substances, rotten wooden rod-shaped cobalt MOFs doping as the dopant, cobalt naphthenate as the drier, and n-butanol as the solvent, and mixing them, then stirring at high speed to obtain the alkyd resin varnish doped with rotten wooden rod-shaped cobalt MOFs. This varnish has a relatively high corrosion potential, a relatively low corrosion current, a relatively large impedance, and a relatively high hardness. This varnish can be applied to the anti-corrosion projects of metal parts of electrical equipment such as air conditioners, electric water heaters, air conditioners, refrigerators, etc., 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 the following components: alkyd resin 40-60 wt%, pigment 10-20 wt%, functional filler 10-20 wt%, additive 0.5-2 wt%, and the solvent makes up the balance. When the weight ratio of the alkyd resin, the pigment, and the 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, talcum powder, and the weight ratio of calcium carbonate, diatomaceous earth, and talcum powder is 1:(1-2):(0.5-1), the dry time of the alkyd paint can be further reduced.

[0009] By adding additives to the paint, the performance of the paint can be improved. According to the required performance, the required additives can be selected to make the paint have corresponding performance. Based on this, the present invention provides a green and environmentally friendly paint, which has excellent corrosion resistance and other properties. Summary of the Invention

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

[0011] The object of the present invention is to provide a green and environment-friendly paint.

[0012] Another object of the present invention is to provide a preparation method of a green and environment-friendly paint.

[0013] The above object of the present invention is achieved by the following technical solutions:

[0014] A green and environment-friendly paint comprises the following raw materials in parts by weight:

[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] 0.02-0.04 parts of zinc rosinate;

[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 of leveling agent;

[0022] 0.4-0.6 parts of dispersant;

[0023] 0.5-0.7 parts of defoaming agent;

[0024] 1-2 parts of drier.

[0025] In the present invention, in a preferred technical solution, the preparation method of the Cu-modified MIL-100(Fe) comprises the following steps:

[0026] Copper salts, iron salts and trimesic acid were added to deionized water, stirred for a certain time, then transferred to a hydrothermal reaction kettle for hydrothermal reaction, cooled to room temperature, 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, the iron salt is at least one of ferric chloride, ferric acetate and ferric nitrate, and 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 °C for 12-16 h; the drying is carried out at 80-100 °C for 10-14 h.

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

[0030] (1) Nickel salts, molybdates, thiourea and hydroxylamine hydrochloride were added to deionized water, then transferred to a hydrothermal reaction kettle for hydrothermal reaction, cooled to room temperature, filtered, washed and dried to obtain Ni-doped molybdenum sulfide nanosheets;

[0031] (2) The Ni-doped molybdenum sulfide nanosheets obtained in step (1) and mercaptoacetic acid were ultrasonically dispersed in deionized water, ultrasonically treated for 2-4 h, then stirred for 25-35 h, filtered, washed, and dried at 60-80 °C for 12-16 h 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, the pH of the dispersion was adjusted, and then the reaction was carried out at 85-95 °C for 6-8 h, cooled to room temperature, filtered, dried at 60-80 °C for 14-18 h to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets, then the p-phenylenediamine-modified molybdenum sulfide nanosheets were dispersed in a 0.7-0.9 mol / L hydrochloric acid solution, then aniline was added and rapidly stirred for 30-50 min, then ammonium persulfate was added, stirred at a rotation speed of 500-1000 rpm for 20-40 min, and reacted at 0 °C for 6-12 h while maintaining the rotation speed, filtered, washed, and vacuum dried at 60-80 °C for 8-12 h 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 h; the drying is carried out at 60 - 80 °C for 12 - 16 h.

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

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

[0037] Based on the above-mentioned preparation method of a green and environmentally friendly paint, the preparation method includes the following steps:

[0038] Stir and mix alkyd resin, diethylene glycol tert-butyl ether, and diethylene glycol butyl ether at a stirring speed of 2500 - 3500 rpm for 5 - 15 min, then add the remaining raw materials, and continue to stir at a rotation speed of 2000 - 3000 rpm for 30 - 50 min to obtain a green and environmentally friendly paint.

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

[0040] By adding zinc rosinate, the corrosion resistance of the paint can be improved. By adding the self-made Cu-modified MIL-100(Fe) and PANI@Ni-doped molybdenum sulfide composite materials, the contact between the outside and the metal surface is effectively blocked, thereby effectively improving the corrosion resistance. Moreover, the surface drying time of the paint prepared by the present invention is also excellent, that is, the comprehensive performance is relatively good and it has a wide range of applications. Specific Embodiments

[0041] The following specific examples are used to further illustrate the present invention, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.

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

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

[0044] Example 1

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

[0046] 120 parts of alkyd resin;

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

[0048] 15 parts of diethylene glycol butyl ether;

[0049] 0.03 part of zinc rosinate;

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

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

[0052] 1.5 parts of leveling agent;

[0053] 0.5 part of dispersant;

[0054] 0.6 part of defoaming agent;

[0055] 1.6 parts of drier.

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

[0057] Add 0.2 mol of copper nitrate, 1.8 mol of ferric chloride and 1 mol of trimesic acid to 200 mL of deionized water, stir for 30 min, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction at 160 °C for 14 h, cool to room temperature, filter, wash, and dry at 90 °C for 12 h to obtain Cu-modified MIL-100(Fe).

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

[0059] (1) Add 0.06 mol of nickel chloride, 1 mol of sodium molybdate, 4.5 mol of thiourea and 2 mol of hydroxylamine hydrochloride to 250 mL of deionized water, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction 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) Ultrasonically disperse 10 g of the Ni-doped molybdenum sulfide nanosheets obtained in step (1) and 60 g of mercaptoacetic acid in 150 mL of deionized water, ultrasonicate for 3 h, then stir for 30 h, filter, wash, and dry at 70 °C for 14 h to obtain carboxylated Ni-doped molybdenum sulfide nanosheets;

[0061] (3) Ultrasonically disperse 10 g of the carboxylated Ni-doped molybdenum sulfide nanosheets obtained in step (2) into 150 mL of deionized water to obtain a dispersion, then add 40 g of p-phenylenediamine, adjust the pH of the dispersion to pH = 10, then react at 90 °C for 7 h, cool to room temperature, filter, and dry at 70 °C for 16 h to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets. Then disperse 10 g of the p-phenylenediamine-modified molybdenum sulfide nanosheets into 100 mL of 0.8 mol / L hydrochloric acid solution, then add 110 g of aniline and stir rapidly for 40 min, subsequently add 130 g of ammonium persulfate, stir at a rotation speed of 800 rpm for 30 min, and react at 0 °C for 10 h while maintaining the rotation speed, filter, wash, and vacuum dry at 70 °C for 10 h to obtain the PANI@Ni-doped molybdenum sulfide composite material.

[0062] A preparation method of a green environmental protection paint comprises the following steps:

[0063] Stir and mix alkyd resin, diethylene glycol tert-butyl ether, and diethylene glycol butyl ether at a stirring speed of 3000 rpm for 10 min, then add the remaining raw materials, and continue to stir at a rotation speed of 2500 rpm for 40 min to obtain the green environmental protection paint.

[0064] Example 2

[0065] A green environmental protection 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 part of zinc rosinate;

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

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

[0072] 2 parts of leveling agent;

[0073] 0.4 part of dispersant;

[0074] 0.7 part of defoaming agent;

[0075] 1 part of drier.

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

[0077] Add 0.3 mol of copper chloride, 1.7 mol of iron acetate, and 1 mol of benzene-1,3,5-tricarboxylic acid to 200 mL of deionized water, stir for 40 min, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction at 180 °C for 12 h, cool to room temperature, filter, wash, and dry at 100 °C for 10 h to obtain Cu-modified MIL-100(Fe).

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

[0079] The preparation method of a green environmental protection paint is the same as that in Example 1.

[0080] Example 3

[0081] A green environmental protection paint, by weight, comprises the following raw materials:

[0082] 100 parts of alkyd resin;

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

[0084] 10 parts of diethylene glycol butyl ether;

[0085] 0.04 part of zinc rosinate;

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

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

[0088] 1 part of leveling agent;

[0089] 0.6 part of dispersant;

[0090] 0.5 part of defoaming agent;

[0091] 2 parts of drier.

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

[0093] Add 0.1 mol of copper acetate, 1.9 mol of iron nitrate, and 1 mol of benzene-1,3,5-tricarboxylic acid to 200 mL of deionized water, stir for 20 min, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction at 140 °C for 16 h, cool to room temperature, filter, wash, and dry at 80 °C for 14 h to obtain Cu-modified MIL-100(Fe). The copper salt is at least one of copper nitrate, copper chloride, and copper acetate, the iron salt is at least one of ferric chloride, iron acetate, and iron nitrate, and the molar ratio of the copper salt, iron salt, and benzene-1,3,5-tricarboxylic acid is 0.1:1.9:1.

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

[0095] The preparation method of a green environmental protection paint is the same as that of Example 1.

[0096] Control Example 1

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

[0098] Add 2 mol of ferric chloride and 1 mol of trimesic acid to 200 mL of deionized water, stir for 30 min, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction at 160 °C for 14 h, cool to room temperature, filter, wash, and dry at 90 °C for 12 h to obtain MIL-100(Fe).

[0099] Control Example 2

[0100] Control Example 2 is basically the same as Example 1. The differences are as follows: Step (1) in the preparation method of the molybdenum sulfide composite material is as follows: Add 1.06 mol of sodium molybdate, 4.5 mol of thiourea, and 2 mol of hydroxylamine hydrochloride to 250 mL of deionized water, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction at 200 °C for 24 h, cool to room temperature, filter, wash, and dry at 70 °C for 14 h to obtain molybdenum sulfide nanosheets.

[0101] Control Example 3

[0102] Control Example 3 is basically the same as Example 1. The differences are as follows: The preparation method of the PANI@Ni-doped molybdenum sulfide composite material includes the following steps:

[0103] (1) Add 0.06 mol of nickel chloride, 1 mol of sodium molybdate, 4.5 mol of thiourea, and 2 mol of hydroxylamine hydrochloride to 250 mL of deionized water, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction 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) Ultrasonically disperse 10 g of the Ni-doped molybdenum sulfide nanosheets obtained in step (1) into 150 mL of deionized water to obtain a dispersion, then add 40 g of p-phenylenediamine, adjust the pH of the dispersion to pH = 10, then react at 90 °C for 7 h, cool to room temperature, filter, and dry at 70 °C for 16 h to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets. Then disperse 10 g of the p-phenylenediamine-modified molybdenum sulfide nanosheets into 100 mL of 0.8 mol / L hydrochloric acid solution, then add 110 g of aniline and stir rapidly for 40 min. Subsequently, add 130 g of ammonium persulfate, stir at a rotation speed of 800 rpm for 30 min, and under the condition of maintaining the rotation speed, react at 0 °C for 10 h, filter, wash, and vacuum dry at 70 °C for 10 h to obtain the PANI@Ni-doped molybdenum sulfide composite material.

[0105] Comparative Example 4

[0106] Comparative Example 4 is basically the same as Example 1, and the differences are as follows: an equal amount of Ni-doped molybdenum sulfide composite material is used to replace the 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 of nickel chloride, 1 mol of sodium molybdate, 4.5 mol of thiourea, and 2 mol of hydroxylamine hydrochloride to 250 mL of deionized water, then transfer to a hydrothermal reaction kettle, carry out hydrothermal reaction 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) Ultrasonically disperse 10 g of the Ni-doped molybdenum sulfide nanosheets obtained in step (1) and 60 g of mercaptoacetic acid into 150 mL of deionized water, sonicate for 3 h, then stir for 30 h, filter, wash, and dry at 70 °C for 14 h to obtain carboxylated Ni-doped molybdenum sulfide nanosheets.

[0109] Comparative Example 5

[0110] Comparative Example 5 is basically the same as Example 1, and the differences are as follows: it does not contain Cu-modified MIL-100(Fe), and zinc rosinate is 0.08 part.

[0111] Comparative Example 6

[0112] Comparative Example 6 is basically the same as Example 1, and the differences are as follows: it does not contain Cu-modified MIL-100(Fe), and the PANI@Ni-doped molybdenum sulfide composite material is 0.11 part.

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

[0114] Among them, the surface drying time and the actual drying time are tested according to the method of GB / T 1728-1979;

[0115] The salt spray test is carried out according to the method of GB / T 1771-2007.

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

[0117] Table 1

[0118] Skin drying time h Through drying 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 Control example 1 4.7 17.6 163h Control example 2 4.5 17.2 166h Control example 3 5.2 18.3 158h Control example 4 5.4 18.6 152h Control example 5 5.8 19.1 144h Control example 6 5.7 18.8 146h

[0119] The hardness of Examples 1-3 is tested by the method of GB / T 1730-2007B. 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] It can be seen from Table 1 that by comparing Example 1 with Comparative Examples 1-6, the green environmental protection paint prepared by the present invention has excellent corrosion resistance, and the surface drying time and the actual drying time are also excellent. It can be seen from Table 2 that the environmental protection paint prepared by the present invention also has excellent hardness. In summary, the green environmental protection paint prepared by the present invention has good comprehensive performance and is widely used.

[0123] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A green environmentally friendly paint, characterized by: By weight, it includes the following raw materials: 100-140 parts of alkyd resin; 5-15 parts of diethylene glycol tert-butyl ether; 10-20 parts of diethylene glycol butyl ether; 0.02-0.04 parts of zinc rosinate; Cu-modified MIL-100 (Fe) 0.04 to 0.08 parts; PANI@Ni doped molybdenum sulfide composite material 0.03-0.07 parts; 1-2 parts of leveling agent; Dispersant 0.4-0.6 parts; Defoaming agent 0.5-0.7 parts; 1 to 2 parts of drying agent.

2. The green environmental protection paint according to claim 1, characterized in that: The method for preparing the Cu-modified MIL-100 (Fe) comprises the following steps: Copper salt, iron salt and trimesic acid are added to deionized water, stirred for a certain period of time, and then transferred to a hydrothermal reactor for hydrothermal reaction, cooled to room temperature, filtered, washed and dried to obtain Cu-modified MIL-100 (Fe).

3. The green 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, the iron salt is at least one of iron chloride, iron acetate and iron nitrate, and 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 environmentally friendly paint according to claim 2, characterized in that: The stirring time is 20-40 minutes, the hydrothermal reaction is carried out at 140-180° C. for 12-16 hours, and the drying is carried out at 80-100° C. for 10-14 hours.

5. The green environmentally friendly paint according to claim 1, characterized in that: The preparation method of the PANI@Ni doped molybdenum sulfide composite material comprises the following steps: (1) adding nickel salt, molybdate, thiourea and hydroxylamine hydrochloride into deionized water, then transferring to a hydrothermal reactor for hydrothermal reaction, cooling to room temperature, filtering, washing and drying to obtain Ni-doped molybdenum sulfide nanosheets; (2) ultrasonically dispersing the Ni-doped molybdenum sulfide nanosheets and thioglycolic acid obtained in step (1) into deionized water, ultrasonically dispersing for 2 to 4 hours, then stirring for 25 to 35 hours, filtering, washing, and drying at 60 to 80° C. for 12 to 16 hours to obtain carboxylated Ni-doped molybdenum sulfide nanosheets; (3) Ultrasonic dispersion of the carboxylated Ni-doped molybdenum sulfide nanosheets obtained in step (2) into deionized water to obtain a dispersion, then adding p-phenylenediamine, adjusting the pH of the dispersion, then reacting at 85-95° C. for 6-8 hours, cooling to room temperature, filtering, and drying at 60-80° C. for 14-18 hours to obtain p-phenylenediamine-modified molybdenum sulfide nanosheets, then dispersing the p-phenylenediamine-modified molybdenum sulfide nanosheets into a 0.7-0.9 mol / L hydrochloric acid solution, then adding aniline and rapidly stirring for 30-50 minutes, then adding ammonium persulfate, stirring at a speed of 500-1000 rpm for 20-40 minutes, and reacting at 0° C. for 6-12 hours while maintaining the speed, filtering, washing, and vacuum drying at 60-80° C. for 8-12 hours to obtain a PANI@Ni-doped molybdenum sulfide composite material.

6. The green environmentally friendly paint according to claim 5, characterized in that: 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.

7. The green environmentally friendly paint according to claim 5, characterized in that: 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.

8. The green environmentally friendly paint according to claim 5, characterized in that: In step (2), the mass ratio of the Ni-doped molybdenum sulfide nanosheets to thioglycolic acid is 1:4-8.

9. The green environmentally friendly paint according to claim 5, characterized in that: In step (3), the pH is 9-11; the mass ratio of the carboxylated Ni-doped molybdenum sulfide nanosheets and p-phenylenediamine is 1:3-5; the mass ratio of the p-phenylenediamine-modified molybdenum sulfide nanosheets, aniline, and ammonium persulfate is 1:10-12:12-14.

10. A method for preparing a green environmentally friendly paint according to any one of claims 1 to 9, characterized in that: The preparation method comprises the following steps: The alkyd resin, diethylene glycol tert-butyl ether and diethylene glycol butyl ether are stirred and mixed at a stirring speed of 2500-3500 rpm for 5-15 minutes, and then the remaining raw materials are added and stirred at a speed of 2000-3000 rpm for 30-50 minutes to obtain a green environmentally friendly paint.