Two-component aerosol spray paint and preparation method thereof

Abstract

The invention discloses a kind of two-component aerosol spray paint and preparation method thereof, relate to the field of spray paint.The two-component aerosol spray paint prepared by the present invention, including component A and component B, component A includes modified acrylate copolymer, modified multi-walled carbon nanotube, environmentally friendly solvent, rheological additive, leveling agent, propellant, hydroxy acrylic resin, and component B includes isocyanate curing agent, solvent;Wherein modified acrylate copolymer is by methyl methacrylate, n-butyl acrylate, dimethylallylamine under initiator initiation, obtain acrylate copolymer, then react with chloromethyl (methyl) phosphinoyl chloride, then react with 5-amino-2-chloropyrimidine, then react with 3-methoxy-2-(tributyltin alkyl) pyridine, finally obtained by demethylation of boron tribromide;Modified multi-walled carbon nanotube is by chlorinated multi-walled carbon nanotube grafted chitosan, after sodium periodate oxidation and 2-amino-4,6-di-tert-butylphenol reaction.

Description

Technical Field

[0001] The invention relates to the field of spray paint, in particular to a two-component aerosol spray paint and a preparation method thereof. Background Art

[0002] Two-component aerosol spray paint is an important product type in the current coatings field. There are many types of paints on the market, mainly including one-component paint and two-component paint. One-component paint generally does not require cross-linking and curing. It usually has only one package and can be used immediately after opening and directly forming a film. This type of paint is simple to operate, but its performance is relatively limited.

[0003] Two-component paint is a coating made from a mixture of two different ingredients, one of which is a base coating and the other is a curing agent. Although two-component paint is superior to single-component paint in performance, the two-component aerosol spray paint currently on the market still has some shortcomings. For example, for spray paint used on metal surfaces, the coating formed by the spray paint needs to be able to prevent moisture and oxygen in the air from invading the metal surface and causing metal corrosion; coatings used outdoors for a long time are very likely to age and crack under ultraviolet radiation, thereby leading to a decrease in coating performance. Therefore, in order to overcome these shortcomings, it is particularly important to develop two-component aerosol spray paints with anti-corrosion and anti-UV aging properties. In addition, the spray paint can also be given antibacterial and flame retardant properties, which can broaden the application range of two-component spray paints while preventing microbial erosion and improving safety, and meet the different needs of users. Summary of the Invention

[0004] The object of the present invention is to provide a two-component aerosol spray paint and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A two-component aerosol spray paint, comprising component A and component B, wherein component A comprises a modified acrylate copolymer, modified multi-walled carbon nanotubes, an environmentally friendly solvent, a rheological additive, a leveling agent, a propellant, and a hydroxylated acrylic resin; and component B comprises an isocyanate curing agent and a solvent.

[0007] As an optimization, the modified acrylate copolymer is prepared by reacting methyl methacrylate, n-butyl acrylate, and dimethylallylamine under the initiation of an initiator to obtain an acrylate copolymer, reacting the acrylate copolymer with chloromethyl (methyl) phosphinoyl chloride to obtain a quaternized acrylate copolymer; then reacting the copolymer with 5-amino-2-chloropyrimidine to obtain a chloropyrimidinyl acrylate copolymer, then reacting the copolymer with 3-methoxy-2-(tributylstannyl)pyridine to obtain a pre-modified acrylate copolymer, and finally demethylating the copolymer with boron tribromide.

[0008] As an optimization, the modified multi-walled carbon nanotubes are obtained by grafting chitosan onto acyl chloride multi-walled carbon nanotubes, oxidizing with sodium periodate, and reacting with 2-amino-4,6-di-tert-butylphenol.

[0009] A method for preparing a two-component aerosol spray paint comprises the following steps:

[0010] (1) Methyl methacrylate, n-butyl acrylate, dimethylallylamine, and toluene were mixed in a mass ratio of 0.5:4:5.5:(20-30), heated to 80-90°C under nitrogen protection, added with an initiator solution of 0.3 times the volume of toluene, stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene again, stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene again, stirred for 90 minutes, and finally dried in vacuum at 80°C for 24 hours to obtain an acrylate polymer;

[0011] (2) mixing an acrylate polymer, triethylamine, chloromethyl (methyl) phosphinoyl chloride, and dichloromethane in a mass ratio of 1: (0.3-0.5): (0.8-0.9): (20-30), heating to 70-80°C, reacting for 12 hours, adding a saturated sodium bicarbonate aqueous solution equal in volume to the dichloromethane, taking the organic layer and drying it in air at 45°C for 12 hours, and then vacuum drying it at 50°C for 20 hours to obtain a quaternized acrylate copolymer;

[0012] (3) Weighing a quaternized acrylate copolymer and 5-amino-2-chloropyrimidine in a mass ratio of 1:(1-1.2), mixing the quaternized acrylate copolymer and dichloromethane in a mass ratio of 1:(20-30) to obtain a quaternized acrylate copolymer solution, mixing 5-amino-2-chloropyrimidine, triethylamine, and dichloromethane in a mass ratio of 1:(1.2-1.3):(10-12) to obtain a 5-amino-2-chloropyrimidine solution, and adding the 5-amino-2-chloropyrimidine solution dropwise to the quaternized acrylate copolymer solution at a dropping rate of 1 mL / min. After the dropwise addition is completed, the reaction is continued for 2-3 hours, and a 10 wt% hydrochloric acid solution of 10-12 times the mass of the quaternized acrylate copolymer is added, and then a saturated sodium bicarbonate solution of 10-12 times the mass of the quaternized acrylate copolymer is added. The organic phase is taken and subjected to vacuum rotary evaporation to obtain a chloropyrimidyl acrylate copolymer;

[0013] (4) 3-methoxy-2-(tributyltinyl)pyridine, chloropyrimidinyl acrylate copolymer, lithium chloride, and N,N-dimethylformamide are mixed in a mass ratio of 1:(0.3-0.5):(0.1-0.2):(10-12) and degassed, and tetrakis(triphenylphosphine)palladium(0) in an amount of 0.1-0.2 times the mass of 3-methoxy-2-(tributyltinyl)pyridine is added, and the mixture is heated to 100° C. and reacted for 16-18 hours. After the reaction is completed, the pre-modified acrylate copolymer is obtained by rotary evaporation under reduced pressure;

[0014] (5) Under argon protection, anhydrous and oxygen-free conditions, the pre-modified acrylate copolymer and dichloromethane are mixed in a mass ratio of 1: (50-60), cooled to -20 ° C, and 0.3-0.5 times the volume of the pre-modified acrylate copolymer of boron tribromide is added dropwise at a rate of 0.5 mL / min. After the addition is completed, the reaction is continued at -20 ° C for 12 hours. After the reaction is completed, methanol with a volume of 0.1 times that of dichloromethane is added, and then an ice-water mixture with a mass of 3-4 times that of dichloromethane is added. The mixture is filtered and vacuum-dried at 50 ° C for 20 hours to obtain a modified acrylate copolymer;

[0015] (6) Pre-modified multi-walled carbon nanotubes, 2-amino-4,6-di-tert-butylphenol, and anhydrous ethanol were mixed in a mass ratio of 1:(4-5):(50-60), refluxed at 78°C for 5-6 hours, cooled to room temperature after the reaction, filtered, and washed with anhydrous ethanol for 3-4 times, and finally vacuum dried at 60°C for 12 hours to obtain modified multi-walled carbon nanotubes;

[0016] (7) Weigh 15-20 parts by mass of modified acrylate copolymer, 3-5 parts by mass of modified multi-walled carbon nanotubes, 30-40 parts by mass of environmentally friendly solvent, 0.1-0.5 parts by mass of rheological additive, 0.1-0.5 parts by mass of leveling agent, 20-25 parts by mass of propellant, and 20 parts by mass of hydroxy acrylic resin; stir the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, and hydroxy acrylic resin evenly and grind them to a fineness of ≤45 μm. After grinding, put them into the liquid feed end of a two-component aerosol can, continue to add the propellant and seal it to obtain component A; weigh 3-5 parts by mass of isocyanate curing agent and 20-30 parts by mass of solvent, stir the isocyanate curing agent and solvent evenly, put them into the curing agent end of a two-component aerosol can and seal it to obtain component B, press the curing agent end and shake it to mix evenly to obtain a two-component aerosol spray paint.

[0017] As an optimization, the initiator solution in step (1) comprises ammonium persulfate and pure water, wherein the mass ratio of ammonium persulfate to pure water is 1:20.

[0018] As an optimization, the preparation method of the pre-modified multi-walled carbon nanotubes in step (6) is as follows: multi-walled carbon nanotubes and 68wt% concentrated nitric acid are mixed in a mass ratio of 1:30, heated to 120°C and refluxed for 48h, and then washed with pure water for 7-8 times to obtain carboxylated multi-walled carbon nanotubes; carboxylated multi-walled carbon nanotubes and thionyl chloride are mixed in a mass ratio of 1:20, refluxed at 70°C for 24h, cooled to room temperature, filtered, washed with tetrahydrofuran for 5-6 times, and dried at 50-60°C for 12h to obtain chlorinated multi-walled carbon nanotubes; chitosan is dispersed in N,N-dimethylformamide 30 times the mass of chitosan, allowed to stand for 12h, and chitosan is added under nitrogen protection. The chitosan grafted multi-walled carbon nanotubes were prepared by adding 0.3-0.5 times of acyl chloride multi-walled carbon nanotubes, ultrasonically treated for 2 hours, and then reacted for 96 hours. After the reaction, the mixture was filtered and washed three times with a 2wt% acetic acid solution, filtered with a 0.2μm microporous filter membrane, and finally vacuum dried at 60°C for 12 hours to obtain chitosan grafted multi-walled carbon nanotubes; the chitosan grafted multi-walled carbon nanotubes and an acetic acid buffer solution with a pH of 3 were mixed in a mass ratio of 1:80, and under nitrogen protection, a sodium periodate aqueous solution with a mass of 5-6 times that of the chitosan grafted multi-walled carbon nanotubes was added, and the mixture was reacted at 4°C for 44-48 hours, filtered and washed 3-4 times with pure water, and finally vacuum dried at 60°C for 12 hours to obtain pre-modified multi-walled carbon nanotubes.

[0019] As an optimization, the multi-walled carbon nanotube model is L-MWNT-1020; the deacetylation degree of the chitosan is ≥95%.

[0020] As an optimization, the sodium periodate aqueous solution is prepared by mixing sodium periodate and water in a mass ratio of 1:20.

[0021] As an optimization, the model of the hydroxy acrylic resin in step (7) is HU56024; the environmentally friendly solvent is propylene glycol ether acetate; the model of the isocyanate curing agent is Basonat HB100; the model of the leveling agent is YCK-1270N; the model of the rheological additive is BYK-7410; the model of the propellant is HFC-134a; and the solvent is acetone.

[0022] The beneficial effects of the present invention are as follows:

[0023] The present invention prepares a two-component aerosol spray paint. First, methyl methacrylate, n-butyl acrylate, and dimethylallylamine are reacted with an initiator to obtain an acrylate copolymer. The acrylate copolymer is reacted with chloromethyl (methyl) phosphinoyl chloride to obtain a quaternized acrylate copolymer. The quaternized acrylate copolymer is reacted with 5-amino-2-chloropyrimidine to obtain a chloropyrimidyl acrylate copolymer. The quaternized acrylate copolymer is reacted with 3-methoxy-2-(tributylstannyl)pyridine to obtain a pre-modified acrylate copolymer. Finally, the pre-modified acrylate copolymer is demethylated with boron tribromide to obtain a modified acrylate copolymer. Acrylate copolymer; secondly, acyl chloride multi-walled carbon nanotubes are grafted onto chitosan, and after oxidation with sodium periodate, they are reacted with 2-amino-4,6-di-tert-butylphenol to obtain modified multi-walled carbon nanotubes; finally, the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, propellant, and hydroxyl acrylic resin are loaded into the feed liquid end of a two-component aerosol can, and the isocyanate curing agent and solvent are loaded into the curing agent end of the two-component aerosol can, and the curing agent end is pressed and shaken to mix evenly to obtain a two-component aerosol spray paint.

[0024] First, methyl methacrylate, n-butyl acrylate, and dimethylallylamine are induced by an initiator to obtain an acrylate copolymer, wherein the dimethylallylamine makes the side chain of the acrylate copolymer have a tertiary amine structure, and the acrylate copolymer is reacted with chloromethyl (methyl) phosphinoyl chloride to obtain a quaternized acrylate copolymer, and the chloromethyl group on the chloromethyl (methyl) phosphinoyl chloride reacts with the tertiary amine to form a quaternary ammonium salt with antibacterial properties, which can give the spray paint antibacterial properties, and the introduction of phosphorus elements can give the spray paint flame retardant properties, and the phosphoramide group on the quaternized acrylate copolymer undergoes an amidation reaction with the amino group on 5-amino-2-chloropyrimidine to obtain a chloropyrimidyl acrylate copolymer, and then The pre-modified acrylate copolymer is reacted with 3-methoxy-2-(tributyltinyl)pyridine to obtain a pre-modified acrylate copolymer. The methoxypyridine functional group on the 3-methoxy-2-(tributyltinyl)pyridine is grafted onto 5-amino-2-chloropyrimidine. Finally, the modified acrylate copolymer is demethylated with boron tribromide. Boron tribromide removes the methyl group on the 3-methoxy-2-(tributyltinyl)pyridine to generate a hydroxyl group. The hydroxyl group is located at the ortho position of the nitrogen element on the pyrimidine group and can form an intramolecular chelate ring with the nitrogen element. When exposed to ultraviolet light, the light energy is converted into heat energy and dissipated, thereby improving the material's resistance to ultraviolet aging. The divalent structure formed by pyridine and pyrimidine has a good complexing effect on metals.

[0025] Secondly, chitosan is grafted onto acyl chloride multi-walled carbon nanotubes. Multi-walled carbon nanotubes have excellent electrical conductivity. When they are uniformly dispersed in the coating, good electrochemical contact will form a conductive network, which greatly enhances the electrochemical protection ability of the coating. It can also form a shielding structure in the coating formed by spray painting, effectively preventing the penetration and diffusion of corrosive media, and improving the physical anti-corrosion properties of the coating; chitosan, as a natural polysaccharide, has good hydrophilicity and adhesion, which can enhance the affinity between the spray paint and the substrate. Chitosan is oxidized by sodium periodate to form a dialdehyde group, which reacts with 2-amino-4,6-di-tert-butylphenol to form a Schiff base to obtain modified multi-walled carbon nanotubes; the Schiff base and the adjacent hydroxyl group have a good complexing effect on metal ions.

[0026] Finally, the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, hydroxy acrylic resin, and propellant are loaded into the liquid feed end of the two-component aerosol can, and the isocyanate curing agent and solvent are loaded into the curing agent end of the two-component aerosol can, and the curing agent end is pressed and shaken to mix evenly to obtain a two-component aerosol spray paint; the metal ligands on the modified acrylate copolymer and the modified multi-walled carbon nanotubes can be coordinated and complexed with metal ions. For metal substrates, they can undergo physical and chemical adsorption with the metal substrate before corrosion occurs, forming a dense protective film on the surface of the substrate, which plays a more excellent physical barrier role. During the corrosion process, they can undergo chelation reaction with free metal ions to generate stable organic chelates. Such organic chelates have good compatibility with the coating and are not prone to phase separation, thereby delaying further corrosion. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] The initiator solution used in the following examples and comparative examples is prepared by mixing ammonium persulfate and pure water in a mass ratio of 1:20; the multi-walled carbon nanotubes used are L-MWNT-1020; the deacetylation degree of the chitosan used is ≥95%; the sodium periodate solution used is prepared by mixing sodium periodate and water in a mass ratio of 1:20; the hydroxylated acrylic resin used is HU56024; the environmentally friendly solvent used is propylene glycol ether acetate; the isocyanate curing agent used is Basonat HB100; the leveling agent used is YCK-1270N; the rheological additive used is BYK-7410; the propellant used is HFC-134a; and the solvent used is acetone.

[0029] Example 1:

[0030] A method for preparing a two-component aerosol spray paint, comprising the following steps:

[0031] (1) Methyl methacrylate, n-butyl acrylate, dimethylallylamine, and toluene were mixed in a mass ratio of 0.5:4:5.5:20, heated to 90°C under nitrogen protection, added with an initiator solution of 0.3 times the volume of toluene, stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene again, stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene again, stirred for 90 minutes, and finally dried in vacuum at 80°C for 24 hours to obtain an acrylate polymer;

[0032] (2) The acrylate polymer, triethylamine, chloromethyl (methyl) phosphinoyl chloride, and dichloromethane were mixed in a mass ratio of 1:0.3:0.8:20, heated to 80°C, reacted for 12 hours, and an equal volume of saturated sodium bicarbonate aqueous solution to the dichloromethane was added. The organic layer was dried in air at 45°C for 12 hours, and then vacuum dried at 50°C for 20 hours to obtain a quaternized acrylate copolymer;

[0033] (3) Weighing a quaternized acrylate copolymer and 5-amino-2-chloropyrimidine in a mass ratio of 1:1, mixing the quaternized acrylate copolymer and dichloromethane in a mass ratio of 1:20 to obtain a quaternized acrylate copolymer solution, mixing 5-amino-2-chloropyrimidine, triethylamine, and dichloromethane in a mass ratio of 1:1.2:10 to obtain a 5-amino-2-chloropyrimidine solution, and adding the 5-amino-2-chloropyrimidine solution dropwise to the quaternized acrylate copolymer solution at a dropping rate of 1 mL / min. After the dropwise addition is completed, the reaction is continued for 3 h, and a 10 wt% hydrochloric acid solution of 10 times the mass of the quaternized acrylate copolymer is added, and then a saturated sodium bicarbonate solution of 10 times the mass of the quaternized acrylate copolymer is added. The organic phase is taken and subjected to vacuum rotary evaporation to obtain a chloropyrimidyl acrylate copolymer;

[0034] (4) 3-methoxy-2-(tributyltinyl)pyridine, chloropyrimidinyl acrylate copolymer, lithium chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.3:0.1:10 and degassed, and tetrakis(triphenylphosphine)palladium(0) in an amount 0.1 times the mass of 3-methoxy-2-(tributyltinyl)pyridine was added, and the mixture was heated to 100° C. and reacted for 18 hours. After the reaction was completed, the pre-modified acrylate copolymer was obtained by rotary evaporation under reduced pressure;

[0035] (5) Under argon protection, anhydrous and oxygen-free conditions, the pre-modified acrylate copolymer and dichloromethane were mixed in a mass ratio of 1:50, cooled to -20°C, and 0.3 times the volume of boron tribromide of the pre-modified acrylate copolymer was added dropwise at a rate of 0.5 mL / min. After the addition was completed, the reaction was continued at -20°C for 12 hours. After the reaction was completed, methanol with a volume of 0.1 times that of dichloromethane was added, and then an ice-water mixture with a mass of 3 times that of dichloromethane was added. The mixture was filtered and vacuum-dried at 50°C for 20 hours to obtain a modified acrylate copolymer;

[0036] (6) Multi-walled carbon nanotubes and 68wt% concentrated nitric acid were mixed in a mass ratio of 1:30, heated to 120℃ and refluxed for 48h, and then washed with pure water for 7 times to obtain carboxylated multi-walled carbon nanotubes; carboxylated multi-walled carbon nanotubes and thionyl chloride were mixed in a mass ratio of 1:20, refluxed at 70℃ for 24h, cooled to room temperature, filtered, washed with tetrahydrofuran for 6 times, and dried at 60℃ for 12h to obtain chlorinated multi-walled carbon nanotubes; chitosan was dispersed in N,N-dimethylformamide (30 times the mass of chitosan), allowed to stand for 12h, and chlorinated multi-walled carbon nanotubes (0.3 times the mass of chitosan) were added under nitrogen protection, ultrasonically treated for 2h, and continued to react for 96h. After the reaction was completed, it was filtered and washed with 2wt% acetic acid solution for 3 times, and 0.2μm was used. The mixture was filtered through a microporous membrane and finally vacuum dried at 60°C for 12 hours to obtain chitosan-grafted multi-walled carbon nanotubes; the chitosan-grafted multi-walled carbon nanotubes and an acetic acid buffer solution with a pH of 3 were mixed in a mass ratio of 1:80, and under nitrogen protection, a sodium periodate aqueous solution 5 times the mass of the chitosan-grafted multi-walled carbon nanotubes was added, and the mixture was reacted at 4°C for 48 hours, filtered and washed with pure water 4 times, and finally vacuum dried at 60°C for 12 hours to obtain pre-modified multi-walled carbon nanotubes; the pre-modified multi-walled carbon nanotubes, 2-amino-4,6-di-tert-butylphenol, and anhydrous ethanol were mixed in a mass ratio of 1:4:50, refluxed at 78°C for 6 hours, and after the reaction, cooled to room temperature, filtered and washed with anhydrous ethanol 4 times, and finally vacuum dried at 60°C for 12 hours to obtain modified multi-walled carbon nanotubes;

[0037] (7) Weigh 15 parts of modified acrylate copolymer, 3 parts of modified multi-walled carbon nanotubes, 30 parts of environmentally friendly solvent, 0.1 parts of rheological additive, 0.1 parts of leveling agent, 20 parts of hydroxy acrylic resin, and 20 parts of propellant by weight; stir the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, and hydroxy acrylic resin evenly and grind them to a fineness of ≤45 μm. After grinding, put them into the liquid feed end of a two-component aerosol can, continue to add propellant and seal it to obtain component A; weigh 3 parts of isocyanate curing agent and 20 parts of solvent by weight, stir the isocyanate curing agent and solvent evenly, put them into the curing agent end of a two-component aerosol can and seal it to obtain component B, press the curing agent end and shake it to mix evenly, and obtain a two-component aerosol spray paint.

[0038] Example 2:

[0039] A method for preparing a two-component aerosol spray paint, comprising the following steps:

[0040] (1) Methyl methacrylate, n-butyl acrylate, dimethylallylamine, and toluene were mixed in a mass ratio of 0.5:4:5.5:25, heated to 85°C under nitrogen protection, added with an initiator solution 0.3 times the volume of toluene, stirred for 90 minutes, then added with an initiator solution 0.3 times the volume of toluene again, stirred for 90 minutes, then added with an initiator solution 0.3 times the volume of toluene again, stirred for 90 minutes, and finally dried in vacuum at 80°C for 24 hours to obtain an acrylate polymer;

[0041] (2) The acrylate polymer, triethylamine, chloromethyl (methyl) phosphinoyl chloride, and dichloromethane were mixed in a mass ratio of 1:0.4:0.85:25, heated to 75°C, reacted for 12 hours, and an equal volume of saturated sodium bicarbonate aqueous solution to the dichloromethane was added. The organic layer was dried in air at 45°C for 12 hours, and then vacuum dried at 50°C for 20 hours to obtain a quaternized acrylate copolymer;

[0042] (3) Weighing a quaternized acrylate copolymer and 5-amino-2-chloropyrimidine in a mass ratio of 1:1.1, mixing the quaternized acrylate copolymer and dichloromethane in a mass ratio of 1:25 to obtain a quaternized acrylate copolymer solution, mixing 5-amino-2-chloropyrimidine, triethylamine, and dichloromethane in a mass ratio of 1:1.25:11 to obtain a 5-amino-2-chloropyrimidine solution, and adding the 5-amino-2-chloropyrimidine solution dropwise to the quaternized acrylate copolymer solution at a dropping rate of 1 mL / min. After the dropwise addition is completed, the reaction is continued for 2.5 h, and a 10 wt% hydrochloric acid solution of 11 times the mass of the quaternized acrylate copolymer is added, and then a saturated sodium bicarbonate solution of 11 times the mass of the quaternized acrylate copolymer is added. The organic phase is taken and subjected to vacuum rotary evaporation to obtain a chloropyrimidyl acrylate copolymer;

[0043] (4) 3-methoxy-2-(tributyltinyl)pyridine, chloropyrimidinyl acrylate copolymer, lithium chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.4:0.15:11 and degassed, and tetrakis(triphenylphosphine)palladium(0) in an amount of 0.15 times the mass of 3-methoxy-2-(tributyltinyl)pyridine was added, and the mixture was heated to 100° C. and reacted for 17 hours. After the reaction was completed, the pre-modified acrylate copolymer was obtained by rotary evaporation under reduced pressure;

[0044] (5) Under argon protection, anhydrous and oxygen-free conditions, the pre-modified acrylate copolymer and dichloromethane were mixed in a mass ratio of 1:55, cooled to -20°C, and 0.4 times the volume of boron tribromide of the pre-modified acrylate copolymer was added dropwise at a rate of 0.5 mL / min. After the addition was completed, the reaction was continued at -20°C for 12 hours. After the reaction was completed, methanol with a volume of 0.1 times that of dichloromethane was added, and then an ice-water mixture with a mass of 3.5 times that of dichloromethane was added. The mixture was filtered and vacuum dried at 50°C for 20 hours to obtain a modified acrylate copolymer;

[0045] (6) Multi-walled carbon nanotubes and 68wt% concentrated nitric acid were mixed in a mass ratio of 1:30, heated to 120℃ and refluxed for 48h, and then washed with pure water for 7 times to obtain carboxylated multi-walled carbon nanotubes; carboxylated multi-walled carbon nanotubes and thionyl chloride were mixed in a mass ratio of 1:20, refluxed at 70℃ for 24h, cooled to room temperature, filtered, washed with tetrahydrofuran for 5 times, and dried at 55℃ for 12h to obtain chlorinated multi-walled carbon nanotubes; chitosan was dispersed in N,N-dimethylformamide (30 times the mass of chitosan), allowed to stand for 12h, and chlorinated multi-walled carbon nanotubes (0.4 times the mass of chitosan) were added under nitrogen protection, ultrasonically treated for 2h, and continued to react for 96h. After the reaction was completed, it was filtered and washed with 2wt% acetic acid solution for 3 times, and a 0.2μm microporous Filter the mixture with a filter membrane, and finally vacuum dry it at 60°C for 12 hours to obtain chitosan-grafted multi-walled carbon nanotubes; mix the chitosan-grafted multi-walled carbon nanotubes and an acetic acid buffer solution with a pH of 3 in a mass ratio of 1:80, add a sodium periodate aqueous solution 5.5 times the mass of the chitosan-grafted multi-walled carbon nanotubes under nitrogen protection, react at 4°C for 45 hours, filter and wash with pure water three times, and finally vacuum dry it at 60°C for 12 hours to obtain pre-modified multi-walled carbon nanotubes; mix the pre-modified multi-walled carbon nanotubes, 2-amino-4,6-di-tert-butylphenol, and anhydrous ethanol in a mass ratio of 1:4.5:55, reflux at 78°C for 5.5 hours, cool to room temperature, filter and wash with anhydrous ethanol three times, and finally vacuum dry it at 60°C for 12 hours to obtain modified multi-walled carbon nanotubes;

[0046] (7) Weigh 17 parts of modified acrylate copolymer, 4 parts of modified multi-walled carbon nanotubes, 35 parts of environmentally friendly solvent, 0.3 parts of rheological additive, 0.3 parts of leveling agent, 20 parts of hydroxy acrylic resin, and 23 parts of propellant by weight; stir the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, and hydroxy acrylic resin evenly and grind them to a fineness of ≤45 μm. After grinding, put them into the liquid feed end of a two-component aerosol can, continue to add propellant and seal it to obtain component A; weigh 4 parts of isocyanate curing agent and 25 parts of solvent by weight, stir the isocyanate curing agent and solvent evenly, put them into the curing agent end of a two-component aerosol can and seal it to obtain component B, press the curing agent end and shake it to mix evenly, and obtain a two-component aerosol spray paint.

[0047] Example 3:

[0048] A method for preparing a two-component aerosol spray paint, comprising the following steps:

[0049] (1) Methyl methacrylate, n-butyl acrylate, dimethylallylamine, and toluene were mixed in a mass ratio of 0.5:4:5.5:30, heated to 80°C under nitrogen protection, added with an initiator solution 0.3 times the volume of toluene, stirred for 90 minutes, then added with an initiator solution 0.3 times the volume of toluene again, stirred for 90 minutes, then added with an initiator solution 0.3 times the volume of toluene again, stirred for 90 minutes, and finally dried in vacuum at 80°C for 24 hours to obtain an acrylate polymer;

[0050] (2) The acrylate polymer, triethylamine, chloromethyl (methyl) phosphinoyl chloride, and dichloromethane were mixed in a mass ratio of 1:0.5:0.9:30, heated to 70°C, reacted for 12 hours, and an equal volume of saturated sodium bicarbonate aqueous solution to the dichloromethane was added. The organic layer was dried in air at 45°C for 12 hours, and then vacuum dried at 50°C for 20 hours to obtain a quaternized acrylate copolymer;

[0051] (3) Weighing a quaternized acrylate copolymer and 5-amino-2-chloropyrimidine in a mass ratio of 1:1.2, mixing the quaternized acrylate copolymer and dichloromethane in a mass ratio of 1:30 to obtain a quaternized acrylate copolymer solution, mixing 5-amino-2-chloropyrimidine, triethylamine, and dichloromethane in a mass ratio of 1:1.3:12 to obtain a 5-amino-2-chloropyrimidine solution, and adding the 5-amino-2-chloropyrimidine solution dropwise to the quaternized acrylate copolymer solution at a dropping rate of 1 mL / min. After the dropwise addition is completed, the reaction is continued for 2 h, and a 10 wt% hydrochloric acid solution of 12 times the mass of the quaternized acrylate copolymer is added, and then a saturated sodium bicarbonate solution of 12 times the mass of the quaternized acrylate copolymer is added. The organic phase is taken and subjected to vacuum rotary evaporation to obtain a chloropyrimidyl acrylate copolymer;

[0052] (4) 3-methoxy-2-(tributyltinyl)pyridine, chloropyrimidinyl acrylate copolymer, lithium chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.5:0.2:12 and degassed, and tetrakis(triphenylphosphine)palladium(0) in an amount 0.2 times the mass of 3-methoxy-2-(tributyltinyl)pyridine was added, and the mixture was heated to 100° C. and reacted for 16 hours. After the reaction was completed, the pre-modified acrylate copolymer was obtained by rotary evaporation under reduced pressure;

[0053] (5) Under argon protection, anhydrous and oxygen-free conditions, the pre-modified acrylate copolymer and dichloromethane were mixed in a mass ratio of 1:60, cooled to -20°C, and 0.5 times the volume of boron tribromide of the pre-modified acrylate copolymer was added dropwise at a rate of 0.5 mL / min. After the addition was completed, the reaction was continued at -20°C for 12 hours. After the reaction was completed, methanol with a volume of 0.1 times that of dichloromethane was added, and then an ice-water mixture with a mass of 3 times that of dichloromethane was added. The mixture was filtered and vacuum-dried at 50°C for 20 hours to obtain a modified acrylate copolymer;

[0054] (6) Multi-walled carbon nanotubes and 68wt% concentrated nitric acid were mixed in a mass ratio of 1:30, heated to 120℃ and refluxed for 48h, and then washed with pure water for 7 times to obtain carboxylated multi-walled carbon nanotubes; carboxylated multi-walled carbon nanotubes and thionyl chloride were mixed in a mass ratio of 1:20, refluxed at 70℃ for 24h, cooled to room temperature, filtered, washed with tetrahydrofuran for 5 times, and dried at 50℃ for 12h to obtain chlorinated multi-walled carbon nanotubes; chitosan was dispersed in N,N-dimethylformamide with a mass of 30 times that of chitosan, allowed to stand for 12h, and chlorinated multi-walled carbon nanotubes with a mass of 0.5 times that of chitosan were added under nitrogen protection, ultrasonically treated for 2h, and continued to react for 96h. After the reaction was completed, it was filtered and washed with 2wt% acetic acid solution for 3 times, and 0.2μm was used. The mixture was filtered through a microporous membrane and finally vacuum dried at 60°C for 12 hours to obtain chitosan-grafted multi-walled carbon nanotubes; the chitosan-grafted multi-walled carbon nanotubes and an acetic acid buffer solution with a pH of 3 were mixed in a mass ratio of 1:80, and under nitrogen protection, a sodium periodate aqueous solution 6 times the mass of the chitosan-grafted multi-walled carbon nanotubes was added, and the mixture was reacted at 4°C for 44 hours, filtered and washed with pure water 3 times, and finally vacuum dried at 60°C for 12 hours to obtain pre-modified multi-walled carbon nanotubes; the pre-modified multi-walled carbon nanotubes, 2-amino-4,6-di-tert-butylphenol, and anhydrous ethanol were mixed in a mass ratio of 1:5:60, refluxed at 78°C for 5 hours, and after the reaction, cooled to room temperature, filtered and washed with anhydrous ethanol 3 times, and finally vacuum dried at 60°C for 12 hours to obtain modified multi-walled carbon nanotubes;

[0055] (7) Weigh 20 parts of modified acrylate copolymer, 5 parts of modified multi-walled carbon nanotubes, 40 parts of environmentally friendly solvent, 0.5 parts of rheological additive, 0.5 parts of leveling agent, 20 parts of hydroxy acrylic resin, and 25 parts of propellant in parts by mass; stir the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, and hydroxy acrylic resin evenly and grind them to a fineness of ≤45 μm. After grinding, put them into the liquid feed end of a two-component aerosol can, continue to add propellant and seal it to obtain component A; weigh 5 parts of isocyanate curing agent and 30 parts of solvent in parts by mass, stir the isocyanate curing agent and solvent evenly, put them into the curing agent end of a two-component aerosol can and seal it to obtain component B, press the curing agent end and shake it to mix evenly to obtain a two-component aerosol spray paint.

[0056] Comparative Example 1:

[0057] The preparation method of the two-component aerosol spray paint of Comparative Example 1 differs from that of Example 2 in that it does not contain steps (2), (3), (4) and (5), and step (1) is modified as follows: methyl methacrylate, n-butyl acrylate, dimethylallylamine and toluene are mixed in a mass ratio of 0.5:4:5.5:25, heated to 85°C under nitrogen protection, added with an initiator solution of 0.3 times the volume of toluene and stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene and stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene and stirred for 90 minutes, and finally dried in vacuo at 80°C for 24 hours to obtain a modified acrylate polymer.

[0058] Comparative Example 2:

[0059] The preparation method of the two-component aerosol spray paint of Comparative Example 2 differs from that of Example 2 in that step (5) is not included, and step (4) is modified as follows: 3-methoxy-2-(tributyltinalkyl)pyridine, chloropyrimidinyl acrylate copolymer, lithium chloride, and N,N-dimethylformamide are mixed in a mass ratio of 1:0.4:0.15:11 and degassed, and 0.15 times the mass of tetrakis(triphenylphosphine)palladium(0) of 3-methoxy-2-(tributyltinalkyl)pyridine is added, the temperature is raised to 100° C. and the reaction is carried out for 17 hours. After the reaction is completed, the modified acrylate copolymer is obtained by rotary evaporation under reduced pressure.

[0060] Comparative Example 3:

[0061] The difference between the preparation method of the two-component aerosol spray paint of Comparative Example 3 and Example 2 is that step (6) is modified as follows: multi-walled carbon nanotubes and 68wt% concentrated nitric acid are mixed in a mass ratio of 1:30, heated to 120°C and refluxed for 48h, and then washed with pure water 7 times to obtain carboxylated multi-walled carbon nanotubes; carboxylated multi-walled carbon nanotubes and thionyl chloride are mixed in a mass ratio of 1:20, refluxed at 70°C for 24h, cooled to room temperature, filtered and washed 5 times with tetrahydrofuran, and dried at 55°C for 12h to obtain chlorinated multi-walled carbon nanotubes; chitosan is dispersed in N,N-dimethylformamide 30 times the mass of chitosan, allowed to stand for 12h, and then precipitated under nitrogen protection. , add 0.4 times the mass of chitosan chloride multi-walled carbon nanotubes, ultrasonically treat for 2 hours, continue to react for 96 hours, after the reaction is completed, filter and wash with 2wt% acetic acid solution three times, filter with 0.2μm microporous filter membrane, and finally vacuum dry at 60℃ for 12h to obtain chitosan grafted multi-walled carbon nanotubes; chitosan grafted multi-walled carbon nanotubes and acetic acid buffer solution with a pH of 3 are mixed in a mass ratio of 1:80, and under nitrogen protection, sodium periodate aqueous solution with a mass of 5.5 times the mass of chitosan grafted multi-walled carbon nanotubes is added, react at 4℃ for 45h, filter and wash with pure water three times, and finally vacuum dry at 60℃ for 12h to obtain modified multi-walled carbon nanotubes.

[0062] Test Example 1:

[0063] Water resistance test:

[0064] Test specimens of the two-component aerosol spray paints prepared in the Examples and Comparative Examples were prepared according to GB / T 9271-2008. The water resistance of the specimens was measured according to GB / T 9274-1988. The specimens were placed in a 25°C constant-temperature water tank with one-third of their length exposed to the liquid surface. The time at which bubbling, shedding, or corrosion occurred was recorded. The results are shown in Table 1.

[0065] Anti-UV aging performance test:

[0066] Test specimens were prepared according to GB / T 9271-2008, with a paint film thickness of 18 μm. The specimens were placed in a UV aging chamber, and the time at which bubbling, peeling, or corrosion occurred was recorded. The temperature in the UV aging chamber was 50°C, the UV light wavelength was 340 nm, the lamp power was 40 W, and the distance between the paint film and the light source was 50 mm. The results are shown in Table 1.

[0067] Table 1 Test results of water resistance and UV aging resistance

[0068] Water resistance / d Anti-ultraviolet aging / d Example 1 15 32 Example 2 14 32 Example 3 15 32 Comparative Example 1 10 25 Comparative Example 2 12 25 Comparative Example 3 10 30

[0069] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the two-component aerosol spray paint prepared in the present invention has good water resistance and anti-ultraviolet aging performance.

[0070] By comparison, the water resistance of Examples 1 to 3 is better than that of Comparative Examples 1 and 3, and the UV aging resistance of Examples 1 to 3 is better than that of Comparative Examples 1 to 2, which shows that first, methyl methacrylate, n-butyl acrylate, and dimethylallylamine are induced by an initiator to obtain an acrylate copolymer, the acrylate copolymer is reacted with chloromethyl (methyl) phosphinoyl chloride to obtain a quaternized acrylate copolymer, the phosphoramide group on the quaternized acrylate copolymer is then amidated with the amino group on 5-amino-2-chloropyrimidine to obtain a chloropyrimidyl acrylate copolymer, and then reacted with 3-methoxy-2-(tributylstannane) to obtain a quaternized acrylate copolymer. The invention relates to a method for preparing a pre-modified acrylate copolymer by reacting 3-methoxy-2-(tributyltinyl)pyridine with 5-amino-2-chloropyrimidine to obtain a methoxypyridine functional group. The methoxypyridine functional group on 3-methoxy-2-(tributyltinyl)pyridine is grafted onto 5-amino-2-chloropyrimidine, and finally demethylated by boron tribromide to obtain a modified acrylate copolymer. Boron tribromide removes the methyl group on 3-methoxy-2-(tributyltinyl)pyridine to generate a hydroxyl group. The hydroxyl group is located at the ortho position of the nitrogen element on the pyrimidine group and can form an intramolecular chelate ring with the nitrogen element. When exposed to ultraviolet light, the light energy is converted into heat energy and dissipated, thereby improving the material's resistance to ultraviolet aging. The divalent structure formed by pyridine and pyrimidine has a good complexing effect on metals.

[0071] Secondly, chitosan is grafted onto chlorinated multi-walled carbon nanotubes. Multi-walled carbon nanotubes have excellent electrical conductivity. When they are evenly dispersed in the coating, they can form a shielding structure in the coating formed by spray painting, effectively preventing the penetration and diffusion of corrosive media and improving the physical anti-corrosion properties of the coating. Chitosan is oxidized by sodium periodate to form a dialdehyde group, which reacts with 2-amino-4,6-di-tert-butylphenol to form a Schiff base to obtain modified multi-walled carbon nanotubes. The Schiff base and the adjacent hydroxyl groups have a good complexing effect on metal ions.

[0072] Finally, the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, hydroxyl acrylic resin, and propellant are placed into the liquid feed end of a two-component aerosol can. The isocyanate curing agent and solvent are placed into the curing agent end of the two-component aerosol can, pressed down on the curing agent end, and then shaken to mix evenly, thereby obtaining a two-component aerosol spray paint. The metal ligands on the modified acrylate copolymer and modified multi-walled carbon nanotubes can form coordination complexes with metal ions. For metal substrates, they can undergo physical and chemical adsorption with the metal substrate before corrosion occurs, forming a dense protective film on the substrate surface, providing a more effective physical barrier. During the corrosion process, they can undergo a chelation reaction with free metal ions to form stable organic chelates. These organic chelates are highly compatible with the coating and are less likely to undergo phase separation, thereby delaying further corrosion.

[0073] Test Example 2:

[0074] Antibacterial performance test:

[0075] The two-component aerosol spray paints prepared in the examples and comparative examples were prepared into samples according to GB / T 9271-2008, and the antibacterial rates of the samples were tested according to GB / T 21866-2008. The results are shown in Table 2.

[0076] Table 2 Test results of antibacterial properties

[0077] Antibacterial rate Antibacterial rate Example 1 95.91％ Comparative Example 1 24.1％ Example 2 95.64％ Comparative Example 2 95.24％ Example 3 96.03％ Comparative Example 3 95.47％

[0078] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the two-component aerosol spray paint prepared in the present invention has good antibacterial properties.

[0079] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that first, methyl methacrylate, n-butyl acrylate, and dimethylallylamine are reacted with an initiator to obtain an acrylate copolymer, wherein dimethylallylamine causes the side chain of the acrylate copolymer to have a tertiary amine structure, and the acrylate copolymer is reacted with chloromethyl (methyl) phosphinoyl chloride to obtain a quaternized acrylate copolymer, and the chloromethyl group on the chloromethyl (methyl) phosphinoyl chloride reacts with the tertiary amine to form a quaternary ammonium salt with antibacterial properties, which can impart antibacterial properties to the spray paint.

[0080] Test Example 3:

[0081] Flame retardant performance test:

[0082] The two-component aerosol spray paints prepared in the examples and comparative examples were prepared into samples according to GB / T 9271-2008, and the limiting oxygen index of the samples was tested using a limiting oxygen index instrument according to the standard GB / T 2406.2-2009.

[0083] Table 3 Test results of limiting oxygen index

[0084] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 28.30 Comparative Example 1 22.41 Example 2 28.32 Comparative Example 2 27.96 Example 3 28.51 Comparative Example 3 28.04

[0085] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 3, it can be found that the two-component aerosol spray paint prepared in the present invention has good flame retardant properties.

[0086] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 1, indicating that first, methyl methacrylate, n-butyl acrylate, and dimethylallylamine are reacted with an initiator to obtain an acrylate copolymer, wherein dimethylallylamine causes the side chain of the acrylate copolymer to have a tertiary amine structure, and the acrylate copolymer is reacted with chloromethyl (methyl) phosphinoyl chloride to obtain a quaternized acrylate copolymer, and the chloromethyl group on the chloromethyl (methyl) phosphinoyl chloride reacts with the tertiary amine to form a quaternary ammonium salt with antibacterial properties, and the introduction of phosphorus element can give the spray paint flame retardant properties.

[0087] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A two-component aerosol spray paint, characterized in that: The invention comprises components A and B, wherein the component A comprises a modified acrylate copolymer, modified multi-walled carbon nanotubes, an environmentally friendly solvent, a rheological additive, a leveling agent, a propellant, and a hydroxy acrylic resin; and the component B comprises an isocyanate curing agent and a solvent. The modified acrylate copolymer is prepared by reacting methyl methacrylate, n-butyl acrylate, and dimethylallylamine in the presence of an initiator to obtain an acrylate copolymer, reacting the acrylate copolymer with chloromethyl (methyl) phosphinoyl chloride to obtain a quaternized acrylate copolymer, reacting the copolymer with 5-amino-2-chloropyrimidine to obtain a chloropyrimidyl acrylate copolymer, reacting the copolymer with 3-methoxy-2-(tributylstannyl)pyridine to obtain a pre-modified acrylate copolymer, and finally demethylating the copolymer with boron tribromide. The modified multi-walled carbon nanotubes are obtained by grafting chitosan onto acyl chloride multi-walled carbon nanotubes, oxidizing them with sodium periodate, and reacting them with 2-amino-4,6-di-tert-butylphenol.

2. A method for preparing a two-component aerosol spray paint, characterized in that: The method comprises the following preparation steps: (1) Methyl methacrylate, n-butyl acrylate, dimethylallylamine, and toluene were mixed in a mass ratio of 0.5:4:5.5:(20-30), heated to 80-90°C under nitrogen protection, added with an initiator solution of 0.3 times the volume of toluene, stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene again, stirred for 90 minutes, then added with an initiator solution of 0.3 times the volume of toluene again, stirred for 90 minutes, and finally dried in vacuum at 80°C for 24 hours to obtain an acrylate polymer; (2) mixing an acrylate polymer, triethylamine, chloromethyl (methyl) phosphinoyl chloride, and dichloromethane in a mass ratio of 1: (0.3-0.5): (0.8-0.9): (20-30), heating to 70-80°C, reacting for 12 hours, adding a saturated sodium bicarbonate aqueous solution equal in volume to the dichloromethane, taking the organic layer and drying it in air at 45°C for 12 hours, and then vacuum drying it at 50°C for 20 hours to obtain a quaternized acrylate copolymer; (3) Weighing a quaternized acrylate copolymer and 5-amino-2-chloropyrimidine in a mass ratio of 1:(1-1.2), mixing the quaternized acrylate copolymer and dichloromethane in a mass ratio of 1:(20-30) to obtain a quaternized acrylate copolymer solution, mixing 5-amino-2-chloropyrimidine, triethylamine, and dichloromethane in a mass ratio of 1:(1.2-1.3):(10-12) to obtain a 5-amino-2-chloropyrimidine solution, and adding the 5-amino-2-chloropyrimidine solution dropwise to the quaternized acrylate copolymer solution at a dropping rate of 1 mL / min. After the dropwise addition is completed, the reaction is continued for 2-3 hours, and a 10 wt% hydrochloric acid solution of 10-12 times the mass of the quaternized acrylate copolymer is added, and then a saturated sodium bicarbonate solution of 10-12 times the mass of the quaternized acrylate copolymer is added. The organic phase is taken and subjected to vacuum rotary evaporation to obtain a chloropyrimidyl acrylate copolymer; (4) 3-methoxy-2-(tributyltinyl)pyridine, chloropyrimidinyl acrylate copolymer, lithium chloride, and N,N-dimethylformamide are mixed in a mass ratio of 1:(0.3-0.5):(0.1-0.2):(10-12) and degassed, and tetrakis(triphenylphosphine)palladium(0) in an amount of 0.1-0.2 times the mass of 3-methoxy-2-(tributyltinyl)pyridine is added, and the mixture is heated to 100° C. and reacted for 16-18 hours. After the reaction is completed, the pre-modified acrylate copolymer is obtained by rotary evaporation under reduced pressure; (5) Under argon protection, anhydrous and oxygen-free conditions, the pre-modified acrylate copolymer and dichloromethane are mixed in a mass ratio of 1: (50-60), cooled to -20 ° C, and 0.3-0.5 times the volume of the pre-modified acrylate copolymer of boron tribromide is added dropwise at a rate of 0.5 mL / min. After the addition is completed, the reaction is continued at -20 ° C for 12 hours. After the reaction is completed, methanol with a volume of 0.1 times that of dichloromethane is added, and then an ice-water mixture with a mass of 3-4 times that of dichloromethane is added. The mixture is filtered and vacuum-dried at 50 ° C for 20 hours to obtain a modified acrylate copolymer; (6) Pre-modified multi-walled carbon nanotubes, 2-amino-4,6-di-tert-butylphenol, and anhydrous ethanol were mixed in a mass ratio of 1:(4-5):(50-60), refluxed at 78°C for 5-6 hours, cooled to room temperature after the reaction, filtered, and washed with anhydrous ethanol for 3-4 times, and finally vacuum dried at 60°C for 12 hours to obtain modified multi-walled carbon nanotubes; (7) Weigh 15-20 parts by mass of modified acrylate copolymer, 3-5 parts by mass of modified multi-walled carbon nanotubes, 30-40 parts by mass of environmentally friendly solvent, 0.1-0.5 parts by mass of rheological additive, 0.1-0.5 parts by mass of leveling agent, 20-25 parts by mass of propellant, and 20 parts by mass of hydroxy acrylic resin; stir the modified acrylate copolymer, modified multi-walled carbon nanotubes, environmentally friendly solvent, rheological additive, leveling agent, and hydroxy acrylic resin evenly and grind them to a fineness of ≤45 μm. After grinding, put them into the liquid feed end of a two-component aerosol can, continue to add the propellant and seal it to obtain component A; weigh 3-5 parts by mass of isocyanate curing agent and 20-30 parts by mass of solvent, stir the isocyanate curing agent and solvent evenly, put them into the curing agent end of a two-component aerosol can and seal it to obtain component B, press the curing agent end and shake it to mix evenly to obtain a two-component aerosol spray paint.

3. The method for preparing a two-component aerosol spray paint according to claim 2, characterized in that: The initiator solution in step (1) comprises ammonium persulfate and pure water, wherein the mass ratio of ammonium persulfate to pure water is 1:

20.

4. The method for preparing a two-component aerosol spray paint according to claim 2, characterized in that: The preparation method of the pre-modified multi-walled carbon nanotubes in step (6) is as follows: multi-walled carbon nanotubes and 68wt% concentrated nitric acid are mixed in a mass ratio of 1:30, heated to 120°C and refluxed for 48h, and then washed with pure water 7-8 times to obtain carboxylated multi-walled carbon nanotubes; carboxylated multi-walled carbon nanotubes and thionyl chloride are mixed in a mass ratio of 1:20, refluxed at 70°C for 24h, cooled to room temperature, filtered, washed with tetrahydrofuran 5-6 times, and dried at 50-60°C for 12h to obtain chlorinated multi-walled carbon nanotubes; chitosan is dispersed in N,N-dimethylformamide 30 times the mass of chitosan, allowed to stand for 12h, and chitosan is added under nitrogen protection at a mass of 0 .3-0.5 times the weight of chlorinated multi-walled carbon nanotubes, ultrasonically treated for 2 hours, and then reacted for 96 hours. After the reaction, filtered and washed with 2wt% acetic acid solution for 3 times, filtered with a 0.2μm microporous filter membrane, and finally vacuum dried at 60°C for 12 hours to obtain chitosan-grafted multi-walled carbon nanotubes; chitosan-grafted multi-walled carbon nanotubes and acetic acid buffer solution with a pH of 3 were mixed in a mass ratio of 1:80, and under nitrogen protection, a sodium periodate aqueous solution with a mass of 5-6 times that of the chitosan-grafted multi-walled carbon nanotubes was added, and the mixture was reacted at 4°C for 44-48 hours, filtered and washed with pure water for 3-4 times, and finally vacuum dried at 60°C for 12 hours to obtain pre-modified multi-walled carbon nanotubes.

5. The method for preparing a two-component aerosol spray paint according to claim 4, characterized in that: The model of the multi-walled carbon nanotube is L-MWNT-1020; the deacetylation degree of the chitosan is ≥95%.

6. The method for preparing a two-component aerosol spray paint according to claim 4, characterized in that: The sodium periodate aqueous solution is prepared by mixing sodium periodate and water in a mass ratio of 1:

20.

7. The method for preparing a two-component aerosol spray paint according to claim 2, characterized in that: The model of the hydroxy acrylic resin in step (7) is HU56024; the environmentally friendly solvent is propylene glycol ether acetate; the model of the isocyanate curing agent is Basonat HB100; the model of the leveling agent is YCK-1270N; the model of the rheological additive is BYK-7410; the model of the propellant is HFC-134a; and the solvent is acetone.