Disclosure of Invention
The invention aims to provide an aluminum alloy composite material based on a corrosion-resistant coating and a preparation method thereof, so as to solve the problems in the background technology.
The preparation method comprises the following steps of S1, taking catechol and 4-fluoro-1-aminonaphthalene, adding the catechol and the 4-fluoro-1-aminonaphthalene into absolute methanol, uniformly stirring, heating and refluxing for reaction, removing a solvent to obtain fluorine-containing Schiff base, taking 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1, 4-dioxane and fluorine-containing Schiff base, heating and stirring for reaction, and removing the solvent to obtain the flame retardant;
S2, uniformly stirring and dispersing epoxy resin, an active diluent, modified filler, a flame retardant, a curing agent, imidazole, a leveling agent and a photoinitiator to obtain a corrosion-resistant coating;
And S3, coating the corrosion-resistant coating on the surface of the aluminum alloy material, solidifying, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
More optimally, the fluorine-containing Schiff base comprises, by mass, 1-1.5 parts of catechol, 1.5-2 parts of 4-fluoro-1-aminonaphthalene and 20-30 parts of anhydrous methanol, and the flame retardant comprises, by mass, 2-2.5 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 20-50 parts of 1, 4-dioxane and 2-4 parts of fluorine-containing Schiff base.
More optimally, the corrosion-resistant coating comprises, by mass, 35-45 parts of epoxy resin, 8-12 parts of reactive diluent, 25-30 parts of modified filler, 5-8 parts of flame retardant, 6-10 parts of curing agent (small molecule curing agent, preferably m-xylylenediamine), 1-2 parts of imidazole, 0.5-1 part of leveling agent and 0.1-0.2 part of photoinitiator.
More optimally, the preparation of the modified filler comprises the following steps of taking carboxylated carbon nanotubes, adding thionyl chloride and N, N-dimethylformamide under the protection of nitrogen, stirring for 5-6 min, performing ultrasonic dispersion for 2-3 h at 20-30 ℃, performing reflux reaction for 20-25 h, filtering to obtain solid, washing and drying to obtain the carbon acyl chloride nanotubes;
adding an acyl chloride carbon nano tube into tetrahydrofuran, uniformly stirring, adding trihydroxy heptaoctyl pos, stirring at 40-50 ℃ for reacting for 70-75 hours, filtering to obtain a solid, washing and drying to obtain a composite filler;
Adding the composite filler into an ethanol water mixed solution, uniformly stirring, adding 3- (2, 3-glycidoxy) propyl trimethoxy silane, uniformly mixing, stirring at 60-70 ℃ for reacting for 4-8 hours, filtering, taking solid, and washing to obtain an epoxidized composite filler;
Adding the epoxy composite filler into benzene, adding hydroxyl-terminated methyl vinyl silicone oil and triethanolamine, uniformly stirring, stirring and reacting for 2-3 hours at 100-120 ℃ under the protection of nitrogen, adding hydroxyl fluorine silicone oil, stirring for 2-3 hours under the condition of heat preservation, and removing the solvent and the catalyst to obtain the modified filler.
More optimally, the acyl chloride carbon nano tube comprises the following raw materials, by mass, 0.3-0.5 part of carboxylated carbon nano tube, 50-60 parts of sulfoxide chloride and 1-2 parts of N, N-dimethylformamide;
the composite filler comprises, by mass, 1-2 parts of carbon acyl chloride nanotubes and 1-2 parts of trihydroxy heptaoctyl pos.
More optimally, the epoxidized composite filler comprises the following raw materials, by mass, 10-15 parts of composite filler and 1-2 parts of 3- (2, 3-glycidoxy) propyl trimethoxy silane;
the modified filler comprises, by mass, 10-15 parts of an epoxidized composite filler, 2-4 parts of hydroxyl-terminated vinyl silicone oil, 0.1-0.2 part of triethanolamine and 5-8 parts of hydroxyl-fluorinated silicone oil.
More preferably, the curing conditions are: ultraviolet irradiation is carried out for 1-2 h, and curing is carried out at 80-100℃ and curing for 2-3 hours at 120-130 ℃ for 3-4 hours.
More preferably, the reactive diluent is allyl glycidyl ether.
More preferably, the aluminum alloy material comprises the following components of 0.1-0.3% of Cu, 0.3-0.5% of Mn, 0.2-0.4% of Fe, 0.2-0.4% of Si, 0.6-1% of Mg, 0.01-0.02% of Ti, 0.03-0.05% of Zn, 0.05-0.25% of Cr, and the balance of Al and unavoidable impurities.
Compared with the prior art, the fluorine-containing Schiff base is prepared by reacting catechol and 4-fluoro-1-amino naphthalene, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is introduced by utilizing the reaction of the fluorine-containing Schiff base and P-H to obtain the flame retardant, wherein fluorine can effectively improve the corrosion resistance of an epoxy resin-based material, a naphthalene ring can increase a rigid structure, and the overall heat resistance and strength are improved;
(2) After the carbon nano tube is subjected to acyl chlorination, connecting a trihydroxy heptaoctyl pos, and then modifying by an epoxy silane coupling agent, and grafting vinyl-containing silicone oil and fluorine-containing silicone oil; the introduced organosilicon chain segment has higher thermal stability, can also improve the compatibility of epoxy resin and composite filler, can relieve the too large brittleness problem caused by too much rigid structure due to the flexibility of silicone oil, and enhances the overall impact strength, so that the addition amount of the flame retardant and the modified filler needs to be controlled to balance rigidity and flexibility;
(3) The reactive diluent is allyl glycidyl ether, and double bonds are introduced, so that the subsequent solidification is facilitated, and the compatibility with modified filler is improved;
(4) The step curing process is adopted, ultraviolet irradiation is firstly adopted, double bonds existing in the system are crosslinked in advance, then the temperature is gradually increased for curing, groups in the curing agent and the flame retardant react with epoxy groups, the internal stress can be reduced by the step curing, the coating quality is improved, and the impact strength and the corrosion resistance of the coating are further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials to be used in the present invention are not particularly limited by the manufacturers, and include, for example, ethanol (CAS: 64-17-5), catechol (CAS: 139-85-5), 4-fluoro-1-aminonaphthalene (CAS: 438-32-4), 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (CAS: 35948-25-5), 1, 4-dioxan (CAS: 123-91-1), trihydroxy heptaoctylpos (JH-P302), carboxylated carbon nanotubes (Kelarmare 180117142215), N-dimethylformamide (CAS: 68-12-2), 3- (2, 3-epoxypropoxy) propyltrimethoxysilane (CAS: 2530-83-8), hydroxyl-terminated methylvinylsilicone oil (TA 1203V), triethanolamine (anhydrous stannic chloride), hydroxyfluorosilicone (TPD-FS 8014), epoxy resin (E51, jinan mountain sea chemical), allyl glycidyl ether (CAS: 106-92), and sodium (CAS: 5361-61), and an m-phenylimidazole (CAS: 61-61);
if not specified, the following parts by mass and mass ratios are given;
The aluminum alloy material comprises 0.2% of Cu,0.4% of Mn,0.3% of Fe,0.3% of Si,1% of Mg,0.01% of Ti,0.03% of Zn,0.15% of Cr, and the balance of Al and unavoidable impurities;
1.4 parts of catechol and 1.6 parts of 4-fluoro-1-aminonaphthalene are taken, added into 25 parts of absolute methanol, stirred uniformly, heated to reflux for 8 hours, the solvent is removed to obtain fluorine-containing Schiff base, 2.2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 parts of 1, 4-dioxane and 3 parts of fluorine-containing Schiff base are taken, heated to 70 ℃, stirred and reacted for 6 hours, and the solvent is removed to obtain the flame retardant;
S2, adding 60 parts of thionyl chloride and 1 part of N, N-dimethylformamide under the protection of nitrogen, stirring for 5min, dispersing by ultrasonic at 30 ℃ for 3h, carrying out reflux reaction at 70 ℃ for 24h, filtering, taking out solids, washing and drying to obtain carbon acyl chloride nanotubes, adding 2 parts of carbon acyl chloride nanotubes into 100 parts of tetrahydrofuran, stirring uniformly, adding 1 part of trihydroxy heptaoctyl pos, stirring for 72h at 50 ℃, filtering, taking out solids, washing and drying to obtain a composite filler, adding 10 parts of composite filler into 100 parts of ethanol-water mixed solution (volume ratio of ethanol to water is 7:3), stirring uniformly, adding 1 part of 3- (2, 3-glycidoxy) propyl trimethoxysilane, mixing uniformly, stirring for 8h at 70 ℃, filtering, taking out solids, washing to obtain an epoxy composite filler, adding 12 parts of epoxy composite filler into 100 parts of benzene, adding 3 parts of hydroxyl end-capped methyl vinyl silicone oil, 0.01 part of triethanolamine, stirring for 3h at 120 ℃ under the protection of nitrogen, adding 6 parts of hydroxyl fluorine silicone oil, stirring for 3h, and carrying out heat preservation and carrying out modification to obtain a modified catalyst;
S3, placing 40 parts of epoxy resin, 10 parts of reactive diluent allyl glycidyl ether, 28 parts of modified filler, 6 parts of flame retardant, 8 parts of m-xylylenediamine, 1 part of imidazole, 0.5 part of flatting agent sodium polyacrylate and 0.1 part of photoinitiator into a high-speed dispersing machine for stirring and dispersing to obtain corrosion-resistant paint;
And S4, coating the corrosion-resistant coating on the surface of the aluminum alloy material, irradiating with ultraviolet light with the thickness of 25 mu m and 350nm for 1h, heating to 80 ℃ for 4h, solidifying at 130 ℃ for 2h, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
1 Part of catechol and 1.5 parts of 4-fluoro-1-aminonaphthalene are taken, added into 25 parts of absolute methanol, stirred uniformly, heated to reflux for 8 hours, and the solvent is removed to obtain fluorine-containing Schiff base, 2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 parts of 1, 4-dioxane and 2 parts of fluorine-containing Schiff base are taken, heated to 70 ℃, stirred and reacted for 6 hours, and the solvent is removed to obtain the flame retardant;
S2, adding 60 parts of thionyl chloride and 1 part of N, N-dimethylformamide under the protection of nitrogen, stirring for 5min, dispersing by ultrasonic at 30 ℃ for 3h, carrying out reflux reaction at 70 ℃ for 24h, filtering, taking out solids, washing and drying to obtain carbon acyl chloride nanotubes, adding 2 parts of carbon acyl chloride nanotubes into 100 parts of tetrahydrofuran, stirring uniformly, adding 1 part of trihydroxy heptaoctyl pos, stirring for 72h at 50 ℃, filtering, taking out solids, washing and drying to obtain a composite filler, adding 10 parts of composite filler into 100 parts of ethanol-water mixed solution (volume ratio of ethanol to water is 7:3), stirring uniformly, adding 1 part of 3- (2, 3-glycidoxy) propyl trimethoxysilane, mixing uniformly, stirring for 8h at 70 ℃, filtering, taking out solids, washing to obtain an epoxy composite filler, adding 12 parts of epoxy composite filler into 100 parts of benzene, adding 4 parts of hydroxyl end-capped methyl vinyl silicone oil, 0.01 part of triethanolamine, stirring for 3h at 110 ℃ under the protection of nitrogen, adding 6 parts of hydroxyl fluorine silicone oil, stirring for 3h, and carrying out heat preservation and carrying out modification to obtain a modified catalyst;
s3, placing 38 parts of epoxy resin, 10 parts of reactive diluent allyl glycidyl ether, 30 parts of modified filler, 8 parts of flame retardant, 8 parts of m-xylylenediamine, 1 part of imidazole, 0.5 part of flatting agent sodium polyacrylate and 0.1 part of photoinitiator into a high-speed dispersing machine for stirring and dispersing to obtain corrosion-resistant paint;
and S4, coating the corrosion-resistant coating on the surface of the aluminum alloy material, irradiating with ultraviolet light with the coating thickness of 25 mu m and 350nm for 1h, heating to 100 ℃ for solidification for 3h, solidifying at 120 ℃ for 2h, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
1.5 Parts of catechol and 2 parts of 4-fluoro-1-aminonaphthalene are taken, added into 25 parts of absolute methanol, stirred uniformly, heated to reflux for 8 hours, the solvent is removed to obtain fluorine-containing Schiff base, 2.5 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 parts of 1, 4-dioxane and 4 parts of fluorine-containing Schiff base are taken, heated to 70 ℃, stirred and reacted for 6 hours, and the solvent is removed to obtain the flame retardant;
S2, adding 60 parts of thionyl chloride and 1 part of N, N-dimethylformamide under the protection of nitrogen, stirring for 5min, dispersing by ultrasonic at 30 ℃ for 3h, carrying out reflux reaction at 70 ℃ for 24h, filtering, taking out solids, washing and drying to obtain carbon acyl chloride nanotubes, adding 2 parts of carbon acyl chloride nanotubes into 100 parts of tetrahydrofuran, stirring uniformly, adding 1 part of trihydroxy heptaoctyl pos, stirring for 72h at 50 ℃, filtering, taking out solids, washing and drying to obtain a composite filler, adding 10 parts of composite filler into 100 parts of ethanol-water mixed solution (volume ratio of ethanol to water is 7:3), stirring uniformly, adding 1 part of 3- (2, 3-glycidoxy) propyl trimethoxysilane, mixing uniformly, stirring for 8h at 70 ℃, filtering, taking out solids, washing to obtain an epoxy composite filler, adding 12 parts of epoxy composite filler into 100 parts of benzene, adding 2 parts of hydroxyl-terminated methyl vinyl silicone oil, 0.01 part of triethanolamine, stirring for 3h at 100 ℃ under the protection of nitrogen, adding 6 parts of hydroxyl-terminated methyl silicone oil, stirring for 3h, and carrying out heat preservation and carrying out a modification reaction with a solvent to obtain a modified filler;
S3, placing 45 parts of epoxy resin, 10 parts of reactive diluent allyl glycidyl ether, 30 parts of modified filler, 6 parts of flame retardant, 8 parts of m-xylylenediamine, 1 part of imidazole, 0.5 part of flatting agent sodium polyacrylate and 0.1 part of photoinitiator into a high-speed dispersing machine for stirring and dispersing to obtain corrosion-resistant paint;
and S4, coating the corrosion-resistant coating on the surface of the aluminum alloy material, irradiating with ultraviolet light with the thickness of 25 mu m and 350nm for 1h, heating to 80 ℃ for solidification for 3h, solidifying at 130 ℃ for 3h, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
Comparative example 1 (changing the addition ratio of modified filler and flame retardant, the rest method steps are the same as those of example 1), S1, taking 1.4 parts of catechol and 1.6 parts of 4-fluoro-1-aminonaphthalene, adding into 25 parts of absolute methanol, stirring uniformly, heating to reflux for 8 hours, removing the solvent to obtain fluorine-containing Schiff base, taking 2.2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 parts of 1, 4-dioxane and 3 parts of fluorine-containing Schiff base, heating to 70 ℃, stirring and reacting for 6 hours, and removing the solvent to obtain the flame retardant;
S2, adding 60 parts of thionyl chloride and 1 part of N, N-dimethylformamide under the protection of nitrogen, stirring for 5min, dispersing by ultrasonic at 30 ℃ for 3h, carrying out reflux reaction at 70 ℃ for 24h, filtering, taking out solids, washing and drying to obtain carbon acyl chloride nanotubes, adding 2 parts of carbon acyl chloride nanotubes into 100 parts of tetrahydrofuran, stirring uniformly, adding 1 part of trihydroxy heptaoctyl pos, stirring for 72h at 50 ℃, filtering, taking out solids, washing and drying to obtain a composite filler, adding 10 parts of composite filler into 100 parts of ethanol-water mixed solution (volume ratio of ethanol to water is 7:3), stirring uniformly, adding 1 part of 3- (2, 3-glycidoxy) propyl trimethoxysilane, mixing uniformly, stirring for 8h at 70 ℃, filtering, taking out solids, washing to obtain an epoxy composite filler, adding 12 parts of epoxy composite filler into 100 parts of benzene, adding 3 parts of hydroxyl end-capped methyl vinyl silicone oil, 0.01 part of triethanolamine, stirring for 3h at 120 ℃ under the protection of nitrogen, adding 6 parts of hydroxyl fluorine silicone oil, stirring for 3h, and carrying out heat preservation and carrying out modification to obtain a modified catalyst;
s3, placing 40 parts of epoxy resin, 10 parts of reactive diluent allyl glycidyl ether, 22 parts of modified filler, 10 parts of flame retardant, 8 parts of m-xylylenediamine, 1 part of imidazole, 0.5 part of flatting agent sodium polyacrylate and 0.1 part of photoinitiator into a high-speed dispersing machine for stirring and dispersing to obtain corrosion-resistant paint;
And S4, coating the corrosion-resistant coating on the surface of the aluminum alloy material, irradiating with ultraviolet light with the thickness of 25 mu m and 350nm for 1h, heating to 80 ℃ for 4h, solidifying at 130 ℃ for 2h, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
Comparative example 2 (changing the addition ratio of modified filler and flame retardant, the rest method steps are the same as those of example 1), S1, taking 1.4 parts of catechol and 1.6 parts of 4-fluoro-1-aminonaphthalene, adding into 25 parts of absolute methanol, stirring uniformly, heating to reflux for 8 hours, removing the solvent to obtain fluorine-containing Schiff base, taking 2.2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 parts of 1, 4-dioxane and 3 parts of fluorine-containing Schiff base, heating to 70 ℃, stirring and reacting for 6 hours, and removing the solvent to obtain the flame retardant;
S2, adding 60 parts of thionyl chloride and 1 part of N, N-dimethylformamide under the protection of nitrogen, stirring for 5min, dispersing by ultrasonic at 30 ℃ for 3h, carrying out reflux reaction at 70 ℃ for 24h, filtering, taking out solids, washing and drying to obtain carbon acyl chloride nanotubes, adding 2 parts of carbon acyl chloride nanotubes into 100 parts of tetrahydrofuran, stirring uniformly, adding 1 part of trihydroxy heptaoctyl pos, stirring for 72h at 50 ℃, filtering, taking out solids, washing and drying to obtain a composite filler, adding 10 parts of composite filler into 100 parts of ethanol-water mixed solution (volume ratio of ethanol to water is 7:3), stirring uniformly, adding 1 part of 3- (2, 3-glycidoxy) propyl trimethoxysilane, mixing uniformly, stirring for 8h at 70 ℃, filtering, taking out solids, washing to obtain an epoxy composite filler, adding 12 parts of epoxy composite filler into 100 parts of benzene, adding 3 parts of hydroxyl end-capped methyl vinyl silicone oil, 0.01 part of triethanolamine, stirring for 3h at 120 ℃ under the protection of nitrogen, adding 6 parts of hydroxyl fluorine silicone oil, stirring for 3h, and carrying out heat preservation and carrying out modification to obtain a modified catalyst;
s3, placing 40 parts of epoxy resin, 10 parts of reactive diluent allyl glycidyl ether, 32 parts of modified filler, 4 parts of flame retardant, 8 parts of m-xylylenediamine, 1 part of imidazole, 0.5 part of flatting agent sodium polyacrylate and 0.1 part of photoinitiator into a high-speed dispersing machine for stirring and dispersing to obtain corrosion-resistant paint;
And S4, coating the corrosion-resistant coating on the surface of the aluminum alloy material, irradiating with ultraviolet light with the thickness of 25 mu m and 350nm for 1h, heating to 80 ℃ for 4h, solidifying at 130 ℃ for 2h, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
Comparative example 3 (1, 4-butanediol diglycidyl ether is used as an active diluent and no photoinitiator is added, the rest method steps are the same as those of example 1), S1, 1.4 parts of catechol and 1.6 parts of 4-fluoro-1-aminonaphthalene are added into 25 parts of absolute methanol, the mixture is stirred uniformly, heated to reflux for 8 hours, the solvent is removed to obtain fluorine-containing Schiff base, 2.2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 parts of 1, 4-dioxane and 3 parts of fluorine-containing Schiff base are taken, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 6 hours, and the solvent is removed to obtain the flame retardant;
S2, taking 0.5 part of carboxylated carbon nano tube, adding 60 parts of sulfoxide chloride and 1 part of N, N-dimethylformamide under the protection of nitrogen, stirring for 5min, dispersing by ultrasonic at 30 ℃ for 3h, carrying out reflux reaction at 70 ℃ for 24h, filtering, taking out solid, washing and drying to obtain the carbon nano tube, taking 2 parts of carbon nano tube, adding 100 parts of tetrahydrofuran, stirring uniformly, adding 1 part of trihydroxy heptaoctyl pos, carrying out stirring reaction at 50 ℃ for 72h, filtering, taking out solid, washing and drying to obtain a composite filler, adding 10 parts of composite filler into 100 parts of ethanol-water mixed solution (volume ratio of ethanol to water is 7:3), stirring uniformly, adding 1 part of 3- (2, 3-glycidoxy) propyl trimethoxysilane, mixing uniformly, carrying out stirring reaction at 70 ℃ for 8h, filtering, washing to obtain the solid, obtaining the epoxidized composite filler, adding 12 parts of the epoxidized composite filler into 100 parts of benzene, adding 3 parts of hydroxyl-terminated methyl vinyl silicone oil, 0.01 part of triethanolamine, stirring at 120 ℃ under the protection of nitrogen for 3h, adding 6 parts of hydroxyl fluorine silicone oil, stirring at 3h, stirring under the protection of nitrogen, carrying out stirring, and carrying out stirring reaction with a solvent, and carrying out heat preservation, and carrying out continuous stirring to obtain a catalyst, and removing the catalyst, and carrying out heat preservation, so as to obtain the catalyst.
S3, placing 40 parts of epoxy resin, 10 parts of active diluent 1, 4-butanediol diglycidyl ether, 28 parts of modified filler, 6 parts of flame retardant, 8 parts of m-xylylenediamine, 1 part of imidazole and 0.5 part of flatting agent sodium polyacrylate into a high-speed dispersing machine for stirring and dispersing to obtain corrosion-resistant paint;
And S4, coating the corrosion-resistant coating on the surface of the aluminum alloy material, irradiating with ultraviolet light with the thickness of 25 mu m and 350nm for 1h, heating to 80 ℃ for 4h, solidifying at 130 ℃ for 2h, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
Comparative example 4 (modified filler preparation method is changed, and the rest method steps are the same as in example 1), S1, taking 1.4 parts of catechol and 1.6 parts of 4-fluoro-1-aminonaphthalene, adding into 25 parts of anhydrous methanol, stirring uniformly, heating to reflux for 8 hours, removing the solvent to obtain fluorine-containing Schiff base, taking 2.2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 parts of 1, 4-dioxane and 3 parts of fluorine-containing Schiff base, heating to 70 ℃, stirring and reacting for 6 hours, and removing the solvent to obtain the flame retardant;
S2, adding 60 parts of thionyl chloride and 1 part of N, N-dimethylformamide under the protection of nitrogen, stirring for 5min, dispersing by ultrasonic at 30 ℃ for 3h, carrying out reflux reaction at 70 ℃ for 24h, filtering, taking out solid, washing and drying to obtain carbon acyl chloride nanotubes, adding 2 parts of carbon acyl chloride nanotubes into 100 parts of tetrahydrofuran, stirring uniformly, adding 1 part of trihydroxy heptaoctyl pos, stirring for 72h at 50 ℃, filtering, taking out solid, washing and drying to obtain a composite filler, adding 10 parts of composite filler into 100 parts of ethanol-water mixed solution (volume ratio of ethanol to water is 7:3), stirring uniformly, adding 1 part of 3- (2, 3-glycidoxy) propyl trimethoxysilane, mixing uniformly, stirring for 8h at 120 ℃, filtering, taking out solid, washing to obtain an epoxy composite filler, adding 12 parts of epoxy composite filler into 100 parts of benzene, adding 6 parts of hydroxyl-terminated methyl vinyl silicone oil, 0.01 part of triethanolamine, 3 parts of hydroxyl fluorine silicone oil, continuing stirring for 6h, removing a solvent and a catalyst, and keeping the temperature to obtain a modified filler;
S3, placing 40 parts of epoxy resin, 10 parts of reactive diluent allyl glycidyl ether, 28 parts of modified filler, 6 parts of flame retardant, 8 parts of m-xylylenediamine, 1 part of imidazole, 0.5 part of flatting agent sodium polyacrylate and 0.1 part of photoinitiator into a high-speed dispersing machine for stirring and dispersing to obtain corrosion-resistant paint;
And S4, coating the corrosion-resistant coating on the surface of the aluminum alloy material, irradiating with ultraviolet light with the thickness of 25 mu m and 350nm for 1h, heating to 80 ℃ for 4h, solidifying at 130 ℃ for 2h, drying and cooling to obtain the aluminum alloy composite material with the corrosion-resistant coating on the surface.
The performance test comprises the steps of taking the aluminum alloy composite materials with the corrosion-resistant coating on the surface, which are prepared in the examples 1-3 and the comparative examples 1-4, (1) referring to GB/T1843-2008, testing the impact resistance of the coating, (2) judging the flame retardant performance through testing the limiting oxygen index;
table 1:
(3) The corrosion potentials of examples 1-3 are tested and are shown in Table 2;
table 2:
the conclusion is that the aluminum alloy composite material with the corrosion-resistant coating on the surface has good corrosion resistance, the addition ratio of the modified filler and the flame retardant is changed in comparative example 1 and comparative example 2, so that the performance is reduced, the addition amount is required to be controlled, the 1, 4-butanediol diglycidyl ether is taken as an active diluent and no photoinitiator is added in comparative example 3, the performance is reduced due to the change of the crosslinking degree and the overall compatibility, the preparation method of the modified filler is changed in comparative example 4, the addition amount of two silicone oils is changed, the performance is inferior to that of the example, and the aluminum alloy composite material with the corrosion-resistant coating on the surface has excellent corrosion resistance, flame retardance and impact resistance.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, but may be modified or substituted for some of the technical features thereof by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.