Ship anticorrosive paint and preparation method thereof

Abstract

The invention relates to the technical field of anticorrosive coatings, and particularly discloses a ship anticorrosive coating and a preparation method thereof. The preparation method comprises the following steps: firstly, mixing acidized titanium dioxide and zinc oxide nanoparticles with industrial ethanol and a modifier, stirring, washing, filtering and drying to obtain a functional filler; secondly, when the castor oil-based hyperbranched polyester polyol is prepared, dehydration and carboxylation of castor oil and condensation polymerization of the castor oil, propylene glycol and sodium hydroxide are included; then, fluorine-containing hyperbranched epoxy resin is prepared, castor oil-based hyperbranched polyester polyol and epoxy chloropropane react to form a matrix, and a fluorine-containing compound is introduced to complete modification; and finally, uniformly mixing the fluorine-containing hyperbranched epoxy resin, the functional filler and the auxiliary agent to prepare the anticorrosive paint. The ship anticorrosive paint prepared by the preparation method provided by the invention has excellent salt spray resistance and environmental protection property, and the mechanical strength and wear resistance of the paint are effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-corrosion coatings, and more specifically, to a ship anti-corrosion coating and a preparation method thereof. Background Art

[0002] Metal materials have become the foundation of modern industry with their unique properties and wide applications. However, metals will inevitably suffer from corrosion during use, especially in the shipbuilding industry, because they are mainly composed of steel and are exposed to corrosive environments such as rivers, lakes, and oceans for a long time, so they face serious corrosion problems. In order to extend the service life of ships and reduce the economic losses caused by corrosion, all countries are committed to the research and application of ship anti-corrosion technology. At present, commonly used corrosion protection methods include electrochemical protection, adding corrosion inhibitors and organic coating protection, and organic coating has become one of the most widely used anti-corrosion technologies due to its advantages such as simple construction, wide adaptability, low comprehensive cost and significant anti-corrosion effect. Epoxy resin has an irreplaceable position in the field of metal anti-corrosion due to its excellent mechanical properties, strong adhesion to metal surfaces and excellent corrosion resistance. However, traditional epoxy resins have some inherent defects, such as insufficient toughness, large brittleness and excessive viscosity. Due to its large molecular weight, a large amount of solvent is required to adjust the viscosity during the coating process, which does not meet the requirements of green environmental protection and its elongation at break is low, resulting in easy brittle cracking of the coating. In view of the above situation, the present invention proposes a new ship anti-corrosion coating and a preparation method thereof. Summary of the invention

[0003] In order to solve the limitations of existing ship anti-corrosion coatings, including great difficulty in technical implementation, high viscosity, easy brittle cracking of the coating, poor mechanical strength and low environmental protection, the present invention provides a ship anti-corrosion coating and a preparation method thereof.

[0004] In a first aspect, the present invention provides a method for preparing a ship anticorrosion coating, which adopts the following technical scheme:

[0005] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0006] S1. Preparation of functional fillers:

[0007] The zinc oxide nanoparticles and the titanium dioxide nanoparticles are mixed and then treated with acid solution, and then washed and filtered to obtain an acid-treated filler; the acid-treated filler is dispersed in industrial ethanol, a modifier is added, and the mixture is continuously stirred at 50-80° C. for 2-4 hours, and then washed, filtered, and dried to obtain a functional filler;

[0008] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0009] S21, heating the castor oil at 100-120° C. in a vacuum environment, and keeping the temperature for 20-40 minutes to remove moisture to obtain dry castor oil;

[0010] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 120-150° C. and stirring for 4-8 hours, and then distilling under reduced pressure to obtain carboxylated castor oil;

[0011] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide into a reaction kettle, heating to 160-200° C. and stirring for 4-6 hours, then removing the unreacted solvent by distillation under reduced pressure, and repeating this reaction step 5-8 times to obtain a castor oil-based hyperbranched polyester polyol;

[0012] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0013] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a crosslinking agent and a catalyst, heating to 80-100° C. under nitrogen protection, stirring for 3-6 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix;

[0014] S32, using dichloromethane to dissolve glycidyl 2,2,3,3-tetrafluoropropyl ether and a hyperbranched epoxy resin matrix respectively, adding the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution, adding N,N-dimethylbenzylamine, stirring continuously at 50-80° C. for 6-8 hours, and then distilling under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0015] S4. Evenly mix the fluorine-containing hyperbranched epoxy resin, functional filler, curing agent, anti-rust pigment, dispersant, plasticizer and deionized water to obtain a ship anti-corrosion coating.

[0016] Preferably, the modifier in step S1 is composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 10-15:1.

[0017] Preferably, in step S31, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 1-3:1.

[0018] Preferably, the catalyst in step S31 is composed of triethylamine and 2-methylimidazole in a molar ratio of 6-10:1.

[0019] Preferably, in step S4, the components by weight include 80-100 parts of fluorine-containing hyperbranched epoxy resin, 18-22 parts of functional filler, 10-30 parts of curing agent, 5-10 parts of rust-proof pigment, 1-3 parts of dispersant, 1-3 parts of plasticizer, and 40-60 parts of deionized water.

[0020] Preferably, the curing agent in step S4 is at least one of triethylenetetramine, 4,4'-diaminodiphenylmethane and hexamethylenediamine.

[0021] Preferably, the anti-rust pigment in step S4 is at least one of zinc powder, zinc phosphate and mica iron oxide.

[0022] Preferably, the dispersant in step S4 is a polyester dispersant.

[0023] Preferably, the plasticizer in step S4 is at least one of dioctyl phthalate, dinonyl phthalate and didecyl phthalate.

[0024] In a second aspect, the present invention also provides a ship anti-corrosion coating, which adopts the following technical solution:

[0025] A ship anticorrosive coating is prepared by the above preparation method.

[0026] In summary, the present invention has the following beneficial effects:

[0027] 1. A method for preparing a ship anticorrosion coating proposed by the present invention, wherein a fluorine-containing hyperbranched epoxy resin, a functional filler, a curing agent, an antirust pigment, a dispersant, a plasticizer and deionized water are mixed to prepare a ship anticorrosion coating. The modified functional filler helps to form a durable and effective protective layer, and the strong interface bonding force formed between the modified functional filler and the coating matrix increases the hardness, wear resistance and impact resistance of the coating, so that the coating is not easily damaged when subjected to physical impact or wear, and can not only resist the erosion and biofouling of seawater, but also cope with the challenges of complex marine environments, thereby extending the service life of the ship surface and reducing the maintenance frequency and cost. Using castor oil-based hyperbranched polyester polyol as an important raw material for preparing fluorine-containing hyperbranched epoxy resin, the coating is endowed with good flexibility and impact resistance, while maintaining a high hardness, improving the overall mechanical properties, and providing comprehensive protective performance for ship anticorrosion coatings through its unique structural design and the introduction of functional groups, which not only improves the protective efficacy of the coating, but also improves its construction performance and environmental protection attributes. The ship anti-corrosion coating made of functional fillers, fluorinated hyperbranched epoxy resins and additives has excellent anti-corrosion properties, enhanced mechanical strength and wear resistance, good adhesion and density, and greatly reduces volatile organic compound emissions.

[0028] 2. The fluorine-containing hyperbranched epoxy resin of the present invention is prepared by heating and dehydrating castor oil, carboxylating and polycondensing castor oil to form a castor oil-based hyperbranched polyester polyol, then reacting with epichlorohydrin under nitrogen protection to form a matrix, and introducing a fluorine-containing monomer for modification. Wherein castor oil is a natural renewable resource. Compared with traditional petroleum-based raw materials, using castor oil as a basic material is more environmentally friendly and conforms to the principle of green chemistry. The introduction of fluorine element significantly improves the chemical stability of the resin, so that it shows stronger corrosion resistance in corrosive environments such as salt spray and seawater. The cross-linking agent composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether can react with the active points in the hyperbranched epoxy resin to form a highly cross-linked network structure, thereby improving the mechanical strength and toughness of the coating. The synergistic effect of the catalyst triethylamine and 2-methylimidazole can accelerate the curing process of the epoxy resin, shorten the construction period, and improve production efficiency. As a key component of ship anti-corrosion coatings, fluorinated hyperbranched epoxy resin not only improves the various performance indicators of the coatings, but also significantly enhances the corrosion resistance and service life of the ship surface, making it suitable for use in harsh marine environments.

[0029] 3. The present invention adopts zinc oxide nanoparticles and titanium dioxide nanoparticles to prepare functional fillers through acid treatment and modifier treatment. By using a modifier composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate, the interaction between zinc oxide nanoparticles and titanium dioxide nanoparticles and the coating matrix can be effectively promoted, thereby promoting the uniform dispersion of the filler in the coating, reducing the pores and cracks in the coating, thereby improving the density of the coating and enhancing the protective effect of the coating. Since zinc oxide and titanium dioxide nanoparticles themselves have good antibacterial properties and ultraviolet light absorption energy capabilities, the modified filler can significantly improve the mechanical properties of the coating. DETAILED DESCRIPTION

[0030] 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 described embodiments 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 creative work are within the scope of protection of the present invention.

[0031] The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used are purchased from conventional biochemical reagent stores unless otherwise specified. The quantitative tests in the following examples were repeated three times, and the data are the average or average ± standard deviation of the three repeated experiments.

[0032] Example 1

[0033] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0034] S1. Preparation of functional fillers:

[0035] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 34% HCl solution was added, and the mixture was ultrasonically dispersed at 30 kHz for 20 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 34% HCl solution was 1:1:10; the acid-treated filler was dispersed in industrial ethanol, a modifier was added, the stirring speed was controlled to be 300 r / min, and the mixture was continuously stirred at 50°C for 4 hours, and then washed, filtered and dried to obtain a functional filler, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 18:70:1, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 10:1;

[0036] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0037] S21, heating castor oil at 100° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0038] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 120° C. and stirring for 8 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 100:45:20:5;

[0039] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 80:20:5, heating to 160° C. and stirring for 6 hours, then distilling under reduced pressure to remove unreacted solvent to obtain an intermediate product, maintaining a ratio of 80:20:5, adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, and repeating the reaction step 5 times under the same experimental conditions to obtain a castor oil-based hyperbranched polyester polyol;

[0040] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0041] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 80° C. under nitrogen protection and stirring for 6 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 20:6:2:0.5, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 1:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 6:1;

[0042] S32, according to parts by weight, using 80 parts of dichloromethane to dissolve 20 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 80 parts of dichloromethane to dissolve 40 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.33 g / min, 3 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 50° C. for 8 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0043] S4. According to weight parts, 80 parts of fluorine-containing hyperbranched epoxy resin, 18 parts of functional filler, 10 parts of 4,4'-diaminodiphenylmethane, 5 parts of mica iron oxide, 1 part of BYK-190 dispersant, 1 part of dinonyl phthalate and 40 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30°C for 40 minutes to obtain a ship anti-corrosion coating.

[0044] Example 2

[0045] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0046] S1. Preparation of functional fillers:

[0047] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 35% by mass HCl solution was added, and the mixture was ultrasonically dispersed at 35 kHz for 17 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 35% by mass HCl solution was 2:1:11; the acid-treated filler was dispersed in industrial ethanol, and a modifier was added, and the stirring speed was controlled to be 300 r / min. After continuous stirring at 60°C for 3.5 hours, the mixture was washed, filtered and dried to obtain a functional filler, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 19:72:3, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 11:1;

[0048] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0049] S21, heating castor oil at 105° C. in a vacuum environment, and keeping the temperature for 35 minutes to remove moisture to obtain dry castor oil;

[0050] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 130° C. and stirring for 7 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 105:47:22:6;

[0051] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 85:25:7, heating to 170° C. and stirring for 5.5 h, then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining a ratio of 80:20:5, adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, and repeating the reaction step 6 times under the same experimental conditions to obtain a castor oil-based hyperbranched polyester polyol;

[0052] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0053] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 85° C. under nitrogen protection and stirring for 5.5 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 22:8:3:0.6, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 2:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 7:1;

[0054] S32, according to parts by weight, using 85 parts of dichloromethane to dissolve 22 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 85 parts of dichloromethane to dissolve 42 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.40 g / min, 4 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 60° C. for 7.5 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0055] S4. According to weight parts, 85 parts of fluorine-containing hyperbranched epoxy resin, 19 parts of functional filler, 10 parts of 4,4'-diaminodiphenylmethane, 5 parts of mica iron oxide, 1 part of BYK-190 dispersant, 2 parts of dinonyl phthalate and 45 parts of deionized water were mixed, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30°C for 40 minutes to obtain a ship anti-corrosion coating.

[0056] Example 3

[0057] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0058] S1. Preparation of functional fillers:

[0059] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 36% HCl solution was added, and the mixture was ultrasonically dispersed at 40kHz for 15 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 36% HCl solution was 2:1:12; the acid-treated filler was dispersed in industrial ethanol, and a modifier was added, and the stirring speed was controlled to be 300r / min. After continuous stirring at 70°C for 3 hours, the functional filler was washed, filtered and dried, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 20:73:3, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 12:1;

[0060] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0061] S21, heating castor oil at 110° C. in a vacuum environment, and keeping the temperature for 30 minutes to remove moisture to obtain dry castor oil;

[0062] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 140° C. and stirring for 6 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 107:50:23:7;

[0063] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 90:26:6, heating to 180° C. and stirring for 5 hours, then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, and repeating the reaction step 7 times under the same experimental conditions to obtain a castor oil-based hyperbranched polyester polyol;

[0064] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0065] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 90° C. under nitrogen protection and stirring for 5 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 24:9:3:0.8, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 2:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 8:1;

[0066] S32, according to parts by weight, using 90 parts of dichloromethane to dissolve 24 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 90 parts of dichloromethane to dissolve 48 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.50 g / min, 5 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 65° C. for 7 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0067] S4. According to weight parts, 90 parts of fluorine-containing hyperbranched epoxy resin, 20 parts of functional filler, 10 parts of 4,4'-diaminodiphenylmethane, 5 parts of mica iron oxide, 1 part of BYK-190 dispersant, 3 parts of dinonyl phthalate and 50 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30°C for 40 minutes to obtain a ship anti-corrosion coating.

[0068] Example 4

[0069] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0070] S1. Preparation of functional fillers:

[0071] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 38% by mass HCl solution was added, and the mixture was ultrasonically dispersed at 50 kHz for 10 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 38% by mass HCl solution was 3:1:12; the acid-treated filler was dispersed in industrial ethanol, and a modifier was added, and the stirring speed was controlled to be 300 r / min. After continuous stirring at 80°C for 2 hours, the mixture was washed, filtered and dried to obtain a functional filler, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 22:75:3, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 15:1;

[0072] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0073] S21, heating castor oil at 120° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0074] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 150° C. and stirring for 4 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 110:55:24:7;

[0075] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 100:30:8, heating to 200° C. and stirring for 4 hours, and then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, and adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, under the same experimental conditions, repeating this reaction step 6 times to obtain a castor oil-based hyperbranched polyester polyol;

[0076] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0077] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 100° C. under nitrogen protection and stirring for 3 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 25:10:4:1, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 3:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 10:1;

[0078] S32, according to parts by weight, using 100 parts of dichloromethane to dissolve 25 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 100 parts of dichloromethane to dissolve 50 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.50 g / min, 7 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 80° C. for 6 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0079] S4. According to parts by weight, 100 parts of fluorine-containing hyperbranched epoxy resin, 22 parts of functional filler, 30 parts of triethylenetetramine, 10 parts of zinc powder, 3 parts of BYK-190 dispersant, 3 parts of dioctyl phthalate and 60 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30° C. for 40 min to obtain a ship anticorrosion coating.

[0080] Comparative Example 1

[0081] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0082] S1. Preparation of functional fillers:

[0083] The zinc oxide nanoparticles were added to a 38% by mass HCl solution, ultrasonically dispersed at 50kHz for 10 minutes, washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 38% HCl solution was 3:1:12; the acid-treated filler was dispersed in industrial ethanol, a modifier was added, and the functional filler was obtained after continuous stirring at 80°C for 2 hours, washed, filtered and dried, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 22:75:3, and the modifier was γ-glycidyloxypropyltrimethoxysilane;

[0084] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0085] S21, heating castor oil at 120° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0086] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 150° C. and stirring for 4 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 110:55:24:7;

[0087] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 100:30:8, heating to 200° C. and stirring for 4 hours, and then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, and adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, under the same experimental conditions, repeating this reaction step 6 times to obtain a castor oil-based hyperbranched polyester polyol;

[0088] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0089] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 100° C. under nitrogen protection and stirring for 3 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 25:10:4:1, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 3:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 10:1;

[0090] S32, according to parts by weight, using 100 parts of dichloromethane to dissolve 25 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 100 parts of dichloromethane to dissolve 50 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.50 g / min, 7 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 80° C. for 6 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0091] S4. According to parts by weight, 100 parts of fluorine-containing hyperbranched epoxy resin, 22 parts of functional fillers, 30 parts of triethylenetetramine, 10 parts of zinc powder, 3 parts of BYK-190 dispersant, 3 parts of dioctyl phthalate and 60 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30° C. for 40 min to obtain a ship anticorrosion coating.

[0092] Comparative Example 2

[0093] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0094] S1. Preparation of functional fillers:

[0095] The titanium dioxide nanoparticles were mixed and then added with a 38% by mass HCl solution, and ultrasonically dispersed at 50kHz for 10 minutes, and washed and filtered to obtain an acid-treated filler, wherein the mass ratio of zinc oxide nanoparticles, titanium dioxide nanoparticles and 38% HCl solution was 3:1:12; the acid-treated filler was dispersed in industrial ethanol, a modifier was added, and the functional filler was obtained after continuous stirring at 80°C for 2 hours, and then washed, filtered and dried, wherein the mass ratio of the acid-treated filler, industrial ethanol and modifier was 22:75:3, and the modifier was aluminum titanate;

[0096] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0097] S21, heating castor oil at 120° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0098] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 150° C. and stirring for 4 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 110:55:24:7;

[0099] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 100:30:8, heating to 200° C. and stirring for 4 hours, and then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, and adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, under the same experimental conditions, repeating this reaction step 6 times to obtain a castor oil-based hyperbranched polyester polyol;

[0100] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0101] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 100° C. under nitrogen protection and stirring for 3 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 25:10:4:1, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 3:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 10:1;

[0102] S32, according to parts by weight, using 100 parts of dichloromethane to dissolve 25 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 100 parts of dichloromethane to dissolve 50 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.50 g / min, 7 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 80° C. for 6 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0103] S4. According to parts by weight, 100 parts of fluorine-containing hyperbranched epoxy resin, 22 parts of functional fillers, 30 parts of triethylenetetramine, 10 parts of zinc powder, 3 parts of BYK-190 dispersant, 3 parts of dioctyl phthalate and 60 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30° C. for 40 min to obtain a ship anticorrosion coating.

[0104] Comparative Example 3

[0105] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0106] S1. Preparation of functional fillers:

[0107] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 38% by mass HCl solution was added, and the mixture was ultrasonically dispersed at 50 kHz for 10 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 38% by mass HCl solution was 3:1:12; the acid-treated filler was dispersed in industrial ethanol, and a modifier was added, and the stirring speed was controlled to be 300 r / min. After continuous stirring at 80°C for 2 hours, the mixture was washed, filtered and dried to obtain a functional filler, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 22:75:3, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 15:1;

[0108] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0109] S21, heating castor oil at 120° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0110] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 150° C. and stirring for 4 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 110:55:24:7;

[0111] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 100:30:8, heating to 200° C. and stirring for 4 hours, and then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, and adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, under the same experimental conditions, repeating this reaction step 6 times to obtain a castor oil-based hyperbranched polyester polyol;

[0112] S3, preparation of hyperbranched epoxy resin:

[0113] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 100° C. under nitrogen protection and stirring for 3 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 25:10:4:1, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 3:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 10:1;

[0114] S4. According to parts by weight, 100 parts of hyperbranched epoxy resin, 22 parts of functional filler, 30 parts of triethylenetetramine, 10 parts of zinc powder, 3 parts of BYK-190 dispersant, 3 parts of dioctyl phthalate and 60 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30° C. for 40 min to obtain a ship anticorrosion coating.

[0115] Comparative Example 4

[0116] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0117] S1. Preparation of functional fillers:

[0118] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 38% by mass HCl solution was added, and the mixture was ultrasonically dispersed at 50 kHz for 10 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 38% by mass HCl solution was 3:1:12; the acid-treated filler was dispersed in industrial ethanol, and a modifier was added, and the stirring speed was controlled to be 300 r / min. After continuous stirring at 80°C for 2 hours, the mixture was washed, filtered and dried to obtain a functional filler, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 22:75:3, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 15:1;

[0119] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0120] S21, heating castor oil at 120° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0121] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 150° C. and stirring for 4 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 110:55:24:7;

[0122] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 100:30:8, heating to 200° C. and stirring for 4 hours, and then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, and adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, under the same experimental conditions, repeating this reaction step 6 times to obtain a castor oil-based hyperbranched polyester polyol;

[0123] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0124] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a crosslinking agent and a catalyst, heating to 100° C. under nitrogen protection and stirring for 3 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, crosslinking agent and catalyst is 25:10:4:1, the crosslinking agent is bisphenol A diglycidyl ether, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 10:1;

[0125] S32, according to parts by weight, using 100 parts of dichloromethane to dissolve 25 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 100 parts of dichloromethane to dissolve 50 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.50 g / min, 7 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 80° C. for 6 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0126] S4. According to parts by weight, 100 parts of fluorine-containing hyperbranched epoxy resin, 22 parts of functional filler, 30 parts of triethylenetetramine, 10 parts of zinc powder, 3 parts of BYK-190 dispersant, 3 parts of dioctyl phthalate and 60 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30° C. for 40 min to obtain a ship anticorrosion coating.

[0127] Comparative Example 5

[0128] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0129] S1. Preparation of functional fillers:

[0130] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 38% by mass HCl solution was added, and the mixture was ultrasonically dispersed at 50 kHz for 10 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 38% by mass HCl solution was 3:1:12; the acid-treated filler was dispersed in industrial ethanol, and a modifier was added, and the stirring speed was controlled to be 300 r / min. After continuous stirring at 80°C for 2 hours, the mixture was washed, filtered and dried to obtain a functional filler, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 22:75:3, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 15:1;

[0131] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0132] S21, heating castor oil at 120° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0133] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 150° C. and stirring for 4 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 110:55:24:7;

[0134] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 100:30:8, heating to 200° C. and stirring for 4 hours, and then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, and adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, under the same experimental conditions, repeating this reaction step 6 times to obtain a castor oil-based hyperbranched polyester polyol;

[0135] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0136] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a crosslinking agent and a catalyst, heating to 100° C. under nitrogen protection and stirring for 3 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, crosslinking agent and catalyst is 25:10:4:1, the crosslinking agent is composed of bisphenol F diglycidyl ether, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 10:1;

[0137] S32, according to parts by weight, using 100 parts of dichloromethane to dissolve 25 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 100 parts of dichloromethane to dissolve 50 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.50 g / min, 7 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 80° C. for 6 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0138] S4. According to parts by weight, 100 parts of fluorine-containing hyperbranched epoxy resin, 22 parts of functional filler, 30 parts of triethylenetetramine, 10 parts of zinc powder, 3 parts of BYK-190 dispersant, 3 parts of dioctyl phthalate and 60 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30° C. for 40 min to obtain a ship anticorrosion coating.

[0139] Comparative Example 6

[0140] A method for preparing a ship anticorrosive coating comprises the following preparation steps:

[0141] S1. Preparation of functional fillers:

[0142] The zinc oxide nanoparticles and the titanium dioxide nanoparticles were mixed, and then a 38% by mass HCl solution was added, and the mixture was ultrasonically dispersed at 50 kHz for 10 minutes, and then washed and filtered to obtain an acid-treated filler, wherein the mass ratio of the zinc oxide nanoparticles, the titanium dioxide nanoparticles and the 38% by mass HCl solution was 3:1:12; the acid-treated filler was dispersed in industrial ethanol, and a modifier was added, and the stirring speed was controlled to be 300 r / min. After continuous stirring at 80°C for 2 hours, the mixture was washed, filtered and dried to obtain a functional filler, wherein the mass ratio of the acid-treated filler, the industrial ethanol and the modifier was 22:75:3, and the modifier was composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 15:1;

[0143] S2, preparation of castor oil-based hyperbranched polyester polyol:

[0144] S21, heating castor oil at 120° C. in a vacuum environment, and keeping the temperature for 40 minutes to remove moisture to obtain dry castor oil;

[0145] S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 150° C. and stirring for 4 hours, and then distilling under reduced pressure to obtain carboxylated castor oil, wherein the mass ratio of tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid is 110:55:24:7;

[0146] S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide to a reactor in a mass ratio of 100:30:8, heating to 200° C. and stirring for 4 hours, and then removing the unreacted solvent by reduced pressure distillation to obtain an intermediate product, maintaining the ratio of 80:20:5, and adding the intermediate product, propylene glycol and sodium hydroxide to the reactor in sequence, under the same experimental conditions, repeating this reaction step 6 times to obtain a castor oil-based hyperbranched polyester polyol;

[0147] S3, preparation of fluorine-containing hyperbranched epoxy resin:

[0148] S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a cross-linking agent and a catalyst, heating to 100° C. under nitrogen protection and stirring for 3 hours, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix, wherein the mass ratio of castor oil-based hyperbranched polyester polyol, epichlorohydrin, cross-linking agent and catalyst is 25:10:4:1, the cross-linking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 3:1, and the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 1:10;

[0149] S32, S32, according to parts by weight, using 100 parts of dichloromethane to dissolve 25 parts of glycidyl 2,2,3,3-tetrafluoropropyl ether, and then using 100 parts of dichloromethane to dissolve 50 parts of hyperbranched epoxy resin matrix, the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution is added dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution at a rate of 0.50 g / min, 7 parts of N,N-dimethylbenzylamine are added, and the mixture is stirred at 80° C. for 6 hours and then distilled under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin;

[0150] S4. According to parts by weight, 100 parts of fluorine-containing hyperbranched epoxy resin, 22 parts of functional filler, 30 parts of triethylenetetramine, 10 parts of zinc powder, 3 parts of BYK-190 dispersant, 3 parts of dioctyl phthalate and 60 parts of deionized water were added, the stirring speed was controlled to 300 r / min, and the stirring was continued at 30° C. for 40 min to obtain a ship anticorrosion coating.

[0151] Performance Testing

[0152] The ship anticorrosion coatings of Examples 1-4 and Comparative Examples 1-6 were sprayed on a 0.1 cm*0.1 cm*0.1 cm iron sheet by spraying. Before spraying, the surface was cleaned with acetone. The spraying thickness was 0.5±0.01 mm, and the coating was cured at 25±2°C.

[0153] The paint films formed by the ship anticorrosion coatings prepared in Examples 1-4 and Comparative Examples 1-6 were subjected to performance tests:

[0154] 1. Adhesion test: The adhesion test of ship anticorrosion coating was carried out according to GB / T5210-2006 standard. The test results are shown in Table 1.

[0155] 2. Salt spray resistance test: The salt spray resistance test of ship anti-corrosion coatings was carried out with reference to GB / T6745-2008 standard. The test results are shown in Table 1.

[0156] 3. Impact strength test: The impact strength test of ship anti-corrosion coating was carried out according to GB / T 1732-1993 standard. The test results are shown in Table 1.

[0157] 4. Artificial aging resistance test: The ship anti-corrosion coating was subjected to an artificial aging resistance test in accordance with GB / T 9276-19966 standard. The test results are shown in Table 1.

[0158] 5. Wear resistance test: The wear resistance test of ship anti-corrosion coating was carried out according to GB / T1768-2006 standard. The test results are shown in Table 1.

[0159] Table 1

[0160] Test items Adhesion / MPa Salt spray resistance / h Impact strength / Kg.cm Artificial aging resistance / h Wear resistance / g Example 1 19.4 1850 75 1300 0.02 Example 2 19.8 1850 77 1300 0.02 Example 3 20.1 1850 82 1300 0.01 Example 4 20.8 1850 85 1300 0.01 Comparative Example 1 17.2 1470 68 1200 0.1 Comparative Example 2 18.1 1320 54 1150 0.07 Comparative Example 3 18.9 820 64 950 0.2 Comparative Example 4 16.9 1280 65 1100 0.08 Comparative Example 5 16.4 1200 57 1050 0.25 Comparative Example 6 15.3 900 50 820 0.3

[0161] From the results shown in Table 1 above, it can be seen that the comprehensive performance of the ship anticorrosion coatings prepared in Examples 1-4 of the present invention is much better than that of Comparative Examples 1-6.

[0162] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing a ship anticorrosive coating, It is characterized in that The method comprises the following preparation steps: S1. Preparation of functional fillers: The zinc oxide nanoparticles and the titanium dioxide nanoparticles are mixed and then treated with acid solution, and then washed and filtered to obtain an acid-treated filler; the acid-treated filler is dispersed in industrial ethanol, a modifier is added, and the mixture is continuously stirred at 50-80° C. for 2-4 hours, and then washed, filtered, and dried to obtain a functional filler; S2, preparation of castor oil-based hyperbranched polyester polyol: S21, in a vacuum environment, heating the castor oil at 100-120° C., and heat-treating for 20-40 minutes to remove moisture to obtain dry castor oil; S22, adding tetrahydrofuran, dry castor oil, phthalic anhydride and p-toluenesulfonic acid into a reaction kettle, heating to 120-150° C. and stirring for 4-8 hours, and then distilling under reduced pressure to obtain carboxylated castor oil; S23, adding carboxylated castor oil, propylene glycol and sodium hydroxide into a reaction kettle, heating to 160-200° C. and stirring for 4-6 hours, then removing the unreacted solvent by distillation under reduced pressure, and repeating this reaction step 5-8 times to obtain a castor oil-based hyperbranched polyester polyol; S3, preparation of fluorine-containing hyperbranched epoxy resin: S31, mixing castor oil-based hyperbranched polyester polyol, epichlorohydrin, a crosslinking agent and a catalyst, heating to 80-100° C. and stirring for 3-6 hours under nitrogen protection, and then distilling under reduced pressure to obtain a hyperbranched epoxy resin matrix; S32, using dichloromethane to dissolve glycidyl 2,2,3,3-tetrafluoropropyl ether and a hyperbranched epoxy resin matrix respectively, adding the dissolved glycidyl 2,2,3,3-tetrafluoropropyl ether / dichloromethane solution dropwise to the hyperbranched epoxy resin matrix / dichloromethane solution, adding N,N-dimethylbenzylamine, stirring continuously at 50-80° C. for 6-8 hours, and then distilling under reduced pressure to obtain a fluorine-containing hyperbranched epoxy resin; S4. Evenly mix the fluorine-containing hyperbranched epoxy resin, functional filler, curing agent, anti-rust pigment, dispersant, plasticizer and deionized water to obtain a ship anti-corrosion coating.

2. The method for preparing the ship anticorrosive coating according to claim 1, It is characterized in that In the step S1, the modifier is composed of γ-glycidyloxypropyltrimethoxysilane and aluminum titanate in a mass ratio of 10-15:

1.

3. The method for preparing the ship anticorrosion coating according to claim 1, It is characterized in that In the step S31, the crosslinking agent is composed of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in a mass ratio of 1-3:

1.

4. The method for preparing the ship anticorrosion coating according to claim 1, It is characterized in that In the step S31, the catalyst is composed of triethylamine and 2-methylimidazole in a molar ratio of 6-10:

1.

5. The method for preparing the ship anticorrosion coating according to claim 1, It is characterized in that In step S4, the components by weight include 80-100 parts of fluorine-containing hyperbranched epoxy resin, 18-22 parts of functional filler, 10-30 parts of curing agent, 5-10 parts of rust-proof pigment, 1-3 parts of dispersant, 1-3 parts of plasticizer, and 40-60 parts of deionized water.

6. The method for preparing the ship anticorrosive coating according to claim 1, It is characterized in that In step S4, the curing agent is at least one of triethylenetetramine, 4,4'-diaminodiphenylmethane and hexamethylenediamine.

7. The method for preparing the ship anticorrosion coating according to claim 1, It is characterized in that In step S4, the anti-rust pigment is at least one of zinc powder, zinc phosphate and mica iron oxide.

8. The method for preparing the ship anticorrosive coating according to claim 1, It is characterized in that The dispersant in step S4 is a polyester dispersant.

9. The method for preparing the ship anticorrosive coating according to claim 1, It is characterized in that In the step S4, the plasticizer is at least one of dioctyl phthalate, dinonyl phthalate and didecyl phthalate.

10. A ship anticorrosive coating, It is characterized in that The carbon-based ceramic friction material is prepared by the method for preparing the additive for mixing with raw materials according to any one of claims 1 to 9.