Marine anticorrosion and antifouling coating and preparation method thereof

Abstract

The invention discloses a marine anticorrosion and antifouling coating and a preparation method thereof, and relates to the technical field of coatings. When preparing the marine anticorrosion and antifouling coating, the present invention reacts triazoline dione monomer and 4-chloro-1-butene to obtain a quaternized triazoline dione monomer; reacts epoxy resin and quaternized triazoline dione monomer to obtain a modified epoxy resin; polymerizes 3-aminopropylmethyl diethoxysilane and indolyl diethoxysilane to obtain oligosiloxane; reacts silicon dioxide with aminopropyl triethoxysilane and cyanamide in sequence to obtain modified silicon dioxide; epoxy resin, modified epoxy resin, oligosiloxane and modified silicon dioxide are uniformly mixed to obtain epoxy coating; epoxy coating is coated and cured to obtain a marine anticorrosion and antifouling coating. The marine anticorrosion and antifouling coating prepared by the present invention has excellent anticorrosion, antifouling and wear resistance.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, in particular to an anti-corrosion and anti-fouling coating for marine use and a preparation method thereof. Background Art

[0002] There are a large number of microorganisms, bacteria and other marine plants and animals in the ocean. Their adhesion, growth and reproduction on the surface of marine equipment are collectively referred to as marine biofouling. Biofouling adhering to the surface of the ship will not only increase the surface roughness but also increase the weight of the hull, which will reduce the speed of navigation and increase fuel consumption, and also increase greenhouse gas emissions. Marine biofouling will also greatly shorten the service life of the ship. Once the antifouling layer on the surface of the hull is damaged, the fouling organisms will directly adhere to the surface of the hull, accelerating the corrosion rate of the surface metal materials. Seawater is an electrolyte solution containing a large amount of chloride ions, calcium ions, magnesium ions, etc. These ions provide conditions for the electrochemical corrosion of metals.

[0003] It is a common technical means to use organic coatings to protect the hull from fouling and corrosion. Organic coatings can form a physical barrier to isolate the corrosive medium from the hull. However, ordinary organic coatings only have a physical barrier effect or a single function. Especially after the coating is damaged by scratches, punctures, wear, etc., the corrosive medium will contact the hull through the defects of the coating, thereby causing corrosion of the hull. Therefore, it is necessary to improve the existing technology so that the coating has excellent antibacterial properties, is not easily damaged, and can be repaired in time after damage, so as to achieve the effect of antifouling and anticorrosion. Summary of the invention

[0004] The purpose of the present invention is to provide a marine anti-corrosion and anti-fouling coating 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 marine anti-corrosion and anti-fouling coating, characterized in that the marine anti-corrosion and anti-fouling coating is prepared by reacting epoxy resin and quaternized triazolinedione monomer to obtain modified epoxy resin; polymerizing 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane to obtain oligosiloxane; reacting pre-modified silica and cyanamide to obtain modified silica; uniformly mixing epoxy resin, modified epoxy resin, oligosiloxane and modified silica to obtain epoxy coating; and coating and curing the epoxy coating to obtain the coating;

[0007] The quaternized triazolinedione monomer is prepared by reacting triazolinedione monomer and 4-chloro-1-butene;

[0008] The triazolinedione monomer is prepared by oxidizing 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione with an oxidant;

[0009] The indolyl diethoxysilane is prepared by reacting 3-aminopropylmethyl diethoxysilane and 3-indolecarboxaldehyde;

[0010] The pre-modified silicon dioxide is prepared by reacting silicon dioxide and aminopropyltriethoxysilane.

[0011] A method for preparing an anti-corrosion and anti-fouling coating for use in the ocean, the method comprising the following preparation steps:

[0012] (1) Under nitrogen protection, 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione, oxidant and dichloromethane are mixed evenly in a mass ratio of 1:(2.4~2.6):(14~16), stirred at 10~30°C and 200~300r / min for 2~2.2h, filtered, washed with dichloromethane 3~5 times, and the filtrate is dried at 36~38°C for 7~8h under vacuum conditions to obtain triazolinedione monomer; triazolinedione monomer and 4-chloro-1-butene are added to toluene with a molar ratio of 1:1 to 14~16 times the mass of triazolinedione monomer, stirred at 45~55°C and 200~300r / min for 2~3h, and dried at 48~50°C for 8~10h under vacuum conditions to obtain quaternized triazolinedione monomer;

[0013] (2) The quaternized triazolinedione monomer, benzoyl peroxide and n-butanol are mixed uniformly in a mass ratio of 1:(0.03-0.05):(6-8) to obtain a monomer reaction liquid; the epoxy resin, ethylene glycol monobutyl ether and n-butanol are mixed uniformly in a mass ratio of 1:(1-2):(2-3), placed in a high pressure reactor, stirred at 100-110°C and 300-500 r / min for 10-20 min, and the monomer reaction liquid of 1-1.2 times the mass of the epoxy resin is added dropwise at a uniform rate within 20 min, the temperature is raised to 120-122°C, the reaction is continued with stirring for 2-3 h, and the mixture is cooled to room temperature to obtain a modified epoxy resin;

[0014] (3) Add 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane in a molar ratio of 1:(0.6~0.8) to a reactor, add deionized water (1.4~1.6 times the mass of 3-aminopropylmethyldiethoxysilane) and lithium hydroxide (0.3~0.5 times the mass of 3-aminopropylmethyldiethoxysilane), raise the temperature to 80~82°C, continue stirring and reacting for 20~22 minutes, add hexamethyldisiloxane (0.1~0.12 times the mass of 3-aminopropylmethyldiethoxysilane), continue stirring and reacting for 6~8 minutes, cool to room temperature, wash with an equal volume of deionized water and toluene, stand for stratification, remove the aqueous phase, repeat washing 3~5 times, take the organic phase and place it in a drying oven, dry it at 58~60°C under vacuum conditions for 8~10 hours to obtain oligosiloxane;

[0015] (4) Pre-modified silica, 10%-12% hydrochloric acid aqueous solution and anhydrous ethanol were mixed uniformly in a mass ratio of 1:(8-10):(50-60), placed in a high-pressure reactor, stirred at 10-30°C and 200-220 r / min for 19-21 min, heated to 78-80°C, and uniformly added with cyanamide aqueous solution in an amount 10-12 times the mass of the pre-modified silica within 15 min, continued to stir and react for 4-5 h, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 60-70°C under vacuum conditions for 8-10 h to obtain modified silica;

[0016] (5) Weigh 36-40 parts of epoxy resin, 44-50 parts of modified epoxy resin, 18-20 parts of oligosiloxane, 3-4 parts of modified silica and 24-26 parts of acetone by mass; mix the epoxy resin, modified epoxy resin, oligosiloxane, modified silica and acetone evenly, and then adjust the viscosity to 180-200 mPa·s with acetone to prepare an epoxy coating; apply and cure the epoxy coating to prepare a marine anticorrosion and antifouling coating.

[0017] As an optimization, the preparation method of the oxidant in step (1) is as follows: bromine and chloroform are mixed evenly at a mass ratio of 1:(90-100) to prepare a bromine chloroform solution; under nitrogen protection, triethylenediamine and chloroform are mixed evenly at a mass ratio of 1:(13-15), and under stirring conditions of 10-30°C and 200-300 r / min, bromine chloroform solution of 3-4 times the mass of triethylenediamine is added dropwise at a uniform rate within 10 minutes, and the stirring reaction is continued for 1-2 hours, filtered, and dried at 40-42°C under vacuum conditions for 10-12 hours to obtain the oxidant.

[0018] As an optimization, the reaction process of the quaternized triazolinedione monomer in step (1) is as follows:

[0019]

[0020] As an optimization, the model of the epoxy resin in step (2) and step (5) is E51.

[0021] As an optimization, the preparation method of the indolyl diethoxysilane in step (3) is: adding 3-aminopropyl methyl diethoxysilane and 3-indole formaldehyde in a molar ratio of 1:1 to N,N-dimethylformamide with a mass of 14 to 16 times that of 3-aminopropyl methyl diethoxysilane, stirring at 50 to 60° C. and 200 to 300 r / min for 3 to 4 hours, and drying at 55 to 65° C. under vacuum conditions for 7 to 9 hours to obtain indolyl diethoxysilane;

[0022] The reaction process is as follows:

[0023] .

[0024] As an optimization, the preparation method of the pre-modified silica in step (4) is as follows: silica and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(66~70), ultrasonically dispersed for 1~1.2h, silane hydrolyzate of 6~8 times the mass of silica is added, stirred at 56~60°C and 180~200r / min for 2~3h, filtered, washed with anhydrous ethanol for 3~5 times, and dried at 68~70°C under vacuum conditions for 9~10h to obtain pre-modified silica.

[0025] As an optimization, the preparation method of the silane hydrolyzate is: aminopropyltriethoxysilane and deionized water are mixed evenly in a mass ratio of 1:(20~22), stirred at 180~200r / min for 8~10min at room temperature, adjusted the pH to 5.8~6 with a 1mol / L oxalic acid aqueous solution, and continued stirring for 28~30min to prepare a silane hydrolyzate.

[0026] As an optimization, the particle size of the silicon dioxide is 2000 mesh, and the manufacturer is Lingshou County Maozhuo Building Materials Co., Ltd.

[0027] As an optimization, the mass fraction of the cyanamide aqueous solution in step (4) is 30% to 32%.

[0028] As an optimization, the coating and curing process parameters of step (5) are as follows: the epoxy coating is coated on the metal substrate, and the coating amount is 0.16~0.2kg / m 2 , dry at 58~60℃ for 6~8h.

[0029] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0030] In the preparation of the marine anticorrosion and antifouling coating, 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione is oxidized with an oxidant to obtain a triazolinedione monomer; the triazolinedione monomer and 4-chloro-1-butene are reacted to obtain a quaternized triazolinedione monomer; epoxy resin and quaternized triazolinedione monomer are reacted to obtain a modified epoxy resin; 3-aminopropylmethyldiethoxysilane and 3-indolecarboxaldehyde are reacted to obtain an indole carboxaldehyde. Indole diethoxysilane; 3-aminopropylmethyldiethoxysilane and indole diethoxysilane are polymerized to obtain oligosiloxane; silicon dioxide and aminopropyltriethoxysilane are reacted to obtain pre-modified silicon dioxide; pre-modified silicon dioxide and cyanamide are reacted to obtain modified silicon dioxide; epoxy resin, modified epoxy resin, oligosiloxane and modified silicon dioxide are uniformly mixed to obtain epoxy coating; the epoxy coating is coated and cured to obtain a marine anti-corrosion and anti-fouling coating.

[0031] First, 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione is oxidized with an oxidant to obtain a triazolinedione monomer, and the tertiary amine structure on the triazolinedione monomer reacts with the chlorine atom on 4-chloro-1-butene to generate a quaternary ammonium salt structure to obtain a quaternized triazolinedione monomer, and a carbon-carbon double bond is introduced into the quaternized triazolinedione monomer; although the epoxy resin does not have an unsaturated double bond, it contains an ether bond, and the aH atom on the ortho-carbon and the H atom on the tertiary carbon atom are relatively active, and free radicals can be formed under the action of an initiator to initiate a graft polymerization reaction, and the quaternized triazolinedione monomer is grafted onto the epoxy resin, and a quaternary ammonium salt structure and a triazolinedione structure are introduced into the molecular side chain of the epoxy resin; when a piece of material is submerged in seawater, some soluble organic matter (sugars, proteins) and inorganic salts will soon be adsorbed on its surface to form a basement membrane, and some simple microorganisms and protozoa will successively attach to it. The quaternary ammonium salt structure can adsorb negatively charged bacteria and has a good bactericidal effect. It can kill bacteria attached to the surface of the coating in time, thereby improving the antifouling performance of the marine anticorrosion and antifouling coating. The triazolinedione structure introduced on the side chain of the modified epoxy resin can react with the indole group introduced on the oligosiloxane to form a reversible CN bond, thereby forming a dynamic cross-linked network in the marine anticorrosion and antifouling coating. When the coating on the outer surface of the metal device is damaged due to scratches, punctures and other factors, the coating can be repaired through the reversible CN bond to prevent the corrosive medium from contacting the metal device through the defects of the coating, thereby improving the anti-corrosion ability of the marine anticorrosion and antifouling coating. The reaction mechanism is as follows:

[0032] .

[0033] Secondly, 3-aminopropylmethyldiethoxysilane and 3-indolecarboxaldehyde are reacted to obtain indolyldiethoxysilane; 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane are polymerized to obtain oligosiloxane; a large number of indole groups and amino groups are introduced into the side chains of the oligosiloxane molecules; the introduced amino groups participate in the curing process of the coating, replace the small molecule curing agent, and form a cross-linked network structure between the oligosiloxane and the epoxy resin, and introduce Si-O-Si segments into the coating. The bond energy of the Si-O bond is greater than that of the CC bond, and it takes more energy to destroy the Si-O bond. The introduction of -Si chain segments makes the coating less likely to be torn by external shear forces, giving the marine anti-corrosion and anti-fouling coating excellent wear resistance; the indole group introduced on the side chain of the oligosiloxane can react with the triazolinedione structure introduced on the modified epoxy resin to generate a reversible CN bond, forming a dynamic cross-linked network in the marine anti-corrosion and anti-fouling coating. When the coating on the outer surface of the metal device is damaged due to scratches, punctures and other factors, the coating can be repaired through reversible CN bonds to prevent the corrosive medium from contacting the metal device through the defects of the coating, thereby improving the corrosion resistance of the marine anti-corrosion and anti-fouling coating.

[0034] Finally, silica and aminopropyltriethoxysilane are reacted to obtain pre-modified silica, and amino groups are introduced into the pre-modified silica; the amino groups on the pre-modified silica are reacted with the cyano groups on cyanamide to obtain modified silica, a guanidine salt structure is generated on the modified silica, and amino groups are introduced; the guanidine salt structure generated on the modified silica has bactericidal ability, which can kill bacteria attached to the surface of the coating in time, thereby improving the antifouling performance of the marine anticorrosion and antifouling coating; the introduction of amino groups into the modified silica allows silica to participate in the curing process of the coating , so that chemical cross-linking is formed between the molecular chains of silica and epoxy resin, the mechanical properties of the coating are improved, the coating is not easily torn by external shear forces, and the marine anti-corrosion and anti-fouling coating has excellent wear resistance; silica is a hard inorganic non-metallic material. Surface modification of silica can improve the compatibility between silica and the matrix resin, make silica evenly dispersed in the coating, avoid the occurrence of agglomeration, give full play to the reinforcing properties of silica, and further improve the wear resistance of marine anti-corrosion and anti-fouling coatings. DETAILED DESCRIPTION

[0035] 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.

[0036] Embodiment 1:

[0037] A method for preparing an anti-corrosion and anti-fouling coating for use in the ocean, the method comprising the following preparation steps:

[0038] (1) Bromine and chloroform were mixed at a mass ratio of 1:90 to prepare a bromine chloroform solution; under nitrogen protection, triethylenediamine and chloroform were mixed at a mass ratio of 1:13, and under stirring conditions of 10°C and 200 r / min, bromine chloroform solution 3 times the mass of triethylenediamine was added dropwise over 10 minutes, and the reaction was continued with stirring for 2 hours, filtered, and dried at 40°C under vacuum conditions for 12 hours to prepare an oxidant; under nitrogen protection, 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione was added dropwise at a rate of 1:13 to obtain a bromine solution; , oxidant, and dichloromethane are mixed evenly in a mass ratio of 1:2.4:14, stirred at 10°C and 200r / min for 2.2h, filtered, washed with dichloromethane 3 times, and the filtrate is dried at 36°C for 8h under vacuum conditions to obtain a triazolinedione monomer; triazolinedione monomer and 4-chloro-1-butene are added to toluene with a mass ratio of 14 times that of the triazolinedione monomer in a molar ratio of 1:1, stirred at 45°C and 200r / min for 3h, and dried at 48°C for 10h under vacuum conditions to obtain a quaternized triazolinedione monomer;

[0039] (2) The quaternized triazolinedione monomer, benzoyl peroxide and n-butanol were mixed evenly in a mass ratio of 1:0.03:6 to obtain a monomer reaction liquid; epoxy resin E51, ethylene glycol monobutyl ether and n-butanol were mixed evenly in a mass ratio of 1:1:2, placed in a high-pressure reactor, stirred at 100°C and 300 r / min for 20 min, and the monomer reaction liquid of 1 times the mass of epoxy resin E51 was uniformly added dropwise within 20 min, the temperature was raised to 120°C, the stirring reaction was continued for 3 h, and the mixture was cooled to room temperature to obtain a modified epoxy resin;

[0040] (3) 3-aminopropylmethyldiethoxysilane and 3-indolecarboxaldehyde were added in a molar ratio of 1:1 to N,N-dimethylformamide (14 times the mass of 3-aminopropylmethyldiethoxysilane), stirred at 50°C and 200 r / min for 4 h, and dried at 55°C under vacuum for 9 h to obtain indolyldiethoxysilane; 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane were added in a molar ratio of 1:0.6 to a reactor, and 3-aminopropylmethyldiethoxysilane was added. 1.4 times the amount of deionized water, 0.3 times the amount of lithium hydroxide of 3-aminopropylmethyldiethoxysilane, heat to 80°C, continue stirring and reacting for 22 minutes, add hexamethyldisiloxane of 0.1 times the amount of 3-aminopropylmethyldiethoxysilane, continue stirring and reacting for 8 minutes, cool to room temperature, wash with an equal volume of deionized water and toluene, stand for stratification, remove the water phase, repeat washing 3 times, take the organic phase and place it in a drying oven, dry it at 58°C for 10 hours under vacuum conditions to obtain oligosiloxane;

[0041] (4) Aminopropyltriethoxysilane and deionized water were mixed at a mass ratio of 1:20, stirred at room temperature at 180 r / min for 10 min, adjusted the pH to 5.8 with a 1 mol / L oxalic acid aqueous solution, and continued to stir for 30 min to prepare a silane hydrolyzate; silicon dioxide and anhydrous ethanol were mixed at a mass ratio of 1:66, ultrasonically dispersed for 1 h, and silane hydrolyzate 6 times the mass of silicon dioxide was added, stirred at 56 ° C, 180 r / min for 3 h, filtered, washed with anhydrous ethanol 3 times, and dried under vacuum for 6 8℃ drying for 10h to obtain pre-modified silica; pre-modified silica, 10% hydrochloric acid aqueous solution and anhydrous ethanol were mixed evenly in a mass ratio of 1:8:50, placed in a high-pressure reactor, stirred at 10℃ and 200r / min for 21min, heated to 78℃, and a 30% cyanamide aqueous solution with a mass fraction of 10 times the mass of the pre-modified silica was uniformly added dropwise within 15min, continued to stir and react for 5h, filtered, washed with anhydrous ethanol 3 times, and dried at 60℃ under vacuum conditions for 10h to obtain modified silica;

[0042] (5) Weigh 36 parts of epoxy resin E51, 44 parts of modified epoxy resin, 18 parts of oligosiloxane, 3 parts of modified silica, and 24 parts of acetone by mass; mix the epoxy resin E51, modified epoxy resin, oligosiloxane, modified silica, and acetone evenly, and then adjust the viscosity to 180 mPa·s with acetone to prepare an epoxy coating; apply the epoxy coating on a metal substrate at a coating amount of 0.16 kg / m 2 , and dried at 58°C for 8h to obtain a marine anti-corrosion and anti-fouling coating.

[0043] Embodiment 2:

[0044] A method for preparing an anti-corrosion and anti-fouling coating for use in the ocean, the method comprising the following preparation steps:

[0045] (1) Bromine and chloroform were mixed at a mass ratio of 1:95 to prepare a bromine chloroform solution; under nitrogen protection, triethylenediamine and chloroform were mixed at a mass ratio of 1:14 to prepare a bromine chloroform solution; at 20°C, 250 r / min stirring conditions, 3.5 times the mass of triethylenediamine bromine chloroform solution was added dropwise over 10 min, stirring was continued for 1.5 h, filtered, and dried at 41°C under vacuum conditions for 11 h to prepare an oxidant; under nitrogen protection, 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-diamine was added dropwise over 10 min. Ketone, oxidant and dichloromethane were mixed evenly in a mass ratio of 1:2.5:15, stirred at 20°C and 250r / min for 2.1h, filtered, washed with dichloromethane 4 times, and the filtrate was dried at 37°C for 7.5h under vacuum conditions to obtain a triazolinedione monomer; triazolinedione monomer and 4-chloro-1-butene were added to toluene with a molar ratio of 1:1 to 15 times the mass of triazolinedione monomer, stirred at 50°C and 250r / min for 2.5h, and dried at 49°C for 9h under vacuum conditions to obtain a quaternized triazolinedione monomer;

[0046] (2) The quaternized triazolinedione monomer, benzoyl peroxide and n-butanol were mixed evenly at a mass ratio of 1:0.04:7 to obtain a monomer reaction liquid; epoxy resin E51, ethylene glycol monobutyl ether and n-butanol were mixed evenly at a mass ratio of 1:1.5:2.5, placed in a high-pressure reactor, stirred at 105°C and 400 r / min for 15 min, and the monomer reaction liquid of 1.1 times the mass of epoxy resin E51 was uniformly added dropwise within 20 min, the temperature was raised to 121°C, the stirring reaction was continued for 2.5 h, and the mixture was cooled to room temperature to obtain a modified epoxy resin;

[0047] (3) 3-aminopropylmethyldiethoxysilane and 3-indolecarboxaldehyde were added in a molar ratio of 1:1 to N,N-dimethylformamide (15 times the mass of 3-aminopropylmethyldiethoxysilane), stirred at 55°C and 250 r / min for 3.5 h, and dried at 60°C under vacuum for 8 h to obtain indolyldiethoxysilane; 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane were added in a molar ratio of 1:0.7 to the reactor, and 3-aminopropylmethyldiethoxysilane was added. 1.5 times the mass of deionized water, 0.4 times the mass of lithium hydroxide of 3-aminopropylmethyldiethoxysilane, heat to 81°C, continue stirring and reacting for 21 minutes, add hexamethyldisiloxane (0.11 times the mass of 3-aminopropylmethyldiethoxysilane), continue stirring and reacting for 7 minutes, cool to room temperature, wash with an equal volume of deionized water and toluene, stand for stratification, remove the water phase, repeat washing 4 times, take the organic phase and place it in a drying oven, dry it at 59°C for 9 hours under vacuum conditions to obtain oligosiloxane;

[0048] (4) Aminopropyltriethoxysilane and deionized water were mixed in a mass ratio of 1:21, stirred at room temperature at 190 r / min for 9 min, adjusted the pH to 5.9 with a 1 mol / L oxalic acid aqueous solution, and continued to stir for 29 min to prepare a silane hydrolyzate; silicon dioxide and anhydrous ethanol were mixed in a mass ratio of 1:68, ultrasonically dispersed for 1.1 h, and silane hydrolyzate 7 times the mass of silicon dioxide was added, stirred at 58 ° C, 190 r / min for 2.5 h, filtered, washed with anhydrous ethanol 4 times, and under vacuum conditions. Dry at 69°C for 9.5h to obtain pre-modified silica; mix pre-modified silica, 11% hydrochloric acid aqueous solution and anhydrous ethanol in a mass ratio of 1:9:55, place in a high-pressure reactor, stir at 20°C and 210r / min for 20min, heat to 79°C, uniformly add 11 times the mass of pre-modified silica and 31% cyanamide aqueous solution within 15min, continue stirring and reacting for 4.5h, filter, wash with anhydrous ethanol 4 times, dry at 65°C under vacuum conditions for 9h to obtain modified silica;

[0049] (5) Weigh 38 parts of epoxy resin E51, 47 parts of modified epoxy resin, 19 parts of oligosiloxane, 3.5 parts of modified silica, and 25 parts of acetone by mass; mix the epoxy resin E51, modified epoxy resin, oligosiloxane, modified silica, and acetone evenly, and then adjust the viscosity to 190 mPa·s with acetone to prepare an epoxy coating; apply the epoxy coating on a metal substrate at a coating amount of 0.18 kg / m 2 , and dried at 59°C for 7h to obtain a marine anti-corrosion and anti-fouling coating.

[0050] Embodiment 3:

[0051] A method for preparing an anti-corrosion and anti-fouling coating for use in the ocean, the method comprising the following preparation steps:

[0052] (1) Bromine and chloroform were mixed at a mass ratio of 1:100 to prepare a bromine chloroform solution; under nitrogen protection, triethylenediamine and chloroform were mixed at a mass ratio of 1:15 to prepare a bromine chloroform solution; at 30°C, 300 r / min stirring conditions, bromine chloroform solution 4 times the mass of triethylenediamine was added dropwise over 10 minutes at a constant rate; stirring was continued for 1 hour, filtered, and dried at 42°C under vacuum conditions for 10 hours to prepare an oxidant; under nitrogen protection, 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5- The diketone, oxidant and dichloromethane were mixed evenly in a mass ratio of 1:2.6:16, stirred at 30°C and 300 r / min for 2 hours, filtered, washed with dichloromethane 5 times, and the filtrate was dried at 38°C for 7 hours under vacuum conditions to obtain a triazolinedione monomer; the triazolinedione monomer and 4-chloro-1-butene were added to toluene with a mass 16 times that of the triazolinedione monomer in a molar ratio of 1:1, stirred at 55°C and 300 r / min for 2 hours, and dried at 50°C for 8 hours under vacuum conditions to obtain a quaternized triazolinedione monomer;

[0053] (2) The quaternized triazolinedione monomer, benzoyl peroxide and n-butanol were mixed evenly at a mass ratio of 1:0.05:8 to obtain a monomer reaction liquid; epoxy resin E51, ethylene glycol monobutyl ether and n-butanol were mixed evenly at a mass ratio of 1:1.5:2.5, placed in a high-pressure reactor, stirred at 105°C and 400 r / min for 15 min, and the monomer reaction liquid of 1.1 times the mass of epoxy resin E51 was uniformly added dropwise within 20 min, the temperature was raised to 121°C, the stirring reaction was continued for 2.5 h, and the mixture was cooled to room temperature to obtain a modified epoxy resin;

[0054] (3) 3-aminopropylmethyldiethoxysilane and 3-indolecarboxaldehyde were added in a molar ratio of 1:1 to N,N-dimethylformamide (16 times the mass of 3-aminopropylmethyldiethoxysilane), stirred at 60°C and 300 r / min for 3 h, and dried at 65°C under vacuum for 7 h to obtain indolyldiethoxysilane; 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane were added in a molar ratio of 1:0.8 to a reactor, and 3-aminopropylmethyldiethoxysilane was added. 1.6 times the amount of deionized water, 0.5 times the amount of lithium hydroxide of 3-aminopropylmethyldiethoxysilane, heat to 82°C, continue stirring and reacting for 20 minutes, add hexamethyldisiloxane of 0.12 times the amount of 3-aminopropylmethyldiethoxysilane, continue stirring and reacting for 6 minutes, cool to room temperature, wash with an equal volume of deionized water and toluene, stand for stratification, remove the water phase, repeat washing 5 times, take the organic phase and place it in a drying oven, dry it at 60°C for 8 hours under vacuum conditions to obtain oligosiloxane;

[0055] (4) Aminopropyltriethoxysilane and deionized water were mixed at a mass ratio of 1:22, stirred at 200 r / min for 8 min at room temperature, adjusted the pH to 6 with 1 mol / L oxalic acid aqueous solution, and continued stirring for 28 min to prepare a silane hydrolyzate; silicon dioxide and anhydrous ethanol were mixed at a mass ratio of 1:70, ultrasonically dispersed for 1 h, and silane hydrolyzate 8 times the mass of silicon dioxide was added, stirred at 60°C and 200 r / min for 2 h, filtered, washed with anhydrous ethanol 5 times, and dried under vacuum at 70 ℃ and dried for 9 hours to obtain pre-modified silica; pre-modified silica, 12% hydrochloric acid aqueous solution and anhydrous ethanol were mixed evenly in a mass ratio of 1:10:60, placed in a high-pressure reactor, stirred at 30℃ and 220r / min for 19 minutes, heated to 80℃, and a 32% cyanamide aqueous solution with a mass fraction of 12 times the mass of the pre-modified silica was uniformly added dropwise within 15 minutes, and the reaction was continued by stirring for 4 hours, filtered, washed with anhydrous ethanol 5 times, and dried at 70℃ under vacuum conditions for 8 hours to obtain modified silica;

[0056] (5) Weigh 40 parts of epoxy resin E51, 50 parts of modified epoxy resin, 20 parts of oligosiloxane, 4 parts of modified silica, and 26 parts of acetone by mass; mix the epoxy resin E51, modified epoxy resin, oligosiloxane, modified silica, and acetone evenly, and then adjust the viscosity to 200 mPa·s with acetone to prepare an epoxy coating; apply the epoxy coating on the metal substrate at a coating amount of 0.2 kg / m 2 , and dried at 60°C for 6 hours to obtain a marine anti-corrosion and anti-fouling coating.

[0057] Comparative Example 1:

[0058] The preparation method of the marine anticorrosion and antifouling coating of Comparative Example 1 is different from that of Example 2 in that step (1) and step (2) are not performed, and step (5) is modified as follows: 85 parts of epoxy resin E51, 19 parts of oligosiloxane, 3.5 parts of modified silica, and 25 parts of acetone are weighed by mass; the epoxy resin E51, oligosiloxane, modified silica, and acetone are mixed uniformly, and then the viscosity is adjusted to 190 mPa·s with acetone to prepare an epoxy coating; the epoxy coating is applied on a metal substrate at a coating amount of 0.18 kg / m 2 The mixture was dried at 59°C for 7 hours to obtain a marine anti-corrosion and anti-fouling coating. The remaining steps were the same as those in Example 2.

[0059] Comparative Example 2:

[0060] The difference between the preparation method of the marine anticorrosion and antifouling coating of Comparative Example 2 and Example 2 lies in the difference in step (3), and step (3) is modified as follows: 3-aminopropylmethyldiethoxysilane and dimethyldiethoxysilane are added to a reaction kettle at a molar ratio of 1:0.7, deionized water of 1.5 times the mass of 3-aminopropylmethyldiethoxysilane and lithium hydroxide of 0.4 times the mass of 3-aminopropylmethyldiethoxysilane are added, the temperature is raised to 81°C, the reaction is continued with stirring for 21 minutes, hexamethyldisiloxane of 0.11 times the mass of 3-aminopropylmethyldiethoxysilane is added, the reaction is continued with stirring for 7 minutes, the temperature is lowered to room temperature, the mixture is washed with an equal volume of deionized water and toluene, the mixture is allowed to stand for stratification, the aqueous phase is removed, the washing is repeated 4 times, the organic phase is placed in a drying oven, and dried at 59°C for 9 hours under vacuum conditions to obtain oligosiloxane. The remaining steps are the same as those of Example 2.

[0061] Comparative Example 3:

[0062] The preparation method of the marine anticorrosion and antifouling coating of Comparative Example 3 is different from that of Example 2 in that step (3) is not performed, and step (5) is modified as follows: 38 parts of epoxy resin E51, 47 parts of modified epoxy resin, 19 parts of hexamethylenediamine, 3.5 parts of modified silica, and 25 parts of acetone are weighed by mass; the epoxy resin E51, the modified epoxy resin, the hexamethylenediamine, the modified silica, and the acetone are uniformly mixed, and then the viscosity is adjusted to 190 mPa·s with acetone to prepare an epoxy coating; the epoxy coating is applied on a metal substrate at a coating amount of 0.18 kg / m 2 The mixture was dried at 59°C for 7 hours to obtain a marine anti-corrosion and anti-fouling coating. The remaining steps were the same as those in Example 2.

[0063] Comparative Example 4:

[0064] The preparation method of the marine anticorrosion and antifouling coating of Comparative Example 4 is different from that of Example 2 in that step (4) is not performed, and step (5) is modified as follows: 38 parts of epoxy resin E51, 47 parts of modified epoxy resin, 19 parts of oligosiloxane, 3.5 parts of silicon dioxide, and 25 parts of acetone are weighed by mass; the epoxy resin E51, the modified epoxy resin, the oligosiloxane, the silicon dioxide, and the acetone are uniformly mixed, and then the viscosity is adjusted to 190 mPa·s with acetone to prepare an epoxy coating; the epoxy coating is applied on a metal substrate at a coating amount of 0.18 kg / m 2 The mixture was dried at 59°C for 7 hours to obtain a marine anti-corrosion and anti-fouling coating. The remaining steps were the same as those in Example 2.

[0065] Test Example 1

[0066] Antifouling performance test

[0067] Test method: The epoxy coatings prepared in the examples and comparative examples were poured into a mold, dried at 60°C for 7 hours, and demoulded to obtain a sample after cooling to room temperature. The sample was sterilized by ultraviolet irradiation for 3 hours; the Escherichia coli strains were activated and prepared to a concentration of 3×10 4 cfu / ml bacterial suspension; put the sample into the bacterial suspension, shake at 300r / min for 5min at room temperature, take 1ml of the bacterial suspension and dilute it to 100 times, take 1ml of the diluted bacterial suspension and inoculate it into agar medium, culture it at 37℃ for 16h, count the colonies according to the method in GB / T15979, and calculate the antibacterial rate, antibacterial rate = (average colony count before sample shaking - average colony count after sample shaking) / average colony count before sample shaking × 100%. The results are shown in Table 1.

[0068] Table 1

[0069] Antibacterial rate Antibacterial rate Example 1 99.57 Comparative Example 1 91.71 Example 2 99.68 Comparative Example 2 99.48 Example 3 99.52 Comparative Example 3 99.50 Comparative Example 4 93.61

[0070] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the marine anticorrosion and antifouling coating prepared by the present invention has good antifouling performance.

[0071] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that the tertiary amine structure on the triazolinedione monomer reacts with the chlorine atom on 4-chloro-1-butene to generate a quaternary ammonium salt structure to obtain a quaternized triazolinedione monomer, and a carbon-carbon double bond is introduced into the quaternized triazolinedione monomer; although the epoxy resin has no unsaturated double bonds but contains ether bonds, the aH atoms on the ortho-carbon and the H atoms on the tertiary carbon atoms are relatively active, and free radicals can be formed under the action of an initiator to initiate a graft polymerization reaction, and the quaternized triazolinedione monomer is grafted onto the epoxy resin, and a quaternary ammonium salt structure is introduced into the molecular side chain of the epoxy resin; when a piece of material When submerged in seawater, some soluble organic matter (sugars, proteins) and inorganic salts will soon be adsorbed on its surface to form a basement membrane. Some simple microorganisms and protozoa will successively attach to the basement membrane and secrete extracellular substances to form a microbial mucosa or biofilm, completing the process of microbial attachment. Prokaryotes, algae spores, and fungi gather on the mucosa. At the same time, some protozoa that feed on these will also attach to it, forming a fouling biological community. The quaternary ammonium salt structure can adsorb negatively charged bacteria and has a good bactericidal effect. It can kill bacteria attached to the surface of the coating in time, thereby improving the antifouling performance of marine anticorrosion and antifouling coatings.

[0072] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 4, indicating that pre-modified silica is prepared by reacting silica and aminopropyltriethoxysilane, and amino groups are introduced into the pre-modified silica; the amino groups on the pre-modified silica react with the cyano groups on cyanamide to prepare modified silica, and a guanidine salt structure is generated on the modified silica; the guanidine salt structure generated on the modified silica has bactericidal ability, which kills bacteria attached to the surface of the coating in time, thereby improving the antifouling performance of the marine anticorrosion and antifouling coating.

[0073] Test Example 2

[0074] Corrosion protection test

[0075] Test method: immerse a stainless steel plate with a size of 6cm×3cm×1cm in the epoxy coating prepared in the embodiment and the comparative example, let it stand for 1min, take it out, dry it at 60℃ for 8h, prepare a test piece, and measure the mass N of the test piece; mix sea salt and deionized water at a mass ratio of 9:250 to obtain artificial seawater; immerse the test piece in artificial seawater, let it stand at room temperature for 7 days, take it out, dry it at 60℃ for 12h under vacuum conditions, and test the mass M of the test piece; scratch a 3cm long scratch on each side of the test piece, let it stand at 50℃ for 10h, immerse the scratched test piece in artificial seawater, let it stand at room temperature for 7 days, take it out, dry it at 60℃ for 12h under vacuum conditions, and test the mass Y of the test piece; calculate the mass loss rate of the test piece in artificial seawater before and after damage; mass loss rate before damage = (NM) / N×100%; mass loss rate after damage = (NY) / N×100%. The results are shown in Table 2.

[0076] Table 2

[0077] Quality loss rate before damage (%) Quality loss rate after damage (%) Quality loss rate before damage (%) Quality loss rate after damage (%) Example 1 0.08 0.29 Comparative Example 1 0.12 1.15 Example 2 0.09 0.27 Comparative Example 2 0.13 1.08 Example 3 0.11 0.31 Comparative Example 3 0.14 1.11 Comparative Example 4 0.12 0.32

[0078] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 2, it can be found that the marine anticorrosion and antifouling coating prepared by the present invention has good anticorrosion performance.

[0079] By comparison, the mass loss rates of the embodiments and comparative examples before damage are both lower than the mass loss rates after damage, indicating that the coating can isolate the corrosive medium. When the coating is damaged, the isolation effect on the corrosive medium becomes worse, and the anti-corrosion effect on stainless steel decreases.

[0080] By comparison, the mass loss rate after damage in Examples 1 to 3 is less than the mass loss rate after damage in Comparative Example 1, indicating that 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione is oxidized with an oxidant to obtain a triazolinedione monomer, and the tertiary amine structure on the triazolinedione monomer reacts with the chlorine atom on 4-chloro-1-butene to obtain a quaternized triazolinedione monomer, and a carbon-carbon double bond is introduced into the quaternized triazolinedione monomer; although the epoxy resin has no unsaturated double bonds but contains ether bonds, the aH atom on the ortho-carbon and the H atom on the tertiary carbon atom thereof are relatively active, and free radicals can be formed under the action of an initiator. Thereby, a grafting polymerization reaction is initiated, and the quaternized triazolinedione monomer is grafted onto the epoxy resin, and a triazolinedione structure is introduced on the molecular side chain of the epoxy resin; the triazolinedione structure introduced on the side chain of the epoxy resin can undergo a "click" reaction with the indole group introduced on the oligosiloxane to form a reversible CN bond, thereby forming a dynamic cross-linking network in the marine anti-corrosion and anti-fouling coating. When the coating on the outer surface of the metal device is damaged due to scratches, punctures and other factors, the coating can be repaired through the reversible CN bond, thereby preventing the corrosive medium from contacting the metal device through the defects of the coating, thereby improving the corrosion resistance of the marine anti-corrosion and anti-fouling coating.

[0081] By comparison, the mass loss rate of Examples 1 to 3 after damage is less than that of Comparative Examples 2 to 3 after damage, indicating that 3-aminopropylmethyldiethoxysilane and 3-indolecarboxaldehyde are reacted to obtain indolyldiethoxysilane; 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane are polymerized to obtain oligosiloxane; a large number of indole groups are introduced into the side chains of the oligosiloxane molecules; the indole groups introduced into the side chains of the oligosiloxane can react with the triazolinedione structure introduced into the modified epoxy resin to generate reversible CN bonds, thereby forming a dynamic cross-linked network in the marine anticorrosion and antifouling coating. When the coating on the outer surface of the metal device is damaged due to scratches, punctures and other factors, the coating can be repaired through reversible CN bonds to prevent the corrosive medium from contacting the metal device through the defects of the coating, thereby improving the corrosion resistance of the marine anticorrosion and antifouling coating.

[0082] Test Example 3

[0083] Wear resistance test

[0084] Test method: Pour the epoxy coating prepared in the embodiment and the comparative example into a mold, dry at 60°C for 7h, and demould to obtain a sample after cooling to room temperature. The wear resistance of the sample is measured on an M-200 friction and wear tester according to GB / T3960-2016. The material of the grinding ring in the test is 45# steel, and the radius is 40mm; the size of the sample is 30mm×7mm×6mm; the speed of the lower shaft in the test is 200r / min, the load is 20kg, the grinding is 2h, and the wear rate is calculated. The results are shown in Table 3.

[0085] Table 3

[0086] <![CDATA[Wear rate (×10 -5 m 3 / Nm)]]> <![CDATA[Wear rate (×10 -5 m 3 / Nm)]]> Example 1 0.157 Comparative Example 1 0.185 Example 2 0.152 Comparative Example 2 0.179 Example 3 0.163 Comparative Example 3 0.268 Comparative Example 4 0.273

[0087] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the marine anticorrosion and antifouling coating prepared by the present invention has good wear resistance.

[0088] By comparison, the wear rates of Examples 1 to 3 are lower than that of Comparative Example 3, indicating that 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane are polymerized to prepare oligosiloxane; a large number of amino groups are introduced into the side chains of the oligosiloxane molecules; the introduced amino groups participate in the curing process of the coating, replacing the small molecule curing agent, so that the oligosiloxane and the epoxy resin form a cross-linked network structure, and Si-O-Si segments are introduced into the coating. The bond energy of the Si-O bond is greater than that of the CC bond, and more energy is required to destroy the Si-O bond. The introduction of the Si-O-Si segment makes the coating not easily torn by external shear force, thereby giving the marine anti-corrosion and anti-fouling coating excellent wear resistance.

[0089] By comparison, the wear rates of Examples 1 to 3 are lower than that of Comparative Example 4, indicating that modified silica is prepared by reacting silica with aminopropyltriethoxysilane and cyanamide in sequence, and amino groups are introduced into the modified silica; the amino groups introduced into the modified silica allow silica to participate in the curing process of the coating, so that chemical crosslinks are formed between the silica and epoxy resin molecular chains, thereby improving the mechanical properties of the coating, making the coating less likely to be torn by external shear forces, and giving the marine anticorrosion and antifouling coating excellent wear resistance; silica is a hard inorganic non-metallic material, and surface modification of silica can improve the compatibility between silica and the matrix resin, make silica uniformly dispersed in the coating, avoid the occurrence of agglomeration, give full play to the reinforcing properties of silica, and further improve the wear resistance of the marine anticorrosion and antifouling coating.

[0090] 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 marine anticorrosion and antifouling coating, characterized in that: The marine anticorrosion and antifouling coating is prepared by reacting epoxy resin and quaternized triazolinedione monomer to obtain modified epoxy resin; polymerizing 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane to obtain oligosiloxane; reacting pre-modified silicon dioxide and cyanamide to obtain modified silicon dioxide; uniformly mixing epoxy resin, modified epoxy resin, oligosiloxane and modified silicon dioxide to obtain epoxy coating; and coating and curing the epoxy coating to obtain the coating; The quaternized triazolinedione monomer is prepared by reacting triazolinedione monomer and 4-chloro-1-butene; The triazolinedione monomer is prepared by oxidizing 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione with an oxidant; The indolyl diethoxysilane is prepared by reacting 3-aminopropylmethyl diethoxysilane and 3-indolecarboxaldehyde; The pre-modified silica is prepared by reacting silica and aminopropyltriethoxysilane; The model of the epoxy resin is epoxy resin E51.

2. A method for preparing a marine anticorrosion and antifouling coating, characterized in that: The method for preparing the marine anticorrosion and antifouling coating comprises the following preparation steps: (1) Under nitrogen protection, 4-[4-(dimethylamino)phenyl]-1,2,4-triazolidine-3,5-dione, oxidant and dichloromethane are mixed evenly in a mass ratio of 1:(2.4~2.6):(14~16), stirred at 10~30°C and 200~300r / min for 2~2.2h, filtered, washed with dichloromethane 3~5 times, and the filtrate is dried at 36~38°C for 7~8h under vacuum conditions to obtain triazolinedione monomer; triazolinedione monomer and 4-chloro-1-butene are added to toluene with a molar ratio of 1:1 to 14~16 times the mass of triazolinedione monomer, stirred at 45~55°C and 200~300r / min for 2~3h, and dried at 48~50°C for 8~10h under vacuum conditions to obtain quaternized triazolinedione monomer; (2) The quaternized triazolinedione monomer, benzoyl peroxide and n-butanol are mixed uniformly in a mass ratio of 1:(0.03-0.05):(6-8) to obtain a monomer reaction liquid; the epoxy resin, ethylene glycol monobutyl ether and n-butanol are mixed uniformly in a mass ratio of 1:(1-2):(2-3), placed in a high pressure reactor, stirred at 100-110°C and 300-500 r / min for 10-20 min, and the monomer reaction liquid of 1-1.2 times the mass of the epoxy resin is added dropwise at a uniform rate within 20 min, the temperature is raised to 120-122°C, the reaction is continued with stirring for 2-3 h, and the mixture is cooled to room temperature to obtain a modified epoxy resin; (3) Add 3-aminopropylmethyldiethoxysilane and indolyldiethoxysilane in a molar ratio of 1:(0.6~0.8) to a reactor, add deionized water (1.4~1.6 times the mass of 3-aminopropylmethyldiethoxysilane) and lithium hydroxide (0.3~0.5 times the mass of 3-aminopropylmethyldiethoxysilane), raise the temperature to 80~82°C, continue stirring and reacting for 20~22 minutes, add hexamethyldisiloxane (0.1~0.12 times the mass of 3-aminopropylmethyldiethoxysilane), continue stirring and reacting for 6~8 minutes, cool to room temperature, wash with an equal volume of deionized water and toluene, stand for stratification, remove the aqueous phase, repeat washing 3~5 times, take the organic phase and place it in a drying oven, dry it at 58~60°C under vacuum conditions for 8~10 hours to obtain oligosiloxane; (4) Pre-modified silica, 10%-12% hydrochloric acid aqueous solution and anhydrous ethanol were mixed uniformly in a mass ratio of 1:(8-10):(50-60), placed in a high-pressure reactor, stirred at 10-30°C and 200-220 r / min for 19-21 min, heated to 78-80°C, and uniformly added with cyanamide aqueous solution in an amount 10-12 times the mass of the pre-modified silica within 15 min, continued to stir and react for 4-5 h, filtered, washed with anhydrous ethanol for 3-5 times, and dried at 60-70°C under vacuum conditions for 8-10 h to obtain modified silica; (5) Weigh 36-40 parts of epoxy resin, 44-50 parts of modified epoxy resin, 18-20 parts of oligosiloxane, 3-4 parts of modified silica and 24-26 parts of acetone by mass; mix the epoxy resin, modified epoxy resin, oligosiloxane, modified silica and acetone evenly, and then adjust the viscosity to 180-200 mPa·s with acetone to prepare an epoxy coating; apply and cure the epoxy coating to prepare a marine anticorrosion and antifouling coating.

3. The method for preparing a marine anticorrosion and antifouling coating according to claim 2, characterized in that: The preparation method of the oxidant in step (1) is as follows: bromine and chloroform are uniformly mixed in a mass ratio of 1:(90-100) to prepare a bromine chloroform solution; Under nitrogen protection, triethylenediamine and chloroform are uniformly mixed in a mass ratio of 1:(13~15), and under stirring conditions of 10~30℃ and 200~300r / min, a chloroform solution of bromine 3~4 times the mass of triethylenediamine is uniformly added dropwise within 10min, and the reaction is continued with stirring for 1~2h. The mixture is filtered and dried at 40~42℃ under vacuum conditions for 10~12h to obtain an oxidant.

4. The method for preparing a marine anticorrosion and antifouling coating according to claim 2, characterized in that: The model of the epoxy resin in step (2) and step (5) is E51.

5. The method for preparing a marine anticorrosion and antifouling coating according to claim 2, characterized in that: The preparation method of the indolyl diethoxysilane in step (3) is as follows: 3-aminopropylmethyl diethoxysilane and 3-indole formaldehyde are added in a molar ratio of 1:1 to N,N-dimethylformamide with a mass that is 14 to 16 times that of 3-aminopropylmethyl diethoxysilane, and the mixture is stirred at 50 to 60° C. and 200 to 300 r / min for 3 to 4 hours, and dried at 55 to 65° C. under vacuum conditions for 7 to 9 hours to obtain indolyl diethoxysilane.

6. The method for preparing a marine anticorrosion and antifouling coating according to claim 2, characterized in that: The preparation method of the pre-modified silica in step (4) is as follows: silica and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(66~70), ultrasonically dispersed for 1~1.2h, silane hydrolyzate of 6~8 times the mass of silica is added, stirred at 56~60°C and 180~200r / min for 2~3h, filtered, washed with anhydrous ethanol for 3~5 times, and dried at 68~70°C under vacuum conditions for 9~10h to obtain pre-modified silica.

7. The method for preparing a marine anticorrosion and antifouling coating according to claim 6, characterized in that: The preparation method of the silane hydrolyzate is as follows: aminopropyltriethoxysilane and deionized water are uniformly mixed in a mass ratio of 1:(20-22), stirred at 180-200 r / min for 8-10 min at room temperature, adjusted the pH to 5.8-6 with an aqueous solution of oxalic acid with a concentration of 1 mol / L, and continued stirring for 28-30 min to prepare the silane hydrolyzate.

8. The method for preparing a marine anticorrosion and antifouling coating according to claim 6, characterized in that: The particle size of the silicon dioxide is 2000 mesh.

9. The method for preparing a marine anticorrosion and antifouling coating according to claim 2, characterized in that: The mass fraction of the cyanamide aqueous solution in step (4) is 30% to 32%.

10. The method for preparing a marine anticorrosion and antifouling coating according to claim 2, characterized in that: The process parameters of the coating and curing in step (5) are as follows: the epoxy coating is coated on the metal substrate with a coating amount of 0.16-0.2 kg / m 2 , dry at 58~60℃ for 6~8h.

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