Special coating for preventing biological invasion and preparation method thereof

Abstract

The invention relates to a special coating for preventing biological invasion and a preparation method thereof, and belongs to the technical field of coatings, and the preparation method comprises the following steps: combining methacryloyl chloride with a natural bactericide to obtain a modified bactericide; the preparation method comprises the following steps: combining a modified bactericide, silanized zinc molybdate nanoparticles and 3-sulfydryl-1, 2-propylene glycol to obtain a bactericidal and corrosion-resistant copolymer; the bactericidal corrosion-resistant copolymer, isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane and polyether glycol are combined, and filler and auxiliaries are added to obtain the special coating for preventing biological attack. According to the technical scheme, the modified bactericide and the silanized zinc molybdate nanoparticles are combined, so that the biological adhesion prevention performance and the antibacterial performance of the coating are improved; the bactericidal corrosion-resistant copolymer, the isophorone diisocyanate, the hydroxyl-terminated fluoropolysiloxane and the polyether glycol are combined, so that the corrosion resistance, the mechanical property and the adhesion property of the coating are further improved, the coating is green and environment-friendly, and the comprehensive performance of the coating is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and in particular, relates to a special coating for preventing biological invasion and a preparation method thereof. Background Art

[0002] The shells below the waterline of ships and docks are in contact with seawater for a long time, which makes them susceptible to corrosion and biological attachment. The attachment of marine organisms such as shellfish, algae, and barnacles in seawater not only increases the ship's travel resistance, reduces the ship's speed, and increases fuel consumption, but also the acidic substances released by the attached organisms will corrode the equipment, causing the malfunction of facilities and instruments in the ocean, reducing the service life of these equipment and affecting their normal functions, thus causing varying degrees of economic losses. Therefore, coating the surface of these marine facilities with special coatings that prevent biological invasion can effectively solve such problems.

[0003] In the prior art, fungicides are usually added to coatings to prepare special coatings for preventing biological invasion. However, commonly used fungicides contain heavy metal ions such as tin and copper. Although they have good antibacterial properties and can prevent the adsorption of marine organisms on the coatings, they still have the following defects: 1) The fungicide exists in the coating in the form of free ions. When the coating is used in seawater, as the fungicide gradually dissolves into the seawater, the anti-biological adhesion performance of the coating will gradually decrease; 2) Such fungicides are toxic and long-term use will cause pollution to the marine environment. Therefore, it is necessary to prepare a special coating for preventing biological invasion that has good anti-biological adhesion performance, corrosion resistance and antibacterial properties, and good adhesion to various structural materials. Summary of the invention

[0004] The object of the present invention is to provide a special coating for preventing biological invasion and a preparation method thereof. The modified bactericide is obtained by combining methacryloyl chloride with a natural bactericide. The natural bactericide is capsaicin, which can effectively improve the anti-biological adhesion performance of the coating, and has a certain antibacterial function, is non-toxic and harmless, and will not cause pollution and harm to the marine environment. The modified bactericide, silylated zinc molybdate nanoparticles, and 3-mercapto-1,2-propylene glycol are combined to obtain a bactericidal and corrosion-resistant copolymer. The silylated zinc molybdate nanoparticles not only effectively improve the dispersion performance of the zinc molybdate nanoparticles, provide reaction sites for subsequent reactions, but also can play a synergistic antibacterial role with the natural antibacterial agent. The invention discloses a novel coating composition comprising a novel method for preparing a special coating for preventing biological invasion; the coating composition comprises ...

[0005] Technical problem to be solved by the present invention: In the prior art, bactericides are usually added to coatings to prepare special coatings for preventing biological invasion. However, commonly used bactericides contain heavy metal ions such as tin and copper. Although they have good antibacterial properties and can prevent the adsorption of marine organisms on the coatings, they still have the following defects: 1) The bactericide exists in the coating in the form of free ions. When the coating is used in seawater, as the bactericide gradually dissolves into the seawater, the anti-biological adhesion performance of the coating will gradually decrease; 2) Such bactericides are toxic and long-term use will cause pollution to the marine environment. Therefore, it is necessary to prepare a special coating for preventing biological invasion that has good anti-biological adhesion performance, corrosion resistance and antibacterial performance, and good adhesion to various structural materials.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a special coating for preventing biological invasion comprises the following steps: S1: Modified fungicide is obtained by combining methacryloyl chloride with natural fungicide; S2: combining the modified bactericide, silanized zinc molybdate nanoparticles, and 3-mercapto-1,2-propanediol to obtain a bactericidal and corrosion-resistant copolymer; S3: Combine the bactericidal and corrosion-resistant copolymer, isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane and polyether diol, add fillers and additives, and stir evenly to obtain a special coating for preventing biological invasion.

[0007] Furthermore, step S1 is specifically as follows: The natural fungicide and triethylamine are dissolved in xylene, and then stirred in an ice-water bath until the system temperature reaches 4-5°C, and then methacryloyl chloride is added, and the reaction is carried out at room temperature for 22-24 hours. After filtering, a cationic adsorption resin is added, and the modified fungicide is finally obtained by vacuum distillation.

[0008] In the above reaction process, the natural fungicide has a hydroxyl group, and methacryloyl chloride has a carbon-carbon double bond and a chlorine atom. The chlorine atom in methacryloyl chloride can combine with the hydroxyl group in the natural fungicide to obtain a modified fungicide.

[0009] Furthermore, the mass ratio of the natural fungicide, triethylamine and xylene is 0.8-1.2:1-1.4:30-40.

[0010] Furthermore, the natural fungicide is capsaicin.

[0011] Furthermore, step S2 is specifically as follows: The modified bactericide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propanediol and azobisisobutyronitrile are mixed, and then tetrahydrofuran is added. The mixed solution is purged with nitrogen for 20-40 minutes, and then immersed in an oil bath at 65-75°C to react for 13-15 hours. After the reaction is completed, the mixed solution is precipitated with n-hexane, and the obtained precipitate is dissolved in tetrahydrofuran to finally obtain a bactericidal and corrosion-resistant copolymer.

[0012] In the above reaction process, the modified fungicide and silylated zinc molybdate nanoparticles both have carbon-carbon double bonds, 3-mercapto-1,2-propylene glycol has hydroxyl groups and thiol groups, the thiol groups in 3-mercapto-1,2-propylene glycol can undergo a "click" reaction with the carbon-carbon double bonds in the modified fungicide and silylated zinc molybdate nanoparticles, and at the same time, the carbon-carbon double bonds in the modified fungicide undergo a free radical polymerization reaction with the carbon-carbon double bonds in the silylated zinc molybdate nanoparticles, thereby combining the modified fungicide, silylated zinc molybdate nanoparticles and 3-mercapto-1,2-propylene glycol together to finally obtain a bactericidal and corrosion-resistant copolymer.

[0013] Furthermore, the mass ratio of the modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propanediol, and azobisisobutyronitrile is 0.8-1.2: 1.8-2.2: 0.016-0.02: 0.005-0.009.

[0014] Furthermore, the preparation method of the silanized zinc molybdate nanoparticles comprises the following steps: The zinc molybdate nanoparticles and the silane coupling agent are mixed, the pH value of the mixture is adjusted to 8-9 with a sodium hydroxide solution, and then an ethanol / deionized water mixed solution is added and reacted at 55-65° C. for 0.5-1.5 h, filtered, washed with ethanol, and finally dried to obtain silanized zinc molybdate nanoparticles.

[0015] In the above reaction process, the surface of zinc molybdate nanoparticles has hydroxyl groups, and the silane coupling agent has silanol groups after hydrolysis, which can combine with the hydroxyl groups on the surface of zinc molybdate nanoparticles, so that the silane coupling agent is grafted onto the surface of zinc molybdate nanoparticles, and finally silanized zinc molybdate nanoparticles are obtained.

[0016] Furthermore, the mass ratio of the zinc molybdate nanoparticles to the silane coupling agent is 1-3:0.5-1.

[0017] Furthermore, the silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane mixed in a mass ratio of 1:1.

[0018] Furthermore, the preparation method of the zinc molybdate nanoparticles comprises the following steps: Zinc chloride was dissolved in deionized water, and then hexadecyltrimethylammonium bromide and deionized water were added. After stirring evenly, sodium molybdate was added, and ultrasonic treatment was performed for 25-35 minutes. The mixture was placed in an autoclave at 160° C. for 3-5 hours to obtain a white precipitate. The mixture was cooled to room temperature, washed with ethanol and deionized water in turn, and finally dried to obtain zinc molybdate nanoparticles.

[0019] Furthermore, the mass ratio of the zinc chloride to deionized water is 0.14-0.18:2-4.

[0020] Furthermore, step S3 is specifically as follows: Under a nitrogen atmosphere, isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane, polyether diol and tetrahydrofuran are mixed evenly and stirred at 70-80°C for 2-4 hours to obtain a prepolymer, and then the bactericidal and corrosion-resistant copolymer, chain extender and catalyst are added to the prepolymer, and the reaction is continued at 70-80°C for 2-4 hours to obtain a polymer solution, and then fillers and additives are added and stirred evenly to finally obtain a special coating for preventing biological invasion.

[0021] In the above reaction process, isophorone diisocyanate has an isocyanate group, hydroxyl-terminated fluoropolysiloxane has a hydroxyl group and a fluorine atom, polyether diol, bactericidal and corrosion-resistant copolymer and chain extender all have hydroxyl groups, and the isocyanate in isophorone diisocyanate can be combined with the hydroxyl groups in the hydroxyl-terminated fluoropolysiloxane, polyether diol, bactericidal and corrosion-resistant copolymer and chain extender. By combining isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane, bactericidal and corrosion-resistant copolymer and chain extender, a special coating for preventing biological invasion is finally obtained.

[0022] Furthermore, the mass ratio of isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane, polyether diol and tetrahydrofuran is 0.5-0.7:1.4-1.6:0.5-0.7:20-30.

[0023] Furthermore, the hydroxyl-terminated fluoropolysiloxane is a hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane).

[0024] Furthermore, the chain extender is 2,2-dihydroxymethylbutyric acid.

[0025] Furthermore, the catalyst is dibutyltin dilaurate.

[0026] Furthermore, the filler is at least one of nano-silicon dioxide, zeolite, bentonite and talc.

[0027] Furthermore, the auxiliary agent is at least one of a defoaming agent, a leveling agent, and a dispersant.

[0028] Furthermore, the defoaming agent is calcium oxide.

[0029] Furthermore, the leveling agent is polyether-modified polydimethylsiloxane.

[0030] Furthermore, the dispersant is sodium polyacrylate.

[0031] Beneficial effects of the present invention: (1) In the technical scheme of the present invention, a modified fungicide is obtained by combining methacryloyl chloride with a natural fungicide; the natural fungicide is capsaicin, which has a strong spicy taste. This characteristic makes marine organisms such as barnacles, seaweed, and shellfish strongly repel it, thereby playing a repelling role and effectively preventing these marine organisms from attaching to marine facilities such as ships and docks, thereby improving the anti-biological adhesion performance of the coating. Capsaicin has a certain antibacterial function and can inhibit the growth of microorganisms such as bacteria, further improving the antibacterial performance of the coating. At the same time, capsaicin is a natural plant extract, which is non-toxic and harmless and will not cause pollution and harm to the marine environment; the modified fungicide, silanized zinc molybdate nanoparticles, and 3-mercapto-1,2-propanediol are added to the mixture. Combined to obtain a bactericidal and corrosion-resistant copolymer; in the silylated zinc molybdate nanoparticles, the silane coupling agent not only effectively improves the dispersion performance of the zinc molybdate nanoparticles and prevents them from agglomerating, but also provides reaction sites for subsequent reactions. At the same time, the zinc molybdate nanoparticles are environmentally friendly and non-toxic, have good corrosion resistance, and can play a synergistic antibacterial role with natural antibacterial agents. 3-Mercapto-1,2-propylene glycol can not only combine the modified bactericide and the silylated zinc molybdate nanoparticles, but also provide reaction sites for subsequent reactions. The bactericidal and corrosion-resistant copolymer obtained by combining the modified bactericide, the silylated zinc molybdate nanoparticles and the 3-mercapto-1,2-propylene glycol can better improve the corrosion resistance, antibacterial properties and mechanical properties of the coating.

[0032] (2) In the technical scheme of the present invention, a special coating for preventing biological invasion is obtained by combining a bactericidal and corrosion-resistant copolymer, isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane and polyether diol, adding fillers and additives, and stirring evenly; isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane and polyether diol are combined to generate polyurethane, which has good adhesion properties and can increase the adhesion of the coating; and the fluorine atoms in the hydroxyl-terminated fluoropolysiloxane can enhance the antifouling properties of the coating, thereby increasing the bactericidal and corrosion-resistant The addition of the anti-corrosion copolymer to the polyurethane chain segment not only increases the corrosion resistance and antibacterial properties of the coating, but also can better control the release capacity of natural bactericides. The chain extender added during the preparation process, which is 2,2-dihydroxymethylbutyric acid, makes the coating have higher flexibility, elongation and mechanical strength. The bactericidal and corrosion-resistant copolymer, isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane and polyether diol are combined to further improve the antibacterial properties, anti-biological attachment properties, corrosion resistance and mechanical properties of the coating.

[0033] (3) In the technical scheme of the present invention, methacryloyl chloride is combined with a natural bactericide, and then combined with silanized zinc molybdate nanoparticles and 3-mercapto-1,2-propylene glycol to obtain a bactericidal and corrosion-resistant copolymer, which is then combined with isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane, and polyether diol, and fillers and additives are added to finally obtain a special coating for preventing biological invasion. The obtained special coating for preventing biological invasion has good anti-biological adhesion performance, corrosion resistance, antibacterial performance and mechanical properties, good adhesion to various structural materials, and is green and environmentally friendly, reducing pollution and harm to the marine environment, and has good overall comprehensive performance. DETAILED DESCRIPTION

[0034] 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.

[0035] The specific parameters of the raw materials used in the present invention are as follows: Hydroxyl terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), CAS: 68607-77-2, provided by Zhengzhou Alpha Chemical Co., Ltd.; polyether diol (DL-2000D), provided by Shandong Bluestar Dongda Co., Ltd.; isophorone diisocyanate, CAS: 4098-71-9, provided by Shanghai McLean Biochemical Co., Ltd.; capsaicin, CAS: 2444-46-4, provided by Shanghai McLean Biochemical Co., Ltd.; zinc chloride, CAS: 7646-85-7, provided by Shanghai McLean Biochemical Co., Ltd.

[0036] Example 1 The specific steps for preparing a special coating for preventing biological invasion are as follows: S1: Dissolve capsaicin and triethylamine in xylene at a mass ratio of 0.8:1:30, then stir in an ice-water bath until the system temperature reaches 4°C, add methacryloyl chloride (the mass of methacryloyl chloride is equal to the mass of capsaicin), react at room temperature for 22 hours, filter to remove the ammonium salt produced by the reaction, add a cationic adsorption resin to remove unreacted monomers (the mass of the cationic adsorption resin is 50wt% of the mass of xylene), remove the solvent by reduced pressure distillation, and finally obtain a modified fungicide; S2: According to the mass ratio of modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propylene glycol and azobisisobutyronitrile of 0.8:1.8:0.016:0.005, the modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propylene glycol and azobisisobutyronitrile were mixed, and then tetrahydrofuran (the mass of tetrahydrofuran was 20 times the mass of the modified fungicide) was added, and the mixed solution was purged with nitrogen for 20 minutes, and then immersed in an oil bath at 65°C for reaction for 13 hours. After the reaction, the mixed solution was precipitated with n-hexane (the mass of n-hexane was 10 times the mass of the modified fungicide), and the obtained precipitate was dissolved in tetrahydrofuran (tetrahydrofuran was 20 times the mass of the modified fungicide), and the precipitation and dissolution operations were repeated 3 times to finally obtain a bactericidal and corrosion-resistant copolymer; The preparation method of silanized zinc molybdate nanoparticles comprises the following steps: According to the mass ratio of zinc molybdate nanoparticles to the silane coupling agent being 1:0.5, zinc molybdate nanoparticles and the silane coupling agent are mixed, the pH value of the mixture is adjusted to 8 with a 0.1M sodium hydroxide solution, and then an ethanol / deionized water mixed solution is added (the volume ratio of ethanol to deionized water is 1:4, and the mass of the ethanol / deionized water mixed solution is 5 times the mass of the zinc molybdate nanoparticles), and the mixture is reacted at 55°C for 0.5h, filtered, washed with ethanol 3 times (the mass of ethanol each time is 5 times the mass of the zinc molybdate nanoparticles), and finally dried for 24h to obtain silylated zinc molybdate nanoparticles, wherein the silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane mixed in a mass ratio of 1:1; The method for preparing zinc molybdate nanoparticles comprises the following steps: According to the mass ratio of zinc chloride to deionized water being 0.14:2, zinc chloride was dissolved in deionized water, and then hexadecyltrimethylammonium bromide (the mass of hexadecyltrimethylammonium bromide was 1.3 times the mass of zinc chloride) and deionized water (the mass of deionized water was 150 times the mass of zinc chloride) were added, and after stirring evenly, sodium molybdate (the mass of sodium molybdate was 1.5 times the mass of zinc chloride) was added, and ultrasonic treatment was performed for 25 minutes (ultrasonic frequency was 40kHz), and the mixture was placed in an autoclave at 160°C for 3 hours to obtain a white precipitate, which was cooled to room temperature, and washed with ethanol and deionized water three times respectively (the mass of ethanol and deionized water each time was 50 times the mass of zinc chloride), and finally dried to obtain zinc molybdate nanoparticles; S3: According to the mass ratio of isophorone diisocyanate, hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), polyether diol and tetrahydrofuran of 0.5:1.4:0.5:20, isophorone diisocyanate, hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), polyether diol and tetrahydrofuran are mixed evenly under nitrogen atmosphere, and stirred at 70°C for 2h to obtain a prepolymer, and then the bactericidal and corrosion-resistant copolymer (the mass of the bactericidal and corrosion-resistant copolymer is 35wt% of the mass of isophorone diisocyanate) is added. %), 2,2-dihydroxymethylbutyric acid (the mass of 2,2-dihydroxymethylbutyric acid is 17wt% of the mass of isophorone diisocyanate) and dibutyltin dilaurate (the mass of dibutyltin dilaurate is 3.5wt% of the mass of isophorone diisocyanate) are added to the prepolymer, and the reaction is continued at 70°C for 2h to obtain a polymer solution, and zeolite (the mass of zeolite is 1.5 times the mass of isophorone diisocyanate) and calcium oxide (the mass of calcium oxide is 10wt% of the mass of isophorone diisocyanate) are added and stirred evenly to obtain a special coating for preventing biological invasion.

[0037] Example 2 The specific steps for preparing a special coating for preventing biological invasion are as follows: S1: Dissolve capsaicin and triethylamine in xylene in a mass ratio of 1:1.2:35, then stir in an ice-water bath until the system temperature reaches 4.5°C, add methacryloyl chloride (the mass of methacryloyl chloride is equal to the mass of capsaicin), react at room temperature for 23 hours, filter to remove the ammonium salt produced by the reaction, add a cationic adsorption resin to remove unreacted monomers (the mass of the cationic adsorption resin is 50wt% of the mass of xylene), remove the solvent by reduced pressure distillation, and finally obtain a modified fungicide; S2: According to the mass ratio of modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propylene glycol and azobisisobutyronitrile of 1:2:0.018:0.007, the modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propylene glycol and azobisisobutyronitrile were mixed, and then tetrahydrofuran (the mass of tetrahydrofuran was 20 times the mass of the modified fungicide) was added, and the mixed solution was purged with nitrogen for 30 minutes, and then immersed in an oil bath at 70°C for reaction for 14 hours. After the reaction, the mixed solution was precipitated with n-hexane (the mass of n-hexane was 10 times the mass of the modified fungicide), and the obtained precipitate was dissolved in tetrahydrofuran (tetrahydrofuran was 20 times the mass of the modified fungicide), and the precipitation and dissolution operations were repeated 3 times to finally obtain a bactericidal and corrosion-resistant copolymer; The preparation method of silanized zinc molybdate nanoparticles comprises the following steps: According to the mass ratio of zinc molybdate nanoparticles to the silane coupling agent being 2:0.7, zinc molybdate nanoparticles and the silane coupling agent are mixed, the pH value of the mixture is adjusted to 8.5 with a 0.1M sodium hydroxide solution, and then an ethanol / deionized water mixed solution is added (the volume ratio of ethanol to deionized water is 1:4, and the mass of the ethanol / deionized water mixed solution is 5 times the mass of the zinc molybdate nanoparticles), and the mixture is reacted at 60°C for 1 hour, filtered, washed with ethanol 3 times (the mass of ethanol each time is 5 times the mass of the zinc molybdate nanoparticles), and finally dried for 24 hours to obtain silylated zinc molybdate nanoparticles, wherein the silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane mixed in a mass ratio of 1:1; The method for preparing zinc molybdate nanoparticles comprises the following steps: According to the mass ratio of zinc chloride to deionized water being 0.16:3, zinc chloride was dissolved in deionized water, and then hexadecyltrimethylammonium bromide (the mass of hexadecyltrimethylammonium bromide was 1.3 times the mass of zinc chloride) and deionized water (the mass of deionized water was 150 times the mass of zinc chloride) were added, and after stirring evenly, sodium molybdate (the mass of sodium molybdate was 1.5 times the mass of zinc chloride) was added, and ultrasonic treatment was performed for 30 minutes (ultrasonic frequency was 40kHz), and the mixture was placed in an autoclave at 160°C for 4 hours to obtain a white precipitate, which was cooled to room temperature, and washed with ethanol and deionized water three times respectively (the mass of ethanol and deionized water each time was 50 times the mass of zinc chloride), and finally dried to obtain zinc molybdate nanoparticles; S3: According to the mass ratio of isophorone diisocyanate, hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), polyether diol and tetrahydrofuran of 0.6:1.5:0.6:25, in a nitrogen atmosphere, isophorone diisocyanate, hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), polyether diol and tetrahydrofuran are evenly mixed and stirred at 75°C for 3h to obtain a prepolymer, and then the bactericidal and corrosion-resistant copolymer (the mass of the bactericidal and corrosion-resistant copolymer is 35wt% of the mass of isophorone diisocyanate), 2,2-dihydroxymethylbutyl Acid (the mass of 2,2-dihydroxymethylbutyric acid is 17wt% of the mass of isophorone diisocyanate) and dibutyltin dilaurate (the mass of dibutyltin dilaurate is 3.5wt% of the mass of isophorone diisocyanate) are added to the prepolymer, and the reaction is continued at 75°C for 3h to obtain a polymer solution, and then nano-silica (the mass of nano-silica is 1.5 times the mass of isophorone diisocyanate) and polyether-modified polydimethylsiloxane (the mass of polyether-modified polydimethylsiloxane is 10wt% of the mass of isophorone diisocyanate) are added and stirred evenly to obtain a special coating for preventing biological invasion.

[0038] Example 3 The specific steps for preparing a special coating for preventing biological invasion are as follows: S1: Dissolve capsaicin and triethylamine in xylene in a mass ratio of 1.2:1.4:40 among capsaicin, triethylamine and xylene, and then stir in an ice-water bath until the system temperature reaches 5°C, then add methacryloyl chloride (the mass of methacryloyl chloride is equal to the mass of capsaicin), react at room temperature for 24 hours, remove the ammonium salt produced by the reaction by filtration, add cationic adsorption resin to remove unreacted monomers (the mass of cationic adsorption resin is 50wt% of the mass of xylene), remove the solvent by reduced pressure distillation, and finally obtain a modified fungicide; S2: According to the mass ratio of modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propylene glycol and azobisisobutyronitrile of 1.2:2.2:0.02:0.009, the modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propylene glycol and azobisisobutyronitrile were mixed, and then tetrahydrofuran (the mass of tetrahydrofuran was 20 times the mass of the modified fungicide) was added, and the mixed solution was purged with nitrogen for 40 minutes, and then immersed in an oil bath at 75°C for reaction for 15 hours. After the reaction, the mixed solution was precipitated with n-hexane (the mass of n-hexane was 10 times the mass of the modified fungicide), and the obtained precipitate was dissolved in tetrahydrofuran (tetrahydrofuran was 20 times the mass of the modified fungicide), and the precipitation and dissolution operations were repeated 3 times to finally obtain a bactericidal and corrosion-resistant copolymer; The preparation method of silanized zinc molybdate nanoparticles comprises the following steps: According to the mass ratio of zinc molybdate nanoparticles to the silane coupling agent being 3:1, zinc molybdate nanoparticles and the silane coupling agent are mixed, the pH value of the mixture is adjusted to 9 with a 0.1M sodium hydroxide solution, and then an ethanol / deionized water mixed solution is added (the volume ratio of ethanol to deionized water is 1:4, and the mass of the ethanol / deionized water mixed solution is 5 times the mass of the zinc molybdate nanoparticles), and the mixture is reacted at 65°C for 1.5 hours, filtered, washed with ethanol 3 times (the mass of ethanol each time is 5 times the mass of the zinc molybdate nanoparticles), and finally dried for 24 hours to obtain silylated zinc molybdate nanoparticles, wherein the silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane mixed in a mass ratio of 1:1; The method for preparing zinc molybdate nanoparticles comprises the following steps: According to the mass ratio of zinc chloride to deionized water being 0.18:4, zinc chloride was dissolved in deionized water, and then hexadecyltrimethylammonium bromide (the mass of hexadecyltrimethylammonium bromide was 1.3 times the mass of zinc chloride) and deionized water (the mass of deionized water was 150 times the mass of zinc chloride) were added, and after stirring evenly, sodium molybdate (the mass of sodium molybdate was 1.5 times the mass of zinc chloride) was added, and ultrasonic treatment was performed for 35 minutes (ultrasonic frequency was 40kHz), and the mixture was placed in an autoclave at 160°C for 5 hours to obtain a white precipitate, which was cooled to room temperature, and washed with ethanol and deionized water three times respectively (the mass of ethanol and deionized water each time was 50 times the mass of zinc chloride), and finally dried to obtain zinc molybdate nanoparticles; S3: According to the mass ratio of isophorone diisocyanate, hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), polyether diol and tetrahydrofuran of 0.7:1.6:0.7:30, under a nitrogen atmosphere, isophorone diisocyanate, hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), polyether diol and tetrahydrofuran are uniformly mixed and stirred at 80°C for 4h to obtain a prepolymer, and then a bactericidal and corrosion-resistant copolymer (the mass of the bactericidal and corrosion-resistant copolymer is 35wt% of the mass of isophorone diisocyanate) and 2,2-Dihydroxymethylbutyric acid (the mass of 2,2-dihydroxymethylbutyric acid is 17wt% of the mass of isophorone diisocyanate) and dibutyltin dilaurate (the mass of dibutyltin dilaurate is 3.5wt% of the mass of isophorone diisocyanate) are added to the prepolymer, and the reaction is continued at 80°C for 4 hours to obtain a polymer solution, and talcum powder (the mass of talcum powder is 1.5 times the mass of isophorone diisocyanate) and sodium polyacrylate (the mass of sodium polyacrylate is 10wt% of the mass of isophorone diisocyanate) are added and stirred evenly to obtain a special coating for preventing biological invasion.

[0039] Comparative Example 1 The difference between this comparative example and Example 3 is that when preparing the special coating for preventing biological invasion, the mass of capsaicin in step S1 is replaced by eugenol, and the remaining steps and raw materials are synchronized with Example 3; S1: Dissolve eugenol and triethylamine in xylene at a mass ratio of 1.2:1.4:40, then stir in an ice-water bath until the system temperature reaches 5°C, add methacryloyl chloride (the mass of methacryloyl chloride is equal to the mass of eugenol), and react at room temperature for 24 hours. Remove the ammonium salt produced by the reaction by filtration, add a cationic adsorption resin to remove unreacted monomers (the mass of the cationic adsorption resin is 50wt% of the mass of xylene), remove the solvent by reduced pressure distillation, and finally obtain a modified fungicide.

[0040] Comparative Example 2 The difference between this comparative example and Example 3 is that when preparing the special coating for preventing biological invasion, the modified fungicide and the silanized zinc molybdate nanoparticles in step S2 are directly combined, and the remaining steps and raw materials are synchronized with Example 3; S2: According to the mass ratio of modified fungicide, silylated zinc molybdate nanoparticles and azobisisobutyronitrile of 1.2:2.2:0.009, the modified fungicide, silylated zinc molybdate nanoparticles and azobisisobutyronitrile were mixed, and then tetrahydrofuran was added (the mass of tetrahydrofuran was 20 times the mass of the modified fungicide), the mixed solution was purged with nitrogen for 40 minutes, and then immersed in an oil bath at 75°C for reaction for 15 hours. After the reaction, the mixed solution was precipitated with n-hexane (the mass of n-hexane was 10 times the mass of the modified fungicide), and the obtained precipitate was dissolved in tetrahydrofuran (tetrahydrofuran was 20 times the mass of the modified fungicide), and the precipitation and dissolution operations were repeated 3 times to finally obtain a bactericidal and corrosion-resistant copolymer.

[0041] Comparative Example 3 The difference between this comparative example and Example 3 is that when preparing silanized zinc molybdate nanoparticles, the mass of the silane coupling agent is replaced by γ-methacryloxypropyltrimethoxysilane, and the remaining steps and raw materials are the same as those of Example 3; The preparation method of silanized zinc molybdate nanoparticles comprises the following steps: According to the mass ratio of zinc molybdate nanoparticles to γ-methacryloxypropyltrimethoxysilane being 3:1, zinc molybdate nanoparticles and γ-methacryloxypropyltrimethoxysilane were mixed, the pH value of the mixture was adjusted to 9 with 0.1M sodium hydroxide solution, and then an ethanol / deionized water mixed solution was added (the volume ratio of ethanol to deionized water was 1:4, and the mass of the ethanol / deionized water mixed solution was 5 times the mass of the zinc molybdate nanoparticles), and the mixture was reacted at 65°C for 1.5h, filtered, washed with ethanol 3 times (the mass of ethanol each time was 5 times the mass of the zinc molybdate nanoparticles), and finally dried for 24h to obtain silanized zinc molybdate nanoparticles.

[0042] Comparative Example 4 The difference between this comparative example and Example 3 is that when preparing silanized zinc molybdate nanoparticles, the mass of zinc molybdate nanoparticles is replaced by zinc oxide nanoparticles, and the remaining steps and raw materials are the same as those of Example 3; The preparation method of silanized zinc oxide nanoparticles comprises the following steps: According to the mass ratio of zinc oxide nanoparticles to the silane coupling agent of 3:1, the zinc oxide nanoparticles and the silane coupling agent are mixed, the pH value of the mixture is adjusted to 9 with 0.1M sodium hydroxide solution, and then an ethanol / deionized water mixed solution is added (the volume ratio of ethanol to deionized water is 1:4, and the mass of the ethanol / deionized water mixed solution is 5 times the mass of the zinc oxide nanoparticles), and the mixture is reacted at 65°C for 1.5 hours, filtered, washed with ethanol 3 times (the mass of ethanol each time is 5 times the mass of the zinc oxide nanoparticles), and finally dried for 24 hours to obtain silylated zinc oxide nanoparticles, wherein the silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane mixed in a mass ratio of 1:1.

[0043] Comparative Example 5 The difference between this comparative example and Example 3 is that when preparing the special coating for preventing biological invasion, the hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane) in step S3 is replaced by hydroxypropyl-terminated polydimethylsiloxane, and the remaining steps and raw materials are synchronized with Example 3; S3: According to the mass ratio of isophorone diisocyanate, hydroxypropyl-terminated polydimethylsiloxane, polyether diol and tetrahydrofuran of 0.7:1.6:0.7:30, isophorone diisocyanate, hydroxypropyl-terminated polydimethylsiloxane, polyether diol and tetrahydrofuran are uniformly mixed under nitrogen atmosphere, and stirred at 80°C for 4h to obtain a prepolymer, and then a bactericidal and corrosion-resistant copolymer (the mass of the bactericidal and corrosion-resistant copolymer is 35wt% of the mass of isophorone diisocyanate), 2,2-dihydroxymethylbutyric acid (2,2- Hydroxymethylbutyric acid (the mass of which is 17wt% of the mass of isophorone diisocyanate) and dibutyltin dilaurate (the mass of which is 3.5wt% of the mass of isophorone diisocyanate) are added to the prepolymer, and the reaction is continued at 80°C for 4 hours to obtain a polymer solution, and talcum powder (the mass of which is 1.5 times the mass of isophorone diisocyanate) and sodium polyacrylate (the mass of which is 10wt% of the mass of isophorone diisocyanate) are added and stirred evenly to obtain a special coating for preventing biological invasion.

[0044] Comparative Example 6 The difference between this comparative example and Example 3 is that when preparing the special coating for preventing biological damage, the isophorone diisocyanate, polyether diol and bactericidal and corrosion-resistant copolymer in step S3 are combined, and the remaining steps and raw materials are synchronized with Example 3; S3: According to the mass ratio of isophorone diisocyanate, polyether diol and tetrahydrofuran of 0.7:2.3:30, isophorone diisocyanate, polyether diol and tetrahydrofuran are mixed evenly under nitrogen atmosphere, and stirred at 80°C for 4h to obtain a prepolymer, and then a bactericidal and corrosion-resistant copolymer (the mass of the bactericidal and corrosion-resistant copolymer is 35wt% of the mass of isophorone diisocyanate), 2,2-dihydroxymethylbutyric acid (the mass of 2,2-dihydroxymethylbutyric acid is 10wt% of the mass of isophorone diisocyanate) and a prepolymer are added. The prepolymer is added with talcum powder (the mass of talcum powder is 1.5 times the mass of isophorone diisocyanate) and sodium polyacrylate (the mass of sodium polyacrylate is 10wt% of the mass of isophorone diisocyanate) and stirred evenly to obtain a special coating for preventing biological invasion.

[0045] The anti-biological attack special coatings prepared in Examples 1-3 and Comparative Examples 1-6 are now tested for antibacterial performance, antibacterial durability, corrosion resistance and anti-biological adhesion performance; Antibacterial performance test: The anti-biological attack special coatings prepared in Examples 1-3 and Comparative Examples 1-6 are sprayed on a glass slide using air spray technology to form a coating with a thickness of 100 μm, and cured at 80° C. for 3 h. The nozzle diameter of the spray gun used is 0.4 mm, the spraying distance is 15 cm, and the spraying pressure is 0.2 MPa. After drying, the anti-biological attack coating is obtained. According to the GB / T 31402-2015 test standard, the surface antibacterial performance of the coating samples is tested, and the test strains are Staphylococcus aureus ATCC 6538P and Escherichia coli ATCC 8739; Antibacterial durability test: The antibacterial rate of the special coatings for preventing biological invasion prepared in Examples 1-3 and Comparative Examples 1-6 was tested after being irradiated with an ultraviolet lamp with a wavelength of 253.7 nm for 100 hours; Corrosion resistance test: The salt spray resistance test was carried out according to the GB / T 1771-2007 test standard, and the corrosion resistance of the coating was characterized by the salt spray resistance; Anti-biological adhesion test: The anti-biological adhesion test was carried out according to the GB / T 5370-2007 test standard, and the total coverage rate (percentage) of barnacles, oysters, mussels, lime worms, bryozoans, enteromorpha, hydra, anemones, brown algae, and green algae was used to characterize the anti-biological adhesion performance of the coating. The test results are shown in Tables 1 and 2 below: Table 1 Antibacterial properties of the special coatings for preventing biological invasion prepared in Examples 1-3 and Comparative Examples 1-6

[0046] Table 2 Corrosion resistance and anti-biological adhesion performance of the special coatings for preventing biological invasion prepared in Examples 1-3 and Comparative Examples 1-6

[0047] It can be seen from the data in Table 1 and Table 2 above that, by comparing Comparative Examples 1-2 with Example 3, it can be seen that the special coating for preventing biological invasion is prepared by replacing the mass of capsaicin and the like in step S1 with eugenol or directly combining the modified fungicide and silanized zinc molybdate nanoparticles in step S2. The test results are worse than those in Example 3, indicating that the modified fungicide is prepared by combining capsaicin with methacryloyl chloride. Capsaicin has good antibacterial properties, can inhibit the growth of microorganisms such as bacteria, and can prevent the attachment of organisms to the surface of marine facilities, effectively improving the antibacterial properties and anti-biological adhesion properties of the coating. The modified fungicide, silanized zinc molybdate nanoparticles and 3-mercapto-1,2-propylene glycol are combined to increase the binding force between the modified fungicide, the silanized zinc molybdate nanoparticles and the coating, and further improve the antibacterial properties, anti-biological adhesion properties and corrosion resistance of the coating; By comparing Comparative Examples 3-4 with Example 3, it can be seen that the test results of the special coating for preventing biological invasion are worse than those of Example 3, when the mass of the silane coupling agent is replaced by γ-methacryloxypropyltrimethoxysilane or the mass of the zinc molybdate nanoparticles is replaced by zinc oxide nanoparticles, and finally the special coating for preventing biological invasion is prepared. This indicates that the silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and then combined with zinc molybdate nanoparticles. The silane coupling agent can better disperse the zinc molybdate nanoparticles, and the zinc molybdate nanoparticles have good antibacterial properties, which further improves the corrosion resistance, antibacterial properties and anti-biological adhesion properties of the coating; By comparing Comparative Examples 5-6 with Example 3, it can be seen that the hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxanes and polysiloxanes) in step S3 is replaced with hydroxypropyl-terminated polydimethylsiloxane or the isophorone diisocyanate, polyether diol and bactericidal and corrosion-resistant copolymer in step S3 are combined to prepare a special coating for preventing biological invasion. The test results are worse than those in Example 3, indicating that isophorone diisocyanate, polyether diol, hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxanes and polysiloxanes), and bactericidal and corrosion-resistant copolymers are combined, and the hydroxyl-terminated methyl-3,3,3-trifluoropropyl (siloxanes and polysiloxanes) has fluorine atoms and has good hydrophobicity, which can effectively improve the corrosion resistance of the coating and further improve the anti-biological adhesion performance of the coating.

[0048] It can be seen from Table 1 and Table 2 above that the special coating for preventing biological damage prepared in Examples 1-3 is compared with the special coating for preventing biological damage prepared in Comparative Examples 1-6. By combining methacryloyl chloride with a natural bactericide, and then combining it with silanized zinc molybdate nanoparticles and 3-mercapto-1,2-propylene glycol, a bactericidal and corrosion-resistant copolymer is obtained, and then combined with isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane and polyether diol, fillers and additives are added, and finally a special coating for preventing biological damage is obtained, which meets the test performance requirements, while the special coating for preventing biological damage prepared in Comparative Examples 1-6 does not meet the performance requirements. The special coating for preventing biological damage prepared by the present invention not only has good anti-biological attachment performance, antibacterial performance, corrosion resistance and mechanical properties, but is also green and environmentally friendly, and has good comprehensive performance.

[0049] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0050] 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 special coating for preventing biological invasion, characterized in that: The following steps are involved: S1: Modified fungicide is obtained by combining methacryloyl chloride with natural fungicide; S2: combining the modified bactericide, silanized zinc molybdate nanoparticles, and 3-mercapto-1,2-propanediol to obtain a bactericidal and corrosion-resistant copolymer; S3: Combine the bactericidal and corrosion-resistant copolymer, isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane and polyether diol, add fillers and additives, and stir evenly to obtain a special coating for preventing biological invasion.

2. The method for preparing a special coating for preventing biological damage according to claim 1, characterized in that: Step S1 is specifically as follows: The natural fungicide and triethylamine are dissolved in xylene, and then stirred in an ice-water bath until the system temperature reaches 4-5°C, and then methacryloyl chloride is added, and the reaction is carried out at room temperature for 22-24 hours. After filtering, a cationic adsorption resin is added, and the modified fungicide is finally obtained by vacuum distillation.

3. The method for preparing a special coating for preventing biological damage according to claim 2, characterized in that: The natural fungicide is capsaicin.

4. The method for preparing a special coating for preventing biological invasion according to claim 1, characterized in that: Step S2 is specifically as follows: The modified bactericide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propanediol and azobisisobutyronitrile are mixed, and then tetrahydrofuran is added. The mixed solution is purged with nitrogen for 20-40 minutes, and then immersed in an oil bath at 65-75°C to react for 13-15 hours. After the reaction is completed, the mixed solution is precipitated with n-hexane, and the obtained precipitate is dissolved in tetrahydrofuran to finally obtain a bactericidal and corrosion-resistant copolymer.

5. The method for preparing a special coating for preventing biological invasion according to claim 4, characterized in that: The mass ratio of the modified fungicide, silanized zinc molybdate nanoparticles, 3-mercapto-1,2-propylene glycol and azobisisobutyronitrile is 0.8-1.2: 1.8-2.2: 0.016-0.02: 0.005-0.

009.

6. The method for preparing a special coating for preventing biological invasion according to claim 4, characterized in that: The preparation method of the silanized zinc molybdate nanoparticles comprises the following steps: The zinc molybdate nanoparticles and the silane coupling agent are mixed, the pH value of the mixture is adjusted to 8-9 with a sodium hydroxide solution, and then an ethanol / deionized water mixed solution is added and reacted at 55-65° C. for 0.5-1.5 h, filtered, washed with ethanol, and finally dried to obtain silanized zinc molybdate nanoparticles.

7. The method for preparing a special coating for preventing biological damage according to claim 6, characterized in that: The silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane mixed in a mass ratio of 1:

1.

8. The method for preparing a special coating for preventing biological invasion according to claim 1, characterized in that: Step S3 is specifically as follows: Under a nitrogen atmosphere, isophorone diisocyanate, hydroxyl-terminated fluoropolysiloxane, polyether diol and tetrahydrofuran are mixed evenly and stirred at 70-80°C for 2-4 hours to obtain a prepolymer, and then the bactericidal and corrosion-resistant copolymer, chain extender and catalyst are added to the prepolymer, and the reaction is continued at 70-80°C for 2-4 hours to obtain a polymer solution, and then fillers and additives are added and stirred evenly to finally obtain a special coating for preventing biological invasion.

9. The method for preparing a special coating for preventing biological damage according to claim 8, characterized in that: The chain extender is 2,2-dimethylolbutyric acid.

10. A special coating for preventing biological invasion obtained by the preparation method according to any one of claims 1 to 9.

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