Modified nano-copper antifouling paint and preparation method thereof

Abstract

The application provides a modified nano-copper anti-fouling paint and a preparation method thereof. The paint comprises the following components in parts by weight: 50-80 parts of acrylic resin, 4.5-6 parts of modified nano-copper, 3-5 parts of additives, and 25-40 parts of solvent. The nano-copper is modified by 3-bromopropargyl, azidotrimethylsilane and 2,5-bis(trifluoromethyl) bromobenzene, a triazole ring-based fluorine-containing aromatic hydrocarbon, so that the surface of the nano-copper is successfully grafted with the triazole ring-based fluorine-containing aromatic hydrocarbon. When the triazole ring-based fluorine-containing aromatic hydrocarbon is added into the acrylic resin paint, the triazole ring can destroy the biological membrane of marine organisms to prevent the marine organisms from breeding in the coating formed after the paint is film-formed. The fluorine atom can penetrate the biological membrane of marine fouling organisms, and the strong electronegativity of the fluorine atom can make the genetic development of the marine fouling organisms deviate from the normal direction or prevent the marine fouling organisms from breeding. Through the above double defense mechanisms, the modified nano-copper anti-fouling paint provided by the application has excellent anti-fouling performance.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a modified nano-copper antifouling coating and its preparation method. Background Technology

[0002] Hundreds of thousands of organisms live in the ocean, and when the substrates of artificial facilities come into contact with seawater, they become fouled by marine organisms. Biofouling refers to the process by which non-specific proteins and microorganisms aggregate, adhere, and form biofilms on material surfaces. Generally, marine biofouling includes four stages: In the first stage, organic matter such as proteins, polysaccharides, and lipids, as well as some inorganic matter, adhere to the substrate surface to form a protein film; in the second stage, microorganisms such as bacteria and diatoms attach to the protein film, grow rapidly, and secrete biomolecules (such as proteins and polysaccharides), forming another biofilm; in the third stage, algal spores and protozoa attach to the biofilm and grow; in the fourth stage, a large number of large fouling organisms continue to attach and grow, eventually forming a severe biofouling layer. Once fouling organisms adhere to the hull surface, they make the surface rough and uneven, significantly increasing the resistance during ship navigation. Furthermore, the large total amount of fouling organisms significantly increases the ship's weight, leading to increased fuel consumption. Therefore, marine biofouling has a serious impact on marine vessels. Summary of the Invention

[0003] To address the problem of biofouling on the surface of marine vessels, this invention provides a modified nano-copper antifouling coating and its preparation method.

[0004] According to a first aspect of the present invention, a modified nano-copper antifouling coating is provided, the coating comprising the following components in parts by weight: 50-80 parts of acrylic resin, 4.5-6 parts of modified nano-copper, 3-5 parts of additives, and 25-40 parts of solvent;

[0005] Modified nano-copper was prepared through the following steps:

[0006] S1. Disperse the nano-copper powder uniformly into the alcohol solution to obtain the first mixture;

[0007] S2. The first mixture is mixed with the silane coupling agent solution and reacted at 75-85°C for 4-5 hours. The reaction product is dried to obtain the intermediate product.

[0008] S3. Under ice bath conditions, the intermediate product is dispersed in a tetrahydrofuran solution to obtain a second mixture;

[0009] S4. The second mixture is mixed with 3-bromopropyne, catalyst, and trimethylsilane azido, and reacted at 70-80°C for 4-6 hours. 2,5-bis(trifluoromethyl)benzyl bromide and triethylamine are added to the reaction system and reacted at 70-80°C for 2-3 hours to obtain modified nano-copper.

[0010] The modified nano-antifouling coating provided by this invention uses acrylic resin as the resin matrix and introduces modified nano-copper. The nano-copper used in the preparation process has a large specific surface area and a high number of surface active centers. The nano-copper is modified with 3-bromopropyne, trimethyl azidosilane, and the triazole cyclic fluorinated aromatic hydrocarbon 2,5-bis(trifluoromethyl)bromobenzyl bromide, successfully grafting the triazole cyclic fluorinated aromatic hydrocarbon onto the surface of the nano-copper. On the one hand, the triazole ring can disrupt biofilms to prevent the unchecked proliferation of marine organisms in the coating formed after the coating has formed. On the other hand, the hydrogen-like properties of fluorine atoms allow them to penetrate the biofilm of marine fouling organisms. Furthermore, the strong electronegativity of fluorine allows it to negatively influence the genetic material of marine fouling organisms when it enters the biofilm through the mimicry effect, causing the genetics of marine fouling organisms to develop abnormally or preventing their reproduction. Through the above dual defense mechanism, acrylic resin coatings using the modified nano-copper exhibit excellent antifouling properties and can effectively prevent the attachment of marine fouling organisms such as bacteria, algae, marine plants, and lower animals to the surface of marine vessels.

[0011] Preferably, in step S1 of preparing modified nano-copper, the average particle size of the nano-copper powder is 20-40 nm.

[0012] Preferably, in step S2 of the preparation of modified nano-copper, the mass fraction of the silane coupling agent solution is 0.6-1.0%.

[0013] Preferably, in step S3 of the preparation of modified nano-copper, the mass ratio of the intermediate product to the tetrahydrofuran mixture is 1:15-20.

[0014] Preferably, in step S4 of the preparation of modified nano-copper, the catalyst is a mixture of copper sulfate pentahydrate and sodium L-ascorbate in a mass ratio of 1-2:5-7.

[0015] Preferably, in the preparation step of modified nano-copper, the intermediate product is calculated according to the mass ratio as follows: 3-bromopropyne: trimethylsilyl azido: 2,5-bis(trifluoromethyl)bromobenzyl: triethylamine = 5-15: 2-5: 8-10: 4-7: 30-35.

[0016] Preferably, the additives include at least one of defoamers, dispersants, and wetting agents.

[0017] Preferably, the defoamer includes at least one of dimethyl silicone oil, organosilicon, and polyvinyl acetate.

[0018] Preferably, the dispersant includes at least one of styrene-maleic anhydride sodium salt, sodium dodecyl sulfonate, and sodium polyacrylate.

[0019] Preferably, the wetting agent includes at least one of fatty alcohol polyoxyethylene ether and polyether-modified polydimethylsiloxane.

[0020] Preferably, the solvent includes at least one of aromatic solvents, aliphatic hydrocarbon solvents, ester solvents, alcohol solvents, ether solvents, and ketone solvents.

[0021] Preferably, the aromatic hydrocarbon solvent includes at least one of toluene and xylene.

[0022] Preferably, the aliphatic hydrocarbon solvent includes at least one of hexane and heptane.

[0023] Preferably, the ester solvent includes at least one of ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate.

[0024] Preferably, the alcohol solvent includes at least one of isopropanol and butanol.

[0025] Preferably, the ether solvent includes at least one of dioxane, diethyl ether, and dibutyl ether.

[0026] Preferably, the ketone solvent includes at least one of methyl ethyl ketone and methyl isobutyl ketone.

[0027] Preferably, the acrylic resin is a fluorosilicone modified acrylic resin. The raw materials used to prepare the fluorosilicone modified acrylic resin, calculated by weight, include: 5-17 parts of organofluorine monomer, 5-20 parts of organosilicon monomer, 85-95 parts of acrylate monomer, 1-2 parts of initiator, and 80-100 parts of solvent.

[0028] Compared to fluorine- or silicon-modified acrylic resins alone, the fluorine-silicone-modified acrylic resin used in the nano-copper antifouling coating of this solution has a lower surface energy, which further improves the antifouling performance of the coating after film formation.

[0029] Preferably, the acrylate monomers are composed of methyl methacrylate, ethyl acrylate, n-butyl acrylate, and butyl methacrylate in a mass ratio of 32-40:15-20:15-17:13-18.

[0030] Preferably, the organofluorine monomer includes at least one of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate.

[0031] Preferably, the organosilicon monomer includes at least one of γ-methacryloyloxypropyltrimethylsilane and polydimethylsiloxane methacrylate.

[0032] Preferably, the solvent used in the preparation of fluorosilicone modified acrylic resin is a mixture of xylene and butyl acetate in a mass ratio of 1-2:1-3.

[0033] Preferably, the raw materials used to prepare the fluorosilicone modified acrylic resin further include, by weight, 15-20 parts of: methacrylamide ethyl ethylene urea.

[0034] Preferably, the above-mentioned fluorosilicone modified acrylic resin is prepared by the following steps: under a nitrogen protective atmosphere, the solvent is heated to 80-90°C, acrylate monomers, part of the initiator, organofluorine monomers, organosilicon monomers, and methacrylamide ethyl ethylene urea are added dropwise to the reaction system and kept at 80-90°C for 1-2 hours, the reaction system is heated to 100-120°C and the remaining initiator is added, and kept at 100-120°C for 1-3 hours to obtain the fluorosilicone modified acrylic resin.

[0035] In the modified nano-copper antifouling coating provided by this invention, organosilicon monomers and organofluorine monomers are used to modify acrylic resin and add it to the coating. Although the coating formed after film formation has excellent antifouling performance, the modified acrylic resin has low surface energy, resulting in poor adhesion between the coating and the substrate. In this solution, methacrylamide ethyl ethylene urea, which contains both amine and ethylene urea rings, is introduced during the preparation of the fluorosilicone modified acrylic resin. Methacrylamide ethyl ethylene urea can copolymerize with other monomers. The fluorosilicone modified acrylic resin obtained through polymerization is applied to the nano-copper antifouling coating. This not only imparts excellent antifouling performance to the coating after film formation but also significantly improves the adhesion between the coating and the substrate, thereby further improving the long-term antifouling performance of the coating to a certain extent. Detailed Implementation

[0036] The technical features of the technical solution provided by the present invention will be further clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] Example 1

[0038] A modified nano-copper antifouling coating is prepared by the following steps: 65 parts by weight of acrylic resin, 5 parts by weight of modified nano-copper, 4 parts by weight of additives and 32 parts by weight of solvent are mixed evenly to obtain the modified nano-copper antifouling coating.

[0039] The additives are composed of defoamer, dispersant and wetting agent mixed in a mass ratio of 1:3:2;

[0040] The solvent is ethyl acetate;

[0041] Modified nano-copper was prepared through the following steps:

[0042] S1. Copper nanoparticles with an average particle size of 30 nm are uniformly dispersed in an ethanol solution to obtain the first mixture;

[0043] S2. The first mixture was mixed with a 0.8% (w / w) solution of silane coupling agent KH570 and reacted at 80°C for 4.5 hours. The reaction product was dried to obtain the intermediate product.

[0044] S3. Under ice bath conditions, the intermediate product is dispersed in a tetrahydrofuran solution to obtain a second mixture;

[0045] The mass ratio of the intermediate product to the tetrahydrofuran mixture is 1:18.

[0046] S4. The second mixture was mixed with 3-bromopropyne, a catalyst (made by mixing copper sulfate pentahydrate and sodium L-ascorbate in a mass ratio of 1:6), and trimethylsilane azido, and reacted at 75°C for 5 hours. Then, 2,5-bis(trifluoromethyl)bromobenzyl bromide and triethylamine were added to the reaction system and reacted at 75°C for 2.5 hours to obtain modified nano-copper.

[0047] In the preparation step of modified nano-copper, the intermediate product is calculated by mass ratio as follows: 3-bromopropyne: trimethylsilyl azido: 2,5-bis(trifluoromethyl)bromobenzyl: triethylamine = 10:3:9:6:33.

[0048] Example 2

[0049] A modified nano-copper antifouling coating is prepared by the following steps: 50 parts by weight of acrylic resin, 6 parts by weight of modified nano-copper, 3 parts by weight of additives and 25 parts by weight of solvent are mixed evenly to obtain the modified nano-copper antifouling coating.

[0050] The additives are composed of defoamer, dispersant and wetting agent mixed in a mass ratio of 1:3:2;

[0051] The solvent is ethyl acetate;

[0052] Modified nano-copper was prepared through the following steps:

[0053] S1. Copper nanoparticles with an average particle size of 20 nm are uniformly dispersed in an ethanol solution to obtain the first mixture;

[0054] S2. The first mixture was mixed with a 0.6% (w / w) solution of silane coupling agent KH570 and reacted at 75°C for 5 hours. The reaction product was dried to obtain the intermediate product.

[0055] S3. Under ice bath conditions, the intermediate product is dispersed in a tetrahydrofuran solution to obtain a second mixture;

[0056] The mass ratio of the intermediate product to the tetrahydrofuran mixture is 1:15.

[0057] S4. The second mixture was mixed with 3-bromopropyne, catalyst (made by mixing copper sulfate pentahydrate and sodium L-ascorbate in a mass ratio of 1.5:5), and trimethylsilane azido, and reacted at 70°C for 6 hours. 2,5-bis(trifluoromethyl)bromobenzyl bromide and triethylamine were added to the reaction system and reacted at 70°C for 3 hours to obtain modified nano-copper.

[0058] In the preparation step of modified nano-copper, the intermediate product is calculated by mass ratio as follows: 3-bromopropyne: trimethylsilyl azido: 2,5-bis(trifluoromethyl)bromobenzyl: triethylamine = 5:5:8:4:30.

[0059] Example 3

[0060] A modified nano-copper antifouling coating is prepared by the following steps: 80 parts by weight of acrylic resin, 4.5 parts by weight of modified nano-copper, 5 parts by weight of additives, and 40 parts by weight of solvent are mixed evenly to obtain the modified nano-copper antifouling coating.

[0061] The additives are composed of defoamer, dispersant and wetting agent mixed in a mass ratio of 1:3:2;

[0062] The solvent is ethyl acetate;

[0063] Modified nano-copper was prepared through the following steps:

[0064] S1. Copper nanoparticles with an average particle size of 40 nm are uniformly dispersed in an ethanol solution to obtain the first mixture;

[0065] S2. The first mixture was mixed with a 1.0% (w / w) solution of silane coupling agent KH570 and reacted at 85°C for 4 hours. The reaction product was dried to obtain the intermediate product.

[0066] S3. Under ice bath conditions, the intermediate product is dispersed in a tetrahydrofuran solution to obtain a second mixture;

[0067] The mass ratio of the intermediate product to the tetrahydrofuran mixture is 1:20.

[0068] S4. The second mixture was mixed with 3-bromopropyne, catalyst (a mixture of copper sulfate pentahydrate and sodium L-ascorbate in a mass ratio of 2:7), and trimethylsilane azido, and reacted at 80°C for 4 hours. 2,5-bis(trifluoromethyl)bromobenzyl bromide and triethylamine were added to the reaction system and reacted at 80°C for 2 hours to obtain modified nano-copper.

[0069] In the preparation step of modified nano-copper, the intermediate product is calculated by mass ratio as follows: 3-bromopropyne: trimethylsilyl azido: 2,5-bis(trifluoromethyl)bromobenzyl: triethylamine = 15:2:10:7:35.

[0070] Example 4

[0071] This embodiment provides a modified nano-copper antifouling coating. Compared with Embodiment 1, the difference in composition is that an equal amount of fluorosilicone modified acrylic resin is used instead of acrylic resin.

[0072] The raw materials used to prepare fluorosilicone modified acrylic resin, calculated by weight, include: 12 parts of organofluorine monomer, 13 parts of organosilicon monomer, 90 parts of acrylate monomer, 1.5 parts of initiator, and 90 parts of solvent.

[0073] The above-mentioned fluorosilicone modified acrylic resin was prepared by the following steps: Under a nitrogen protective atmosphere, the solvent was heated to 85°C, and acrylate monomers, a portion of the initiator benzoyl peroxide (accounting for 40% of the total weight of the initiator), the organofluorine monomer hexafluorobutyl acrylate, and the organosilicon monomer γ-methacryloyloxypropyltrimethylsilane were added dropwise to the reaction system and kept at 85°C for 1.5 hours. The reaction system was then heated to 110°C and the remaining initiator was added. The system was kept at 110°C for 2 hours to obtain the fluorosilicone modified acrylic resin.

[0074] The solvent used in the preparation of fluorosilicone modified acrylic resin is a mixture of xylene and butyl acetate in a mass ratio of 1:2.

[0075] The acrylate monomers are composed of methyl methacrylate, ethyl acrylate, n-butyl acrylate, and butyl methacrylate in a mass ratio of 36:17:16:15.

[0076] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 1.

[0077] Example 5

[0078] This embodiment provides a modified nano-copper antifouling coating. Compared with Embodiment 1, the difference in composition is that an equal amount of fluorosilicone modified acrylic resin is used instead of acrylic resin.

[0079] The raw materials used to prepare fluorosilicone modified acrylic resin, calculated by weight, include: 5 parts of organofluorine monomer, 20 parts of organosilicon monomer, 85 parts of acrylate monomer, 1 part of initiator, and 80 parts of solvent.

[0080] The above-mentioned fluorosilicone modified acrylic resin was prepared by the following steps: Under a nitrogen protective atmosphere, the solvent was heated to 80°C, and acrylate monomers, a portion of the initiator benzoyl peroxide (accounting for 40% of the total weight of the initiator), the organofluorine monomer hexafluorobutyl acrylate, and the organosilicon monomer γ-methacryloyloxypropyltrimethylsilane were added dropwise to the reaction system and kept at 80°C for 2 hours. The reaction system was then heated to 100°C and the remaining initiator was added. The system was kept at 100°C for 3 hours to obtain the fluorosilicone modified acrylic resin.

[0081] The solvent used in the preparation of fluorosilicone modified acrylic resin is a mixture of xylene and butyl acetate in a mass ratio of 1.5:1.

[0082] The acrylate monomers are composed of methyl methacrylate, ethyl acrylate, n-butyl acrylate, and butyl methacrylate in a mass ratio of 32:15:17:18.

[0083] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 1.

[0084] Example 6

[0085] This embodiment provides a modified nano-copper antifouling coating. Compared with Embodiment 1, the difference in composition is that an equal amount of fluorosilicone modified acrylic resin is used instead of acrylic resin.

[0086] The raw materials used to prepare fluorosilicone modified acrylic resin, calculated by weight, include: 17 parts of organofluorine monomer, 5 parts of organosilicon monomer, 95 parts of acrylate monomer, 2 parts of initiator, and 100 parts of solvent.

[0087] The above-mentioned fluorosilicone modified acrylic resin was prepared by the following steps: Under a nitrogen protective atmosphere, the solvent was heated to 90°C, and acrylate monomers, a portion of the initiator benzoyl peroxide (accounting for 40% of the total weight of the initiator), the organofluorine monomer hexafluorobutyl acrylate, and the organosilicon monomer γ-methacryloyloxypropyltrimethylsilane were added dropwise to the reaction system and kept at 90°C for 1 hour. The reaction system was then heated to 120°C and the remaining initiator was added. The system was kept at 120°C for 1 hour to obtain the fluorosilicone modified acrylic resin.

[0088] The solvent used in the preparation of fluorosilicone modified acrylic resin is a mixture of xylene and butyl acetate in a mass ratio of 2:3.

[0089] The acrylate monomers are composed of methyl methacrylate, ethyl acrylate, n-butyl acrylate, and butyl methacrylate in a mass ratio of 40:20:15:13.

[0090] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 1.

[0091] Example 7

[0092] This embodiment provides a modified nano-copper antifouling coating. Compared with Example 4, the difference in composition is that the raw materials used to prepare the fluorosilicone modified acrylic resin also include methacrylamide ethyl ethylene urea.

[0093] The raw materials used to prepare fluorosilicone modified acrylic resin, calculated by weight, include: 12 parts of organofluorine monomer, 13 parts of organosilicon monomer, 90 parts of acrylate monomer, 18 parts of methacrylamide ethyl ethylene urea, 1.5 parts of initiator, and 90 parts of solvent.

[0094] The above-mentioned fluorosilicone modified acrylic resin was prepared by the following steps: Under a nitrogen protective atmosphere, the solvent was heated to 85°C, and acrylate monomers, a portion of the initiator benzoyl peroxide (accounting for 40% of the total weight of the initiator), organofluorine monomer hexafluorobutyl acrylate, organosilicon monomer γ-methacryloyloxypropyltrimethylsilane, and methacrylamide ethyl ethylene urea were added dropwise to the reaction system and kept at 85°C for 1.5 hours. The reaction system was then heated to 110°C and the remaining initiator was added. The system was kept at 110°C for 2 hours to obtain the fluorosilicone modified acrylic resin.

[0095] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 4.

[0096] Example 8

[0097] This embodiment provides a modified nano-copper antifouling coating. Compared with Example 4, the difference in composition is that the raw materials used to prepare the fluorosilicone modified acrylic resin also include methacrylamide ethyl ethylene urea.

[0098] The raw materials used to prepare fluorosilicone modified acrylic resin, calculated by weight, include: 12 parts of organofluorine monomer, 13 parts of organosilicon monomer, 90 parts of acrylate monomer, 15 parts of methacrylamide ethyl ethylene urea, 1.5 parts of initiator, and 90 parts of solvent.

[0099] The above-mentioned fluorosilicone modified acrylic resin was prepared by the following steps: Under a nitrogen protective atmosphere, the solvent was heated to 85°C, and acrylate monomers, a portion of the initiator benzoyl peroxide (accounting for 40% of the total weight of the initiator), organofluorine monomer hexafluorobutyl acrylate, organosilicon monomer γ-methacryloyloxypropyltrimethylsilane, and methacrylamide ethyl ethylene urea were added dropwise to the reaction system and kept at 85°C for 1.5 hours. The reaction system was then heated to 110°C and the remaining initiator was added. The system was kept at 110°C for 2 hours to obtain the fluorosilicone modified acrylic resin.

[0100] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 4.

[0101] Example 9

[0102] This embodiment provides a modified nano-copper antifouling coating. Compared with Example 4, the difference in composition is that the raw materials used to prepare the fluorosilicone modified acrylic resin also include methacrylamide ethyl ethylene urea.

[0103] The raw materials used to prepare fluorosilicone modified acrylic resin, calculated by weight, include: 12 parts of organofluorine monomer, 13 parts of organosilicon monomer, 90 parts of acrylate monomer, 20 parts of methacrylamide ethyl ethylene urea, 1.5 parts of initiator, and 90 parts of solvent.

[0104] The above-mentioned fluorosilicone modified acrylic resin was prepared by the following steps: Under a nitrogen protective atmosphere, the solvent was heated to 85°C, and acrylate monomers, a portion of the initiator benzoyl peroxide (accounting for 40% of the total weight of the initiator), organofluorine monomer hexafluorobutyl acrylate, organosilicon monomer γ-methacryloyloxypropyltrimethylsilane, and methacrylamide ethyl ethylene urea were added dropwise to the reaction system and kept at 85°C for 1.5 hours. The reaction system was then heated to 110°C and the remaining initiator was added. The system was kept at 110°C for 2 hours to obtain the fluorosilicone modified acrylic resin.

[0105] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 4.

[0106] Example 10

[0107] This embodiment provides a modified nano-copper antifouling coating. Compared with Example 4, the difference in composition is that the acrylate monomers used in the raw materials for preparing fluorosilicone modified acrylic resin are methyl methacrylate and ethyl acrylate mixed in a mass ratio of 51:33.

[0108] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 4.

[0109] Example 11

[0110] This embodiment provides a modified nano-copper antifouling coating. Compared with Example 4, the difference in composition is that the acrylate monomers used in the raw materials for preparing fluorosilicone modified acrylic resin are mixed from methyl methacrylate, ethyl acrylate, and n-butyl acrylate in a mass ratio of 36:17:31.

[0111] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 4.

[0112] Example 12

[0113] This embodiment provides a modified nano-copper antifouling coating. Compared with Example 4, the difference in composition is that the acrylate monomers used in the raw materials for preparing fluorosilicone modified acrylic resin are mixed from methyl methacrylate, ethyl acrylate, and butyl methacrylate in a mass ratio of 36:33:15.

[0114] Apart from the differences mentioned above, the materials, formulation ratios, and preparation operations used in this embodiment are strictly consistent with those in Example 4.

[0115] Example 13

[0116] A modified nano-copper antifouling coating is prepared by the following steps: 65 parts by weight of fluorosilicone modified acrylic resin, 5 parts by weight of modified nano-copper, 4 parts by weight of additives, and 32 parts by weight of solvent are mixed evenly to obtain the modified nano-copper antifouling coating.

[0117] The additives are composed of defoamer, dispersant and wetting agent mixed in a mass ratio of 1:3:2;

[0118] The solvent is ethyl acetate;

[0119] Modified nano-copper was prepared through the following steps:

[0120] S1. Copper nanoparticles with an average particle size of 30 nm are uniformly dispersed in an ethanol solution to obtain the first mixture;

[0121] S2. The first mixture was mixed with a 0.8% (w / w) solution of silane coupling agent KH570 and reacted at 80°C for 4.5 hours. The reaction product was dried to obtain the intermediate product.

[0122] S3. Under ice bath conditions, the intermediate product is dispersed in a tetrahydrofuran solution to obtain a second mixture;

[0123] The mass ratio of the intermediate product to the tetrahydrofuran mixture is 1:18.

[0124] S4. The second mixture was mixed with 3-bromopropyne, a catalyst (made by mixing copper sulfate pentahydrate and sodium L-ascorbate in a mass ratio of 1:6), and trimethylsilane azido, and reacted at 75°C for 5 hours. Then, 2,5-bis(trifluoromethyl)bromobenzyl bromide and triethylamine were added to the reaction system and reacted at 75°C for 2.5 hours to obtain modified nano-copper.

[0125] In the preparation step of modified nano-copper, the intermediate product is calculated by mass ratio as follows: 3-bromopropyne: trimethylsilyl azido: 2,5-bis(trifluoromethyl)bromobenzyl: triethylamine = 10:3:9:6:33;

[0126] The raw materials used to prepare fluorosilicone modified acrylic resin, calculated by weight, include: 12 parts of organofluorine monomer, 13 parts of organosilicon monomer, 90 parts of acrylate monomer, 18 parts of methacrylamide ethyl ethylene urea, 1.5 parts of initiator, and 90 parts of solvent.

[0127] The above-mentioned fluorosilicone modified acrylic resin was prepared by the following steps: Under a nitrogen protective atmosphere, the solvent was heated to 85°C, and acrylate monomers, a portion of the initiator benzoyl peroxide (accounting for 40% of the total weight of the initiator), organofluorine monomer hexafluorobutyl acrylate, organosilicon monomer γ-methacryloyloxypropyltrimethylsilane, and methacrylamide ethyl ethylene urea were added dropwise to the reaction system and kept at 85°C for 1.5 hours. The reaction system was then heated to 110°C and the remaining initiator was added. The system was kept at 110°C for 2 hours to obtain the fluorosilicone modified acrylic resin.

[0128] The solvent used in the preparation of fluorosilicone modified acrylic resin is a mixture of xylene and butyl acetate in a mass ratio of 1:2.

[0129] The acrylate monomers are composed of methyl methacrylate, ethyl acrylate, n-butyl acrylate, and butyl methacrylate in a mass ratio of 36:17:16:15.

[0130] Comparative Example 1

[0131] This comparative example provides a modified nano-copper antifouling coating. The difference between this and Example 1 is that an equal amount of unmodified nano-copper is used instead of the modified nano-copper. Apart from the above differences, the materials, formulation ratios, and preparation procedures used in this comparative example are strictly consistent with those in Example 1.

[0132] Comparative Example 2

[0133] This comparative example provides a modified nano-copper antifouling coating. The difference in composition compared to Example 1 is that an equal amount of bisphenol A epoxy resin is used instead of acrylic resin. Apart from the above differences, the materials, formulation ratios, and preparation procedures used in this comparative example are strictly consistent with those in Example 1.

[0134] Comparative Example 3

[0135] This comparative example provides a modified nano-copper antifouling coating. The difference in composition compared to Example 1 is that, in the preparation step of the modified nano-copper, an equal amount of 4-(trifluoromethyl)benzyl bromide is used instead of 2,5-bis(trifluoromethyl)benzyl bromide. Apart from the above difference, the materials, formulation ratios, and preparation procedures used in this comparative example are strictly consistent with those in Example 1.

[0136] Test case

[0137] 1. Participants

[0138] This test example uses the modified nano-copper antifouling coatings prepared in Examples 1-13 and Comparative Examples 1-3 as test objects to conduct relevant performance tests.

[0139] 2. Test Content

[0140] (1) Anti-fouling performance

[0141] Referring to the national standard GB / T5370-2007 "Test Method for Shallow Sea Immersion of Antifouling Paint Samples", the prepared samples were fixed in a wooden frame, clearly marked before immersion, and their original state was recorded. The immersion depth of the samples was 1m. The immersed samples were vertically and firmly fixed to the frame, with the sample surface parallel to the main current of the seawater, and the spacing between the frames was greater than or equal to 200nm. After immersion, the attachment area of ​​mussels, mollusks, and algae on the sample was observed periodically. The observation chamber was 20mm away from the edge of the sample to eliminate the edge effect. The observation time was minimized, and the sample surface was photographed to evaluate the antifouling performance of the experimental sample. The sample was immediately immersed in the sea after observation to avoid the death of attached organisms, which would affect the observation results. The coverage area of ​​fouling organisms is measured using a percentage plate with the same observation area as the sample. When evaluating test samples or control samples within the same frame, if the coverage area of ​​fouling organisms differs by 5%, the average value is taken. Otherwise, the average value of the two samples with larger coverage areas of fouling organisms is used to calculate the test result.

[0142] (2) Adhesion

[0143] Refer to national standard GB / T 9286-1998.

[0144] (3) Weather resistance

[0145] The weather resistance of a coating is characterized by the water resistance and salt resistance of the coating film after film formation. The water resistance is defined by the national standard GB / T 1733-1993 (Method A), and the salt resistance is defined by the national standard GB / T 1763-1989.

[0146] 3. Experimental Results

[0147] Table 1. Performance test results of the modified nano-copper antifouling coating

[0148]

[0149] The relevant performance test results of the modified nano-copper antifouling coatings provided in Examples 1-13 and Comparative Examples 1-3 are shown in Table 1.

[0150] The nano-copper antifouling coatings provided in Examples 1-3 exhibit excellent antifouling and biofouling adhesion properties after film formation. After immersion in seawater for 3, 6, 9, 12, 24, and 32 months, the percentage of biofouling coverage in the coating was 1-2%, 4-5%, 6-7%, 8-10%, 11-12%, and 15-17%, respectively. This is mainly because the modified nano-antifouling coatings provided in Examples 1-3 use acrylic resin as the resin matrix and introduce modified nano-copper. The nano-copper used in the preparation process has a large specific surface area and a high number of surface active centers. The nano-copper is modified using 3-bromopropyne, trimethyl azidosilane, and the triazole cyclic fluorinated aromatic hydrocarbon 2,5-bis(trifluoromethyl)bromobenzyl bromide. The modified nano-copper surface is successfully grafted with triazole ring-based fluorinated aromatic hydrocarbons. On the one hand, the triazole ring can disrupt the biofilm to prevent the unchecked reproduction of marine organisms in the coating formed after the coating is applied. On the other hand, the hydrogen-like properties of fluorine atoms allow them to penetrate the biofilm of marine fouling organisms. Furthermore, the strong electronegativity of fluorine allows it to negatively influence the genetic material of marine fouling organisms when it enters the biofilm through the mimicry effect, causing the genetics of marine fouling organisms to develop abnormally or preventing their reproduction. Through the above dual defense mechanism, acrylic resin coatings using the modified nano-copper exhibit excellent antifouling properties and can effectively prevent the attachment of marine fouling organisms such as bacteria, algae, marine plants, and lower animals to the surface of marine vessels.

[0151] Compared to Example 1, the nano-copper used in the nano-copper antifouling coating provided in Comparative Example 1 was unmodified, the resin matrix used in the nano-copper antifouling coating provided in Comparative Example 2 was bisphenol A type epoxy resin, and the modified nano-copper in the modified nano-copper antifouling coating provided in Comparative Example 3 used 4-(trifluoromethyl)benzyl bromide as the triazole cyclic fluorinated aromatic hydrocarbon in the preparation process. The test results showed that the antifouling performance of the modified nano-copper antifouling coatings provided in Comparative Examples 1 to 3 after film formation was lower than that of Example 1.

[0152] Compared with Example 1, the nano-copper antifouling coatings provided in Examples 4-9 use fluorosilicone modified acrylic resin as the resin matrix. The test results show that the antifouling performance of the nano-copper antifouling coatings provided in Examples 4-9 after film formation is better than that of Example 1.

[0153] Among all the tested objects, the modified nano-copper antifouling coating provided in Example 13 uses a fluorosilicone modified acrylic resin prepared from organofluorine monomers, organosilicon monomers, acrylate monomers and methacrylamide ethyl ethylene urea as the resin matrix, and introduces modified nano-copper obtained by modifying 3-bromopropyne, trimethyl azidosilane and triazole cyclofluoroaromatic 2,5-bis(trifluoromethyl)bromobenzyl. The acrylate monomers are composed of methyl methacrylate, ethyl acrylate, n-butyl acrylate and butyl methacrylate in a mass ratio of 36:17:16:15. The test results show that the modified nano-copper antifouling coating provided in Example 13 has the best antifouling performance after film formation.

[0154] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention, but such modifications or substitutions are all within the scope of protection of the present invention.

Claims

1. A modified nano-copper anti-fouling coating, characterized in that, The components include the following weight parts: fluorosilicon modified acrylic resin 50~80 parts, modified nano copper 4.5~6 parts, auxiliary agent 3~5 parts, and solvent 25~40 parts; The modified nano copper is prepared by the following steps: S1. uniformly dispersing nano copper powder into an alcohol solution to obtain a first mixed solution; S2. mixing the first mixed solution with a silane coupling agent solution, and then reacting at 75~85℃ for 4~5 hours, and drying the reaction product to obtain an intermediate product; S3. dispersing the intermediate product into a tetrahydrofuran solution under ice bath conditions to obtain a second mixed solution; S4. mixing the second mixed solution with 3-bromopropargyl, a catalyst, and azidotrimethylsilane, and then reacting at 70~80℃ for 4~6 hours, adding 2,5-bis(trifluoromethyl)benzyl and triethylamine to the reaction system, and then reacting at 70~80℃ for 2~3 hours to obtain the modified nano copper; The raw materials for preparing the fluorosilicon modified acrylic resin include, calculated by weight fraction, organic fluorine monomer 5~17 parts, organic silicon monomer 5~20 parts, acrylic ester monomer 85~95 parts, initiator 1~2 parts, solvent 80~100 parts, and methacrylamide ethyl ethylene urea 15~20 parts; The acrylic ester monomer is mixed by methyl methacrylate, ethyl acrylate, n-butyl acrylate, and butyl methacrylate according to a mass ratio of 32~40:15~20:15~17:13~18; The fluorosilicon modified acrylic resin is prepared by the following steps: under a nitrogen protective atmosphere, heating the solvent to 80~90℃, adding the acrylic ester monomer, part of the initiator, the organic fluorine monomer, the organic silicon monomer, and the methacrylamide ethyl ethylene urea dropwise into the reaction system, and then incubating at 80~90℃ for 1~2 hours, increasing the temperature of the reaction system to 100~120℃, and adding the remaining initiator, and then incubating at 100~120℃ for 1~3 hours to obtain the fluorosilicon modified acrylic resin.

2. The modified nano-copper anti-fouling coating according to claim 1, characterized in that: In the preparation step S1 of the modified nano copper, the average particle size of the nano copper powder is 20~40nm.

3. The modified nano-copper anti-fouling coating according to claim 1, wherein the modified nano-copper anti-fouling coating is characterized by: In the preparation step S2 of the modified nano copper, the mass fraction of the silane coupling agent solution is 0.6~1.0%.

4. The modified nano-copper anti-fouling coating according to claim 1, wherein the coating is characterized by: In the preparation step S3 of the modified nano copper, the mass ratio of the intermediate product to the tetrahydrofuran solution is 1:15~20.

5. The modified nano-copper anti-fouling coating according to claim 1, wherein the coating is characterized by: In the preparation step of the modified nano copper, according to the mass ratio, the intermediate product:3-bromopropargyl:azidotrimethylsilane:2,5-bis(trifluoromethyl)benzyl:triethylamine=5~15:2~5:8~10:4~7:30~35.

6. The modified nano-copper anti-fouling coating according to claim 1, wherein the coating is applied to a surface of a ship. The organic fluorine monomer includes at least one of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate, and / or, The organic silicon monomer includes at least one of γ-methacryloyloxypropyl trimethyl silane and methacrylate polydimethyl siloxane, and / or, The solvent is mixed by xylene and butyl acetate according to a mass ratio of 1~2:1~3.

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