Antibacterial, oxygen-releasing and antifouling coating for mariculture net cage and preparation method of antibacterial, oxygen-releasing and antifouling coating

Abstract

The invention provides an antibacterial, oxygen-releasing and antifouling coating for a mariculture net cage and a preparation method of the antibacterial, oxygen-releasing and antifouling coating, and relates to the technical field of novel functional materials. The specific preparation method of the coating comprises the following steps: S1, cleaning and drying the surface of a culture netting, immersing the culture netting in a hydrolysis reaction solution, adjusting the pH value to 2-6, and carrying out a reaction to obtain a pretreated culture netting; s2, adding water oxygen release type nanoparticles into the block polymer solution, and uniformly stirring to prepare an oxygen release antifouling coating solution; and S3, immersing the pretreated culture netting into the oxygen-releasing antifouling coating solution, taking out the culture netting, curing the culture netting, and carrying out dipping-curing circular treatment for 3-90 times to obtain the culture netting coating. The coating provided by the invention is used for the marine aquaculture net cage netting, and has excellent antibacterial performance, oxygen release ability and antifouling ability. Compared with a single anti-biodeposition coating commonly used in seawater traditional net cage culture, the coating prepared by the method can better adapt to actual use requirements in a complex culture environment, and deposition of fouling organisms on the surface of the netting is reduced.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, and in particular to an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages and its preparation method. Background Technology

[0002] Marine aquaculture, as a vital component of global fisheries, plays a crucial role in meeting the ever-growing demand for aquatic products. However, with the continuous expansion of marine aquaculture scale, biofouling of netting used in cage aquaculture has become an increasingly prominent problem. Biofouling of netting in cage aquaculture refers to the phenomenon where various marine organisms, such as algae, barnacles, mussels, and bryozoans, adhere to the surface of the netting during the cage aquaculture process. The continuous attachment of these fouling organisms significantly increases the weight of the netting, drastically reduces the buoyancy of the cage, and consequently compromises the stability of the cage under the impact of waves, even causing the cage to sink. Furthermore, the attachment of fouling organisms accelerates the wear and tear of the cages, significantly shortening their lifespan and forcing farmers to frequently replace the cages, thus greatly increasing aquaculture costs. More seriously, fouling organisms can clog the mesh, and their excrement, unable to be discharged in time, exacerbates eutrophication in the surrounding waters, reduces dissolved oxygen levels inside the cages, and ultimately leads to mass mortality of aquatic products due to oxygen depletion, causing huge economic losses for farmers. Furthermore, fouled biological communities often carry a variety of pathogens, which can easily spread to farmed aquatic products, affecting their healthy growth and even causing large-scale epidemics. This poses a serious threat to the development of the entire aquaculture industry and, in turn, causes incalculable impacts on the stability of the economic order and the ecological environment.

[0003] In existing technologies, antifouling coatings are commonly used to address fouling organisms in marine aquaculture cages, representing the most economical, simple, and effective method. Early antifouling coating technologies relied on highly active bactericides such as copper (Cu) and cuprous oxide (Cu₂O), which, while providing short-term broad-spectrum protection, easily adversely affected the growth and development of farmed organisms, potentially harming consumer health through the food chain and causing marine environmental pollution. In recent years, international organizations have introduced regulations restricting their use. Nanomaterials such as silver nanoparticles, copper nanoparticles, titanium dioxide, and zinc oxide can generate reactive oxygen species (ROS) that disrupt bacterial cell membranes, DNA, and metabolic functions, achieving broad-spectrum antibacterial effects. However, insufficient light and low dissolved oxygen concentrations in the aquaculture water can affect ROS generation, thus weakening the antibacterial effect. Currently, novel antifouling coating technologies for netting surfaces mainly include low surface energy antifouling coatings, silicate antifouling coatings, and antifouling coatings containing plant extracts. Among these, low surface energy antifouling materials, represented by organosilicon, are non-polar... Si O The main chain gives it significant hydrophobicity, making it difficult for water molecules to spread on its surface, thus exhibiting the advantage of low surface adhesion. It is used in marine antifouling, ship antifouling, building waterproofing and other fields, but it still has shortcomings in terms of broad-spectrum antibacterial properties.

[0004] Therefore, the market urgently needs to develop a new type of antifouling coating that is non-toxic, harmless, and has broad-spectrum protective properties. Summary of the Invention

[0005] Therefore, this invention proposes an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages and its preparation method.

[0006] The technical solution of this invention is implemented as follows: A method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages, the specific preparation method including: S1. After cleaning and drying the surface of the aquaculture netting, immerse it in the hydrolysis reaction solution and adjust the pH value to 2-6 to carry out the reaction, and obtain the pretreated aquaculture netting. The netting of this invention includes polyethylene (PE), polypropylene (PP), and nylon (PA) for nearshore aquaculture, and ultra-high molecular weight polyethylene (UHMWPE), polyethylene terephthalate (PET), and aramid for offshore aquaculture.

[0007] S2. Add water-release oxygen-type nanoparticles to the block polymer solution, stir evenly, and prepare an oxygen-release anti-fouling coating solution. S3. Immerse the pretreated aquaculture netting in an oxygen-releasing antifouling coating solution, remove it and cure it. Repeat the above immersion-curing cycle 3-90 times to obtain the aquaculture netting coating.

[0008] Furthermore, in step S1, the surface cleaning of the aquaculture netting involves sequentially cleaning the netting surface with 0.1-0.5 mol / L hydrochloric acid and isopropanol. The hydrolysis reaction solution is an aminosilane solution and deionized water with a volume ratio of 1:1-20.

[0009] Furthermore, in step S1, the reaction time is 1-600 min and the temperature is 20-30℃.

[0010] Furthermore, the concentration of the aminosilane solution is 0.1wt%-30wt%; The commercially available aminosilane of this invention has a concentration of 99% and is diluted to 0.1wt%-30wt% using an organic solvent.

[0011] The structural formula of the aminosilane is: Silyl (R O)3Si can be any of the following structures: , , , ; R is -CH2CH2CH2-, -CH2CH2-, -C6H4-, or cyclohexyl-C6H 11 -CH2CH2CH2OCH2CH2CH2- or -CH2CH2CH2-NH-CH2CH2-.

[0012] Furthermore, in step S2, the concentration of the block polymer solution is 0.1wt%-10wt%, and the block polymer includes a silicon-containing block polymer or a fluorine-containing block polymer, with a weight-average molecular weight of 3000. 300000; The block polymer solution is prepared by adding the block polymer to an organic solvent, or to a mixture of organic solvent and anhydrous ethanol in a volume ratio of 3-10:1, wherein the organic solvent is any one of ethyl acetate, cyclohexane, dichloromethane, acetone or methylcyclohexane.

[0013] Furthermore, in step S2, the oxygen-releasing nanoparticles include at least one of CaO2, MgO2, SrO2, NiO2, CoO2, BaO2 and ZnO2, and the nanoparticle size is 1-500 nm; the mass ratio of the oxygen-releasing nanoparticles to the block polymer is 0.01-10:10.

[0014] Furthermore, in step S3, the impregnation time is 3-30 minutes, and the curing is performed by hot air treatment at 5-75°C for 1-90 minutes.

[0015] The impregnation process of the present invention includes any one of ordinary impregnation, padding, and vacuum impregnation processes.

[0016] An antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages is prepared by any of the above-described preparation methods.

[0017] Furthermore, the coating thickness is less than 500 μm, the oxygen release is ≤3 mg / L, and the oxygen release duration is 1-216 h.

[0018] Compared with the prior art, the beneficial effects of the present invention are: This invention employs a simple impregnation method to composite water-oxygen-releasing nanoparticles with silicon-containing or fluorine-containing block polymers, gradually growing a novel functional coating on the surface of a mesh. This coating maintains the low surface energy of the block polymer while incorporating the excellent antibacterial and oxygen-releasing properties of the water-oxygen-releasing nanoparticles. Through multiple protective mechanisms, the coating of this invention exhibits excellent antifouling effects, highly efficient antibacterial capabilities, and continuous oxygen-releasing capacity, significantly improving the stability and application value of the coating in actual aquaculture environments.

[0019] Among them, the oxygen-releasing nanoparticles can spontaneously generate ROS without the need for external energy (such as ultraviolet light) to stimulate them, and can slowly hydrolyze and continuously release oxygen in weakly alkaline environments such as seawater. In other words, the coating of the present invention can release a variety of active oxygen with strong oxidizing properties, and is not limited by light conditions and low dissolved oxygen environment in water.

[0020] The coating prepared by this invention can prevent the accumulation and growth of marine microorganisms such as algae and shellfish on the netting of a fish cage, avoiding the reduction of netting pores due to microbial growth, which would affect the growth of marine aquaculture organisms. The coating thickness is less than 500 μm, so it does not affect air circulation. Its inhibitory effect on marine microorganisms is achieved by effectively intervening in the formation of biofilm in the initial stage. The coating of this invention has a killing effect on pathogenic bacteria such as Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa, with an antibacterial rate of over 99%. When in contact with water, the coating of this invention can slowly release oxygen. The released oxygen can not only promote the oxidation of pollutants, but also enhance the degradation ability of in-situ aerobic microorganisms, effectively improving water quality. At the same time, the oxygen released by the coating can significantly increase the dissolved oxygen content in the water, providing a certain oxygen supply for aerobic organisms such as fish, and promoting the growth of aerobic organisms in marine aquaculture.

[0021] The preparation steps of the coating of this invention are simple and easy to operate, which is conducive to large-scale production and application, and has good prospects. Attached Figure Description

[0022] Figure 1 The image shows the infrared spectrum of the pretreated PE mesh in Example 1.

[0023] Figure 2 The images show the SEM and EDS images of the PS-PDMS / CaO2 coating on the mesh surface in Example 1.

[0024] Figure 3 The images show the colony counts and antibacterial rates of PS-PDMS / CaO2 in Example 1, PS-PDMS in Comparative Example 1, and PE in Comparative Example 2 against Pseudomonas aeruginosa on agar plates; where a is the colony count and b is the antibacterial rate.

[0025] Figure 4Optical microscope images of the attachment of *Nyctaginosa cresticulata* to PS-PDMS / CaO2 in Example 1, PS-PDMS in Comparative Example 1, and PE in Comparative Example 2.

[0026] Figure 5 This is a graph showing the oxygen release of the PS-PDMS / CaO2 coating in artificial seawater in Example 1. Detailed Implementation

[0027] To better understand the technical content of this invention, specific embodiments are provided below to further illustrate the invention.

[0028] Unless otherwise specified, the experimental methods used in the embodiments of this invention are all conventional methods.

[0029] Unless otherwise specified, all materials and reagents used in the embodiments of this invention are commercially available.

[0030] In Example 1 of this invention, the Chinese name of APTES is 3-aminopropyltriethoxysilane, and the Chinese name of PS-PDMS is polystyrene-polydimethylsiloxane.

[0031] In Example 2 of this invention, the Chinese name of AEAPTES is N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and the Chinese name of PTFE-b-PMMA is polytetrafluoroethylene-b-polymethyl methacrylate.

[0032] In Example 3 of this invention, the Chinese name of AEAPTMS is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and the Chinese name of PS-b-FNEMA is polystyrene-b-polyfluoroethyl methacrylate.

[0033] In Example 4 of this invention, the Chinese name of AETES is 2-aminoethyltriethoxysilane, and the Chinese name of PFPE-b-PMVS is perfluoropolyether-polymethylvinylsiloxane.

[0034] In Example 5 of this invention, the Chinese name of ABTES is 4-aminobutyltriethoxysilane, and the Chinese name of PEO-PDMS is poly(ethylene oxide-polydimethylsiloxane).

[0035] In Example 6 of this invention, the Chinese name of APTMS is 3-aminopropyltrimethoxysilane, and the Chinese name of PEG-MDI-PDMS is polyethylene glycol-diisocyanate-polydimethylsiloxane.

[0036] Example 1 S1. Using polyethylene (PE) netting from nearshore aquaculture as the substrate, the surface of the netting was cleaned sequentially with distilled water, 0.1 mol / L dilute hydrochloric acid solution, and isopropanol. The netting was then dried in an oven at 40°C for 12 hours for later use. At room temperature, deionized water was added dropwise to a 5 wt% APTES solution (prepared with anhydrous ethanol) to form a hydrolysis reaction solution. The volume ratio of deionized water to 5 wt% APTES solution was 4:1. The pH of the hydrolysis reaction solution was adjusted to 5.2 ± 0.1. The dried PE netting was immersed in the hydrolysis reaction solution and reacted for 480 minutes. After the reaction, the netting was removed and allowed to dry naturally for 24 hours. It was then sealed and stored to obtain the pretreated PE netting. S2. Weigh 0.5 g of block polymer PS-PDMS with a molecular weight of 60000, add it to 50 mL of ethyl acetate, stir well to obtain a 1 wt% polymer solution, weigh 0.1 g of CaO2 nanoparticles (average diameter = 43 nm) and add them to the above polymer solution, stir well to obtain a coating solution, sonicate it at room temperature for 10 min, and continue stirring at 300 rpm for 30 min. S3. Immerse the pretreated PE mesh in the coating solution and keep it for 3 minutes. After taking it out, cure it in hot air at 40°C for 1.5 minutes. Repeat the above dip-coating-curing process 72 times to obtain the aquaculture mesh coating, which is PS-PDMS / CaO2.

[0037] Test Example 1 The pretreated PE mesh obtained in step S1 of Example 1 was subjected to infrared spectroscopy analysis. (See [link to example]) Figure 1 The infrared spectrum shows that the PE mesh modified with aminosilane APTES has four additional absorption peaks, including one at 1606.9 cm⁻¹. -1 The corresponding peak for the NH bending vibration of APTES is 1110.5 cm⁻¹. -1 Corresponding to the Si-O stretching vibration peak, 897.5 cm⁻¹ -1 The corresponding absorption peak for Si-C is 1030 cm⁻¹. -1 The Si-OC bond representing the reaction between PE and APTES indicates that aminosilane APTES has successfully modified the PE mesh.

[0038] The PS-PDMS / CaO2 coating prepared in Example 1 was characterized by SEM and EDS. (See [link to example]). Figure 2 The SEM and EDS images of the PS-PDMS / CaO2 show that the PS-PDMS / CaO2 coating forms a continuous and complete cover layer on the entire mesh surface. Furthermore, Si, C, O, and calcium (Ca) elements are uniformly and continuously distributed across the entire mesh surface.

[0039] Comparative Example 1 The difference from Example 1 is that it is not combined with CaO2 nanoparticles, but otherwise it is the same as Example 1.

[0040] Specifically, S1, using polyethylene (PE) netting from nearshore aquaculture as the substrate, the surface of the netting was cleaned sequentially with distilled water, 0.1 mol / L dilute hydrochloric acid solution, and isopropanol, and then dried in an oven at 40℃ for 12 hours for later use; at room temperature, deionized water was added dropwise to a 5 wt% APTES solution (prepared with anhydrous ethanol) to form a hydrolysis reaction solution, with a volume ratio of deionized water to 5 wt% APTES solution of 4:1, and the pH of the hydrolysis reaction solution was adjusted to 5.2±0.1. The dried PE netting was then immersed in the hydrolysis reaction solution and reacted for 480 minutes. After the reaction was completed, the netting was removed and allowed to dry naturally for 24 hours, then sealed and stored to obtain pretreated PE netting; S2. Weigh 0.5 g of block polymer PS-PDMS with a molecular weight of 60000, add it to 50 mL of ethyl acetate, stir well to obtain a 1 wt% polymer solution, and obtain a coating solution. Sonicate the solution at room temperature for 10 min, and continue stirring at 300 rpm for 30 min. S3. Immerse the pretreated PE mesh in the coating solution and keep it for 3 minutes. After taking it out, cure it in hot air at 40°C for 1.5 minutes. Repeat the above dip-coating-curing process 72 times to obtain the aquaculture mesh coating, which is PS-PDMS.

[0041] Comparative Example 2 Only polyethylene (PE) netting material from near-shore aquaculture is used.

[0042] Test Example 2 The PS-PDMS / CaO2 of Example 1, the PS-PDMS of Comparative Example 1, and the PE of Comparative Example 2 were tested for plate colony count and antibacterial rate against the marine bacterium Pseudomonas aeruginosa (P. sp.). See [link to relevant documentation]. Figure 3 As can be seen, after co-culturing with the bacterial solution for 12 hours, both the PE plate of Comparative Example 2 and the PS-PDMS plate of Comparative Example 1 had a large number of viable colonies, while the PS-PDMS / CaO2 plate of Example 1 had no obvious colonies. This indicates that the PS-PDMS / CaO2 coating of the present invention has excellent antibacterial effect, with an antibacterial rate of 99%.

[0043] The PS-PDMS / CaO2 of Example 1, the PS-PDMS of Comparative Example 1, and the PE of Comparative Example 2 were observed under an optical microscope for attachment to *Nyctaginus crescentis*. (See attached image.) Figure 4 As can be seen, the amount of *Leptochloa crescentis* adhering to the PS-PDMS / CaO2 coating in Example 1 of this invention is significantly reduced.

[0044] The PS-PDMS / CaO2 coating from Example 1 was subjected to oxygen release in artificial seawater, see [link to example]. Figure 5 As can be seen, dense oxygen bubbles still appeared on the surface of the mesh after 24 hours.

[0045] Example 2 S1. Using nylon (PA) mesh from nearshore aquaculture as the substrate, the surface of the mesh was cleaned sequentially with distilled water, 0.1 mol / L dilute hydrochloric acid solution, and isopropanol, and dried in an oven at 40℃ for 12 hours for later use. At room temperature, deionized water was added dropwise to a 30 wt% AEAPTES solution (prepared with anhydrous ethanol) to form a hydrolysis reaction solution with a volume ratio of deionized water to 30 wt% AEAPTES solution of 1:1. The pH of the hydrolysis reaction solution was adjusted to 2.1 ± 0.1. The dried PA mesh was immersed in the hydrolysis reaction solution and reacted for 3 minutes. After the reaction, the mesh was removed and allowed to dry naturally for 24 hours. It was then sealed and stored to obtain the pretreated PA mesh. S2. Weigh 2g of block polymer PTFE-b-PMMA with a molecular weight of 3000, add it to 20 mL of cyclohexane, stir until homogeneous to obtain a 10wt% polymer solution, weigh 1.8g of MgO2 nanoparticles (average diameter = 200nm) and add them to the above polymer solution, stir until homogeneous to obtain a coating solution, sonicate it at room temperature for 10min, and continue stirring at 300rpm for 50min. S3. Immerse the pretreated PA mesh in the coating solution and keep it for 30 minutes. After taking it out, cure it in hot air at 35°C for 90 minutes. Repeat the above dip-coating-curing process 3 times to obtain the aquaculture mesh coating, which is PTFE-PMMA / MgO2.

[0046] Example 3 S1. Using polyethylene terephthalate (PET) mesh from offshore aquaculture as the substrate, the surface of the mesh was cleaned sequentially with distilled water, 0.1 mol / L dilute hydrochloric acid solution, and isopropanol. It was then dried in an oven at 40℃ for 12 hours for later use. At room temperature, deionized water was added dropwise to a 10 wt% AEAPTMS solution (prepared with anhydrous ethanol) to form a hydrolysis reaction solution. The volume ratio of deionized water to 10 wt% AEAPTMS solution was 5:1. The pH of the hydrolysis reaction solution was adjusted to 4.4 ± 0.1. The dried PET mesh was immersed in the hydrolysis reaction solution and reacted for 120 minutes. After the reaction, the mesh was removed and allowed to dry naturally for 24 hours. It was then sealed and stored to obtain the pretreated PET mesh. S2. Weigh 0.02 g of block polymer PS-b-FNEMA with a molecular weight of 200,000, add it to 20 mL of a mixed solvent of cyclohexane and anhydrous ethanol (cyclohexane to anhydrous ethanol volume ratio of 5:1), stir well to obtain a 0.1 wt% polymer solution, weigh 0.01 g of SrO2 nanoparticles (average diameter = 43 nm) and add them to the above polymer solution, stir well to obtain a coating solution, sonicate it at room temperature for 10 min, and continue stirring at 300 rpm for 10 min; S3. Immerse the pretreated PET mesh in the coating solution and keep it for 5 minutes. After taking it out, cure it in hot air at 75°C for 2 minutes. Repeat the above dip-coating-curing process 60 times to obtain the aquaculture mesh coating, which is PS-FNEMA-SrO2.

[0047] Example 4 S1. Using polypropylene (PP) netting from nearshore aquaculture as the substrate, the surface of the netting was cleaned sequentially with distilled water, 0.1 mol / L dilute hydrochloric acid solution, and isopropanol. The netting was then dried in an oven at 40℃ for 12 hours for later use. At room temperature, deionized water was added dropwise to a 15 wt% AETES solution (prepared with anhydrous ethanol) to form a hydrolysis reaction solution. The volume ratio of deionized water to 15 wt% AETES solution was 3:1. The pH of the hydrolysis reaction solution was adjusted to 3.6 ± 0.1. The dried PP netting was immersed in the hydrolysis reaction solution and reacted for 30 minutes. After the reaction, the netting was removed and allowed to dry naturally for 24 hours. It was then sealed and stored to obtain pretreated PP netting. S2. Weigh 1.2g of block polymer PFPE-b-PMVS with a molecular weight of 30000, add it to 40 mL of ethyl acetate, stir well to obtain a 3wt% polymer solution, weigh 1.12g of NiO2 nanoparticles (average diameter = 43nm) and add them to the above polymer solution, stir well to obtain a coating solution, sonicate it at room temperature for 10min, and continue stirring at 300rpm for 30min. S3. Immerse the pretreated PP mesh in the coating solution and keep it for 3 minutes. After taking it out, cure it in hot air at 60°C for 1.5 minutes. Repeat the above dip-coating-curing process 48 times to obtain the aquaculture mesh coating, which is PFPE-PMVS / NiO2.

[0048] Example 5 S1. Using ultra-high molecular weight polyethylene (UHMWPE) netting from offshore aquaculture as the substrate, the surface of the netting was cleaned sequentially with distilled water, 0.1 mol / L dilute hydrochloric acid solution, and isopropanol. The netting was then dried in an oven at 40°C for 12 hours for later use. At room temperature, deionized water was added dropwise to a 0.1 wt% ABTES solution (prepared with anhydrous ethanol) to form a hydrolysis reaction solution. The volume ratio of deionized water to 0.1 wt% ABTES solution was 20:1. The pH of the hydrolysis reaction solution was adjusted to 5.9 ± 0.1. The dried UHMWPE netting was immersed in the hydrolysis reaction solution and reacted for 600 minutes. After the reaction, the netting was removed and allowed to dry naturally for 24 hours. It was then sealed and stored to obtain pretreated UHMWPE netting. S2. Weigh 2g of block polymer PEO-PDMS with a molecular weight of 10000, add it to 40 mL of ethyl acetate, stir well to obtain a 5wt% polymer solution, weigh 1.84g of CoO2 nanoparticles (average diameter = 126nm) and add them to the above polymer solution, stir well to obtain a coating solution, sonicate it at room temperature for 10 min, and continue stirring at 300 rpm for 40 min. S3. Immerse the pretreated UHMWPE mesh in the coating solution and keep it for 5 minutes. After taking it out, cure it in hot air at 45°C for 3 minutes. Repeat the above dip-coating-curing process 24 times to obtain the aquaculture mesh coating, which is PEO-PDMS / CoO2.

[0049] Example 6 S1. Using aramid mesh from offshore aquaculture as the substrate, the surface of the mesh was cleaned sequentially with distilled water, 0.1 mol / L dilute hydrochloric acid solution, and isopropanol, and dried in an oven at 40℃ for 12 hours for later use. At room temperature, deionized water was added dropwise to a 20 wt% APTMS solution (prepared with anhydrous ethanol) to form a hydrolysis reaction solution with a volume ratio of deionized water to 20 wt% APTMS solution of 2:1. The pH of the hydrolysis reaction solution was adjusted to 2.7 ± 0.1. The dried aramid mesh was immersed in the hydrolysis reaction solution and reacted for 10 minutes. After the reaction, the mesh was removed and allowed to dry naturally for 24 hours. It was then sealed and stored to obtain the pretreated PA mesh. S2. Weigh 3.5g of block polymer PEG-MDI-PDMS with a molecular weight of 6000, add it to 50 mL of ethyl acetate, stir well to obtain a 7wt% polymer solution, weigh 1.75g ​​of BaO2 nanoparticles (average diameter = 43nm) and add them to the above polymer solution, stir well to obtain a coating solution, sonicate it at room temperature for 10min, and continue stirring at 300rpm for 50min. S3. Immerse the pretreated aramid mesh in the coating solution and keep it for 5 minutes. After taking it out, cure it in hot air at 45°C for 3 minutes. Repeat the above dip-coating-curing process 36 times to obtain the aquaculture mesh coating, which is PEG-MDI-PDMS / BaO2.

[0050] The coatings prepared in Examples 2-6 above are the same as those prepared in Example 1, exhibiting excellent antifouling effects, high-efficiency antibacterial capabilities, and continuous oxygen release capabilities, which will not be elaborated upon here.

[0051] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages, characterized in that, Specific preparation methods include: S1. After cleaning and drying the surface of the aquaculture netting, immerse it in the hydrolysis reaction solution and adjust the pH value to 2-6 to carry out the reaction, and obtain the pretreated aquaculture netting. S2. Add water-release oxygen-type nanoparticles to the block polymer solution, stir evenly, and prepare an oxygen-release anti-fouling coating solution. S3. Immerse the pretreated aquaculture netting in an oxygen-releasing antifouling coating solution, remove it and cure it. Repeat the above immersion-curing cycle 3-90 times to obtain the aquaculture netting coating.

2. The method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages as described in claim 1, characterized in that, In step S1, the surface cleaning of the aquaculture netting involves sequentially cleaning the netting surface with 0.1-0.5 mol / L hydrochloric acid and isopropanol. The hydrolysis reaction solution is an aminosilane solution and deionized water with a volume ratio of 1:1-20.

3. The method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages as described in claim 1, characterized in that, In step S1, the reaction time is 1-600 min and the temperature is 20-30℃.

4. The method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages as described in claim 2, characterized in that, The concentration of the aminosilane solution is 0.1wt%-30wt%; The structural formula of the aminosilane is: Silyl (R O)3Si can be any of the following structures: 、 、 、 ； R is -CH2CH2CH2-, -CH2CH2-, -C6H4-, or cyclohexyl-C6H 11 -CH2CH2CH2OCH2CH2CH2- or -CH2CH2CH2-NH-CH2CH2-.

5. The method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages as described in claim 1, characterized in that, In step S2, the concentration of the block polymer solution is 0.1wt%-10wt%, and the block polymer includes silicon-containing block polymers or fluorine-containing block polymers with a weight-average molecular weight of 3000. 300000; The block polymer solution is prepared by adding the block polymer to an organic solvent, or to a mixture of organic solvent and anhydrous ethanol in a volume ratio of 3-10:1, wherein the organic solvent is any one of ethyl acetate, cyclohexane, dichloromethane, acetone or methylcyclohexane.

6. The method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages as described in claim 1, characterized in that, In step S2, the oxygen-releasing nanoparticles include at least one of CaO2, MgO2, SrO2, NiO2, CoO2, BaO2 and ZnO2, and the nanoparticle size is 1-500 nm; the mass ratio of the oxygen-releasing nanoparticles to the block polymer is 0.01-10:

10.

7. The method for preparing an antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages as described in claim 1, characterized in that, In step S3, the impregnation time is 3-30 min, and the curing is performed by hot air treatment at 5-75℃ for 1-90 min.

8. An antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.

9. The antibacterial, oxygen-releasing, and antifouling coating for marine aquaculture cages as described in claim 8, characterized in that, The coating thickness is less than 500 μm, the oxygen release is ≤3 mg / L, and the oxygen release duration is 1-216 h.

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