Polymer antifouling coating as well as preparation method and application thereof

Abstract

The invention discloses a polymer antifouling coating as well as a preparation method and application thereof. The method comprises the steps of surface cleaning, preparation of a monomer solution, addition of a cross-linking agent and a photoinitiator, degassing treatment, spraying, ultraviolet irradiation, leaching, surface modification, drying and the like. According to the preparation method, ethylene glycol diacrylate (EGDA) and 2, 2-dimethoxy-2-phenylacetylbenzophenone (DMPAP) are used as a cross-linking agent and a photoinitiator, and trifluoroethanol (TFE) and perfluorooctane (PFO) are combined as solvents, so that a polymer coating with excellent antifouling performance can be prepared. After the coating is subjected to plasma treatment and chemical modification, the adhesive force and the antifouling effect can be remarkably improved, and the coating is suitable for steel plate protection in the marine environment. The application of the novel polymer antifouling coating is not limited to improvement of the antifouling performance of marine facilities, but also can be expanded to a plurality of high-tech fields such as medical health, environmental monitoring, energy production and military defense.

Description

Technical Field

[0001] The invention relates to the technical field of functional coatings, and in particular to a polymer antifouling coating and a preparation method and application thereof. Background Art

[0002] Biofouling is one of the problems currently faced by marine shipping. On the one hand, it increases the resistance of ships to sail (mucus can increase the total resistance by 7% to 9%, and seaweed and shellfish can increase it by another 20% to 30%), and increases fuel consumption, which leads to increased operating costs and environmental pressures; on the other hand, attached organisms sail with ships around the world, posing a risk of "biological invasion" and destroying the ecological balance of the ocean. Therefore, the prevention and control of marine biofouling is imperative and of great significance. Marine antifouling coatings, as a mature and effective antifouling method, have a high market share in the field of antifouling. Traditional antifouling coatings, such as copper-based or organotin coatings, can effectively prevent biological attachment, but their toxicity has caused serious harm to the marine ecosystem, and their scope of application is increasingly restricted. In addition, over time, the antifouling effect of these coatings gradually weakens, especially in harsh marine environments, where the durability of the coatings is difficult to guarantee. Although existing polymer coating materials have made some progress in improving antifouling performance, there are still many problems. First, the preparation process of these coatings is complex, usually requiring multi-step reactions, and strict requirements on environmental and operating conditions, resulting in high production costs. Secondly, the existing antifouling coatings are still insufficient in terms of antifouling effect, especially when facing fouling by various marine organisms, and their antifouling performance is not comprehensive enough. In addition, the coatings are prone to peeling and cracking during long-term use, which reduces the protective effect.

[0003] The invention patent with the authorization publication number CN 113969081 A proposes a method for preparing a polymer-based antifouling coating based on thermal spraying technology, comprising the following steps: (1) roughening the surface of the substrate; (2) preparing a polymer capsaicin coating on the surface of the roughened substrate using thermal spraying technology; (3) remelting the polymer capsaicin coating, and obtaining the polymer-based antifouling coating based on thermal spraying technology after cooling. The preparation method is simple, the raw materials are easily available, the controllability is good, and it is convenient for large-scale production. The obtained polymer-based antifouling coating based on thermal spraying technology has a strong bonding force with the substrate, and the antifouling coating combines the advantages of polymer materials with the antifouling properties of capsaicin, and has an excellent antifouling effect. However, capsaicin is an organic molecule that may degrade in harsh environments, thereby reducing the long-term antifouling effect of the coating. In addition, the method involves multiple steps such as roughening, thermal spraying and remelting, which increases the complexity and cost of the preparation process. Another invention patent with the authorization publication number CN 117025089A proposes an amphiphilic transparent antifouling coating and its preparation method and application. Although this method takes cost issues into consideration, its adhesion may be relatively weak and needs further optimization. In practical applications, it is still necessary to find a balance between transparency and other properties. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a polymer antifouling coating and a preparation method and use thereof.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a method for preparing a polymer antifouling coating, comprising the following steps:

[0007] S1) Surface cleaning: Clean the surface of the steel plate to ensure that there is no oil stain, rust or other impurities;

[0008] S2) preparing a monomer solution: mixing a monomer solution of carboxybetaine methyl methacrylate (CBMA), perfluoropolyether urethane (PFPE) and ethylene glycol diacrylate (EGDA) in trifluoroethanol (TFE) and perfluorooctane (PFO) to form a uniform mixture;

[0009] S3) adding photoinitiator: EGDA and DMPAP added to the mixed solution, and dissolving these substances in acetonitrile;

[0010] S4) degassing: degassing the prepared mixed solution to remove oxygen in the solution;

[0011] S5) Spraying: pour the degassed solution into the container of the spray gun, and use compressed air to evenly spray the polymer solution on the surface of the steel plate;

[0012] S6) UV irradiation: in a closed, oxygen-free sealed chamber, UV light is used for irradiation for different time periods to induce polymerization reaction;

[0013] S7) leaching: After the reaction is completed, the obtained polymer coating is immersed in TFE for 30 minutes to remove unreacted monomers;

[0014] S8) Surface modification: a) Plasma treatment: Place the steel plate coated with the polymer coating in the treatment chamber of the plasma treatment equipment for a certain period of time; b) Chemical modification: Immerse the plasma-treated steel plate in a 3-mercaptopropyltrimethoxysilane (MPTMS) solution for a certain period of time, take out the steel plate, rinse it with ethanol, and remove excess MPTMS solution; c) Drying: Place the steel plate in a 60°C drying oven and dry it for 2 hours to ensure that the chemical modification layer is evenly covered and firmly adhered.

[0015] The zwitterionic structure of CBMA gives it excellent anti-biological fouling properties and can prevent the formation of various biofilms; the perfluoroalkyl chain in the PFPE molecular structure has excellent amphiphilicity, extremely low surface energy and excellent hydrophobic and oleophobic properties. At the same time, the chemical structure of PFPE is very stable, and the strength of the CF bond gives it excellent chemical corrosion resistance and thermal stability, and it can maintain excellent performance underwater and in corrosive environments. These characteristics make CBMA and PFPE important applications in antifouling coatings and can provide lasting protection.

[0016] Preferably, in step S2, the content of CBMA is 15-30wt.%, the content of PFPE is 40-60wt.%, and the content of EGDA is 10-20wt.%.

[0017] As the main anti-biological fouling component, CBMA effectively prevents the formation of biofilm through its zwitterionic structure. Controlling the CBMA content within the range of 15-30wt.% helps to ensure the uniformity of the coating and the balance of other properties while maintaining anti-fouling properties. In addition, the perfluoroalkyl chain structure of PFPE gives the coating excellent hydrophobic, oleophobic and chemical corrosion resistance. Controlling the PFPE content within 40-60wt.% can maximize the low surface energy characteristics of the coating while maintaining its chemical stability and durability. EGDA, as a cross-linking agent, helps to form a three-dimensional cross-linked network structure under ultraviolet light irradiation, enhancing the mechanical properties and stability of the coating. The right amount of EGDA ensures that the coating has sufficient strength and adhesion without being too hard and brittle.

[0018] Preferably, the step S2 is specifically as follows: S2.1) solution preparation: add TFE to a glass beaker, then add PFO with a pipette and stir; S2.2) CBMA dissolution: weigh CBMA and slowly add it to the above mixed solvent, stirring until completely dissolved; S2.3) PFPE dissolution: weigh high-viscosity PFPE and add it to the solution in which CBMA has been dissolved, stir, heat to 40°C and continue stirring and heating until completely dissolved; S2.4) EGDA addition: weigh EGDA and add it to the solution, stirring until evenly mixed; S2.5) solution post-treatment: after the mixed solution is filtered through a 0.22μm filter membrane, it is transferred to a brown glass bottle, sealed and refrigerated to prevent light oxidation or polymerization.

[0019] In a more preferred embodiment, the specific operation of step S2 is as follows: take a 100 mL glass beaker, add 50 mL of trifluoroethanol (TFE) thereto; use a glass pipette to add 20 mL of PFO, and gently stir the two to mix evenly; weigh 10 g of CBMA, slowly add CBMA to the mixed solvent of TFE and PFO, stir the solution at a speed of 300 rpm, and continue stirring for 30 minutes at room temperature (25°C) until CBMA is completely dissolved to form a uniform solution; weigh 5 g of PFPE (note that PFPE may have a higher viscosity), slowly add PFPE to the mixed solution in which CBMA has been dissolved, adjust the speed of the magnetic stirrer to 500 rpm, and place the beaker on a temperature-controlled heating plate, heat to 40°C, and continue stirring and heating for 1 hour until PFPE is completely dissolved; weigh 2 g of EGDA, add EGDA to the solution, continue stirring at 40°C and 500rpm for 30min until the solution is evenly mixed; filter the mixed solution through a 0.22μm filter membrane to remove any insoluble particles or impurities to ensure the purity of the solution; transfer the prepared monomer solution to a water-free, oxygen-free brown glass bottle, seal it, and store it in a refrigerator at 4°C, away from light to prevent photooxidation or polymerization.

[0020] The polarity of TFE and the hydrophobicity of PFO combine to form a uniform solvent system that can stably disperse the two polymers. Through slow stirring and proper temperature control, CBMA can be completely dissolved in the mixed solvent of TFE and PFO to form a uniform solution. This process ensures the uniform distribution of CBMA in the solution, avoiding local over-concentration that affects the final coating performance.

[0021] Preferably, the mass percentages of EGDA and DMPAP in step S2 are 3% and 1%, respectively.

[0022] Preferably, the degassing treatment time in step S4 is 40-60 minutes.

[0023] By degassing the mixed solution in a vacuum environment, oxygen in the solution is removed to prevent oxygen from interfering with the subsequent UV-induced polymerization reaction. Precise control of the degassing time can effectively reduce the bubbles and oxygen content in the solution, thereby improving the uniformity and mechanical properties of the coating and avoiding coating defects caused by bubbles.

[0024] Preferably, the ultraviolet light irradiation time in step S6 is 5-30 minutes.

[0025] The polymerization reaction is initiated by ultraviolet light irradiation to form a uniform polymer coating. The optimization of the irradiation time ensures the sufficiency of the polymerization reaction and guarantees the strength and stability of the coating. Too short a time may lead to incomplete polymerization, while too long a time may cause excessive cross-linking of the coating, affecting its elasticity and adhesion.

[0026] Preferably, the plasma treatment and MPTMS solution treatment time in step S8 are 5-15 min and 20-40 min respectively.

[0027] Plasma treatment is used to improve the activity of the coating surface, so that more active groups are formed on the surface, thereby improving the effect of subsequent chemical modification. Appropriate treatment time ensures that the coating surface has sufficient activity without damaging its integrity. The plasma-treated coating surface is immersed in a 3-mercaptopropyltrimethoxysilane (MPTMS) solution for chemical modification to further enhance the adhesion and durability of the coating. Controlling the treatment time ensures that MPTMS can evenly cover and firmly adhere to the coating surface without causing a decrease in surface performance due to excessive treatment. Its core innovations are mainly reflected in the following aspects:

[0028] 1. Innovation in material combination: The present invention uses a combination of carboxylic acid betaine methyl methacrylate (CBMA) and perfluoropolyether urethane (PFPE). The combination of these two materials gives the coating excellent anti-biological fouling and hydrophobic and oleophobic properties. The molecular structure of CBMA contains zwitterionic groups with adjacent positive and negative charges. This "hydration layer" structure (in an aqueous environment, the surface can quickly adsorb water molecules to form a tight water film, which prevents the attachment of biological molecules. Because many microorganisms (such as algae and bacteria) rely on proteins attached to the surface to begin growth, the hydration layer of CBMA can effectively repel the adsorption of these proteins and inhibit the formation of biofilms. Compared with commonly used hydrophobic materials, such as polydimethylsiloxane (PDMS), the hydrophilicity and electrical neutrality of CBMA make it more effective in the face of various biological fouling. Traditional hydrophobic materials often fail in water due to the accumulation of oil and dirt, while CBMA's The zwitterionic structure maintains the cleanliness and anti-pollution ability of the coating. At the same time, PFPE contains perfluoroalkyl chains, and its surface energy is very low. Almost no common liquids or dirt can firmly contact it. Moreover, its perfluoro structure has very high chemical inertness and can resist the erosion of strong acids, strong bases and various solvents, and can remain stable even in extreme environments. In addition, CBMA provides an active defense mechanism against biological contamination, preventing microbial attachment through its hydrophilic zwitterionic structure, and PFPE further prevents the adsorption of inorganic or organic pollutants through its hydrophobic and oleophobic properties. This synergistic effect forms a dual protection of "anti-pollution-anti-fouling barrier".

[0029] The zwitterionic structure of CBMA effectively prevents the formation of biofilm, while the perfluoroalkyl chain structure of PFPE has extremely low surface energy and excellent hydrophobic and oleophobic properties, as well as excellent chemical corrosion resistance and thermal stability.

[0030] 2. Innovation in preparation process: The present invention provides a novel method for preparing and surface modifying a polymer antifouling coating, including the steps of surface cleaning, preparing a monomer solution, adding a photoinitiator, degassing, spraying, ultraviolet irradiation, leaching, surface modification and drying. The combination and optimization of these steps, especially the ultraviolet irradiation to initiate the polymerization reaction and the subsequent plasma treatment and chemical modification, wherein ultraviolet irradiation can achieve uniform polymerization in a short time, avoiding the common temperature gradient and uneven polymerization problems in the thermal polymerization process, and by controlling the intensity and irradiation time of the ultraviolet light, the polymerization depth can be precisely adjusted, which helps to optimize the thickness and adhesion of the coating. In addition, ultraviolet polymerization has a higher cross-linking density, which makes the coating more excellent in mechanical properties and chemical corrosion resistance.

[0031] 3. Design of multi-layer structure: The antifouling coating disclosed in the present invention has a multi-layer structure, including a polymer layer, a plasma-treated layer and a chemically modified layer. This multi-layer structure design disperses the erosion of different environmental factors (such as water, ultraviolet rays, and chemical substances). The outer chemically modified layer is mainly in direct contact with the external environment and provides anti-pollution properties, while the inner layer serves as a supporting structure to prevent environmental stress from being transmitted to the substrate. Since each layer has different functions and effects, each layer bears the environmental load layer by layer during long-term use, and each layer is tightly combined together through different bonding methods (such as physical adsorption and chemical bonding), so that the coating can maintain a long-term protective effect during its service life.

[0032] 4. Improvement of antifouling performance: Through plasma treatment and MPTMS solution treatment, the surface activity and adhesion of the coating are significantly improved. It has long-term antifouling and anti-algae capabilities, is suitable for underwater and corrosive environments, and has broad application prospects.

[0033] In summary, the innovation of the present invention is reflected in the selection and combination of materials, the optimization of the preparation process, the design of the multilayer structure and the significant improvement of the antifouling performance, etc., which provides a new type of efficient and stable polymer antifouling coating for steel plate protection in marine environments. In particular, after the coating undergoes two processes of specific plasma treatment and chemical modification, the adhesion and antifouling effect are significantly improved.

[0034] 1. Adhesion: 1) Plasma treatment: The plasma interacts with the coating surface, which can clean the impurities on the surface and roughen the surface, increasing the physical bonding between the coating and the steel plate. The active particles in the plasma may also react chemically with the coating molecules to form chemical bonds, thereby enhancing the adhesion from a chemical level. 2) Chemical modification: By reacting with the coating through specific chemical reagents, some functional groups may be introduced on the coating surface. These functional groups can form stronger interactions with substances on the surface of the steel plate, whether covalent bonds, ionic bonds or hydrogen bonds, thereby improving adhesion.

[0035] 2. Antifouling effect: 1) Plasma treatment: Plasma can change the chemical composition and microstructure of the coating surface, making the coating surface have a lower surface energy. Low surface energy can reduce the attachment of marine organisms to the coating surface, thereby improving the antifouling effect. 2) Chemical modification: Chemical modification can construct a special chemical environment on the coating surface, such as introducing functional groups with antibacterial and anti-algae functions. These functional groups can inhibit the growth and attachment of marine organisms on the coating surface, effectively improving the antifouling effect. Due to the improvement in adhesion and antifouling effect, the coating is very suitable for steel plate protection in marine environments, which can extend the service life of steel plates in marine environments and reduce maintenance costs.

[0036] In a second aspect, the present invention provides an antifouling coating obtained by the above preparation and modification method.

[0037] In a third aspect, the present invention can also provide a use of the antifouling coating as described above, such as antifouling applications in ships and marine engineering, medical equipment, flexible electronic devices, biomedical equipment, environmental monitoring equipment, and energy facilities.

[0038] The advantages and beneficial effects of the present invention are as follows:

[0039] 1. In a preparation method of a polymer antifouling coating disclosed in the present invention, the combination of CBMA and PFPE gives the coating excellent anti-biological contamination and hydrophobic and oleophobic properties, which can effectively prevent the formation of biofilm and the adhesion of dirt, and extend the service life of the coating.

[0040] 2. A novel polymer antifouling coating disclosed in the present invention has a multi-layer structure, namely, a polymer layer, a plasma-treated layer, and a chemically modified layer, wherein the interface between the plasma-treated layer and the chemically modified layer is bonded by a strong chemical bond to form a multi-layer structure with high stability. Through the interaction between the layers, the corrosion of the substrate and the base coating by environmental factors is effectively prevented, thereby further improving the durability, stability and comprehensive performance of the coating in extreme environments, and extending the service life of the coating.

[0041] 3. In the preparation method of a polymer antifouling coating disclosed in the present invention, the surface activity and adhesion of the coating are significantly improved through plasma treatment and MPTMS solution treatment, and the coating has long-lasting antifouling and anti-algae capabilities, and is suitable for underwater and corrosive environments. The new polymer antifouling coating has broad application prospects in many fields due to its excellent antifouling performance and environmental friendliness. The following are several potential application directions:

[0042] 1) Marine antifouling: Ships, platforms, pipelines and other facilities in the marine environment are extremely vulnerable to damage by marine organisms, resulting in increased fuel consumption, reduced service life and increased safety risks. The new polymer antifouling coating can effectively prevent the attachment of marine organisms, reduce maintenance costs, and extend the service life of facilities.

[0043] 2) Medical devices: In the medical field, antifouling coatings can be applied to medical devices and implants to reduce the attachment of bacteria and other microorganisms, reduce hospital infection rates, and improve patient safety.

[0044] 3) Flexible electronic devices: With the development of flexible electronic devices, higher requirements are placed on the flexibility and wear resistance of coatings. The high strength and toughness of the new polymer antifouling coating makes it suitable for these devices to provide additional protection.

[0045] 4) Biomedical devices: In the biomedical field, antifouling coatings can be used in wound dressings and biomedical sensors to prevent biological contamination and improve the performance and reliability of the equipment.

[0046] 5) Environmental Monitoring Equipment: Marine sensors and other environmental monitoring equipment can also benefit from anti-fouling coatings to keep the surface of the equipment clean and ensure the accuracy of data collection.

[0047] 6) Energy facilities: The surface coating of energy facilities such as offshore wind farms and nuclear power plants can adopt new polymer antifouling technology to reduce maintenance workload and improve energy efficiency.

[0048] 7) Military applications: Military equipment such as warships and submarines also require anti-fouling coatings to reduce navigation resistance, reduce noise and improve concealment.

[0049] 8) Marine resource development: In emerging fields such as marine ranching and deep-sea mining, antifouling coatings help protect equipment from erosion and biological adhesion in the marine environment.

[0050] In summary, the application of new polymer antifouling coatings is not limited to improving the antifouling performance of marine facilities, but also extends to many high-tech fields such as medical health, environmental monitoring, energy production and military defense. With the deepening of research and the maturity of technology, these coatings are expected to achieve more extensive commercial applications in the future. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 The colony distribution diagrams of bacteria adhered to the surfaces of different samples after dilution culture, including: (a) Example 5; (b) Example 4; (c) bare plate.

[0052] Figure 2 The adhesion of microalgae on the surfaces of different samples, including: (a) bare plate; (b) Example 4; (c) Example 5. DETAILED DESCRIPTION

[0053] The technical solution of the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0054] A method for preparing a polymer antifouling coating comprises the following steps:

[0055] Step S1) Surface cleaning: Clean the surface of the steel plate to ensure that there is no oil stain, rust or other impurities;

[0056] Step S2) preparing a monomer solution: mixing a monomer solution of carboxylic acid betaine methyl methacrylate (CBMA), perfluoropolyether urethane (PFPE) and ethylene glycol diacrylate (EGDA) in trifluoroethanol (TFE) and perfluorooctane (PFO) to form a uniform mixture; in step S2, the content of CBMA is 15-30wt.%, the content of PFPE is 40-60wt.%, and the content of EGDA is 10-20wt.%. The specific operation of step S2 is as follows: take a 100mL glass beaker, add 50mL of trifluoroethanol (TFE) thereto; use a glass pipette to add 20mL of PFO, and gently stir and mix the two; weigh 10g of CBMA, slowly add CBMA to the mixed solvent of TFE and PFO, stir the solution at a speed of 300rpm, and continue stirring for 30min at room temperature (25°C) until CBMA is completely dissolved to form a uniform solution; weigh 5g of PFPE (note that PFPE may have a higher viscosity), slowly add PFPE to the mixed solution in which CBMA has been dissolved, adjust the speed of the magnetic stirrer to 500rpm, and place the beaker on a temperature-controlled heating plate, heat to 40°C, continue stirring and heating for 1h, until PFPE is completely dissolved; weigh 2g EGDA, add EGDA to the solution, continue stirring at 40°C and 500rpm for 30min until the solution is evenly mixed; filter the mixed solution through a 0.22μm filter membrane to remove any insoluble particles or impurities to ensure the purity of the solution; transfer the prepared monomer solution to an anhydrous, oxygen-free brown glass bottle, seal it, and store it in a refrigerator at 4°C, away from light to prevent photooxidation or polymerization. The mass percentages of EGDA and DMPAP in step S2 are 3% and 1%, respectively.

[0057] Step S3) adding photoinitiator: adding EGDA and DMPAP to the mixed solution, and dissolving these substances in acetonitrile;

[0058] Step S4) Degassing: The prepared mixed solution is degassed to remove oxygen in the solution. The degassing time in step S4 is 40-60 minutes.

[0059] Step S5) spraying: pour the degassed solution into the container of the spray gun, and use compressed air to evenly spray the polymer solution on the surface of the steel plate;

[0060] Step S6) UV irradiation: In a closed, oxygen-free sealed chamber, UV irradiation is performed for different time periods to initiate a polymerization reaction; the UV irradiation time in step S6 is 5-30 min.

[0061] Step S7) Leaching: After the reaction is completed, the obtained polymer coating is immersed in TFE for 30 minutes to remove unreacted monomers;

[0062] Step S8) Surface modification: a) Plasma treatment: Place the steel plate coated with the polymer coating in the treatment chamber of the plasma treatment equipment for a certain period of time; b) Chemical modification: Immerse the plasma-treated steel plate in a 3-mercaptopropyltrimethoxysilane (MPTMS) solution for a certain period of time, remove the steel plate, rinse with ethanol, and remove excess MPTMS solution; c) Drying: Place the steel plate in a 60°C drying oven for 2 hours to ensure that the chemical modification layer is evenly covered and firmly attached. The plasma treatment and MPTMS solution treatment times in step S8 are 5-15 minutes and 20-40 minutes, respectively.

[0063] The anti-fouling coating was tested for its antibacterial adhesion performance. The number of colonies adhered to each sample was calculated and then the antibacterial adhesion rate of the coating was calculated using a formula. The anti-diatom adhesion performance test was carried out by measuring the absorbance of chlorophyll using a UV-spectrophotometer. The chlorophyll content on the coating surface was calculated based on the absorbance using a formula, and then the anti-diatom adhesion rate of the coating surface was obtained.

[0064] Example 1

[0065] S1: Surface cleaning: Clean the surface of the steel plate to ensure that there is no oil, rust or other impurities.

[0066] S2: Preparation of monomer solution:

[0067] (S2.1) Take a 100 mL glass beaker and add 50 mL of trifluoroethanol (TFE);

[0068] (S2.2) Add 20 mL of perfluorooctane (PFO) and gently stir to mix;

[0069] (S2.3) Add 10 g of carboxybetaine methyl methacrylate (CBMA) and stir at 300 rpm for 30 min until completely dissolved;

[0070] (S2.4) Add 5 g of perfluoropolyether urethane (PFPE) and stir at 40 °C and 500 rpm for 1 h until it is completely dissolved;

[0071] (S2.5) Add 2 g of ethylene glycol diacrylate (EGDA) and continue stirring for 30 min;

[0072] (S2.6) Filter the solution, transfer it into a water-free, oxygen-free brown glass bottle, and store it at 4°C away from light.

[0073] S3: Adding photoinitiator: Add 3 wt.% EGDA and 1 wt.% DMPAP to the mixed solution and dissolve them in acetonitrile.

[0074] S4: Degassing: Degas the mixed solution for 50 min.

[0075] S5: Spraying: Pour the degassed solution into the spray gun container and use compressed air to spray it evenly on the surface of the steel plate.

[0076] S6: UV irradiation: In a closed, oxygen-free sealed room, use UV irradiation for 20 minutes.

[0077] S7: Leaching: Soak the polymer coating in TFE for 30 min.

[0078] S8: Surface modification:

[0079] (S8.1) plasma treatment for 10 min;

[0080] (S8.2) Immerse the steel plate in 3-mercaptopropyltrimethoxysilane (MPTMS) solution for 30 min and rinse with ethanol;

[0081] (S8.3) Dry in a drying oven at 60°C for 2 h to obtain an antifouling coating I.

[0082] Example 2

[0083] S1: Surface cleaning: same as Example 1.

[0084] S2: Prepare a monomer solution: CBMA content: 20 wt.%, PFPE content: 50 wt.%, EGDA content: 15 wt.%.

[0085] S3: Adding photoinitiator: Same as Example 1.

[0086] S4: Degassing: Degassing for 45 min.

[0087] S5: Spraying: Same as Example 1.

[0088] S6: UV irradiation: irradiation for 25 min.

[0089] S7: Leaching: Same as Example 1.

[0090] S8: Surface modification:

[0091] (S8.1) plasma treatment for 12 min;

[0092] (S8.2) MPTMS solution treatment for 25 min;

[0093] (S8.3) Dry for 2 h to obtain antifouling coating II.

[0094] Example 3

[0095] S1: Surface cleaning: same as Example 1.

[0096] S2: Prepare a monomer solution: CBMA content: 25 wt.%, PFPE content: 45 wt.%, EGDA content: 10 wt.%.

[0097] S3: Adding photoinitiator: Same as Example 1.

[0098] S4: Degassing: Degassing for 50 min.

[0099] S5: Spraying: Same as Example 1.

[0100] S6: UV irradiation: irradiation for 30 minutes.

[0101] S7: Leaching: Same as Example 1

[0102] S8: Surface modification:

[0103] (S8.1) plasma treatment for 15 min;

[0104] (S8.2) MPTMS solution treatment for 20 min;

[0105] (S8.3) Dry for 2 h to obtain an antifouling coating III.

[0106] Example 4

[0107] S1: Surface cleaning: same as Example 1.

[0108] S2: Prepare a monomer solution: CBMA content 30wt.%, PFPE content 40wt.%, EGDA content 15wt.%. S3: Add photoinitiator: Same as Example 1.

[0109] S4: Degassing: Degassing for 55 min.

[0110] S5: Spraying: Same as Example 1.

[0111] S6: UV irradiation: irradiation for 15 minutes.

[0112] S7: Leaching: Same as Example 1.

[0113] S8: Surface modification:

[0114] (S8.1) plasma treatment for 10 min;

[0115] (S8.2) MPTMS solution treatment for 35 min;

[0116] (S8.3) Dry for 2 h to obtain antifouling coating IV.

[0117] Example 5

[0118] S1: Surface cleaning: same as Example 1.

[0119] S2: Prepare a monomer solution: CBMA content 15wt.%, PFPE content 60wt.%, EGDA content 10wt.%. S3: Add photoinitiator: Same as Example 1.

[0120] S4: Degassing: Degassing for 60 min.

[0121] S5: Spraying: Same as Example 1.

[0122] S6: UV irradiation: irradiation for 10 min.

[0123] S7: Leaching: Same as Example 1.

[0124] S8: Surface modification:

[0125] (S8.1) plasma treatment for 5 min;

[0126] (S8.2) MPTMS solution treatment for 40 min;

[0127] (S8.3) Dry for 2 h to obtain an antifouling coating V.

[0128] Example 6

[0129] S1: Surface cleaning: same as Example 1.

[0130] S2: Prepare a monomer solution: CBMA content 18wt.%, PFPE content 52wt.%, EGDA content 12wt.%. S3: Add photoinitiator: Same as Example 1.

[0131] S4: Degassing: Degassing for 48 minutes.

[0132] S5: Spraying: Same as Example 1.

[0133] S6: UV irradiation: irradiation for 22 minutes.

[0134] S7: Leaching: Same as Example 1.

[0135] S8: Surface modification:

[0136] (S8.1) plasma treatment for 8 min;

[0137] (S8.2) MPTMS solution treatment for 28 min;

[0138] (S8.3) Dry for 2 h to obtain an antifouling coating VI.

[0139] Example 7

[0140] S1: Surface cleaning: same as Example 1.

[0141] S2: Prepare a monomer solution: CBMA content 22wt.%, PFPE content 48wt.%, EGDA content 14wt.%. S3: Add photoinitiator: Same as Example 1.

[0142] S4: Degassing: Degassing for 52 min.

[0143] S5: Spraying: Same as Example 1.

[0144] S6: UV irradiation: irradiation for 18 minutes.

[0145] S7: Leaching: Same as Example 1.

[0146] S8: Surface modification:

[0147] (S8.1) plasma treatment for 12 min;

[0148] (S8.2) MPTMS solution treatment for 32 min;

[0149] (S8.3) Dry for 2 h to obtain antifouling coating VII.

[0150] Example 8

[0151] S1: Surface cleaning: same as Example 1.

[0152] S2: Prepare a monomer solution: CBMA content: 28 wt.%, PFPE content: 42 wt.%, EGDA content: 13 wt.%.

[0153] S3: Adding photoinitiator: Same as Example 1.

[0154] S4: Degassing: Degassing for 54 min.

[0155] S5: Spraying: Same as Example 1.

[0156] S6: UV irradiation: irradiation for 20 minutes.

[0157] S7: Leaching: Same as Example 1.

[0158] S8: Surface modification:

[0159] (S8.1) plasma treatment for 14 min;

[0160] (S8.2) MPTMS solution treatment for 30 min;

[0161] (S8.3) Dry for 2 h to obtain antifouling coating VIII.

[0162] According to the test method described above, the performance test of the antifouling coating prepared in each embodiment is carried out, and the performance test results are shown in Table 1. From the performance test results, it can be concluded that the antibacterial adhesion rate and anti-diatom adhesion rate of the antifouling coating V in Example 5 are the highest, of which the high antibacterial adhesion rate of 89% is mainly attributed to the synergistic effect of CBMA and PFPE. CBMA provides antibacterial function, while the low surface energy of PFPE reduces the adhesion of bacteria; the high anti-diatom adhesion rate of 93% is due to the combined effect of the high content of PFPE and the surface modification treatment. The low surface energy of PFPE and the presence of the chemically modified layer make it difficult for diatoms to adhere to the coating surface. Figure 1 It can be clearly seen that the number of colonies adhering to the surface of Example 5 is significantly reduced, indicating that its antibacterial effect is better, while the antibacterial effect of Example 4 is also good, but slightly inferior to that of Example 5. The bare board shows a large number of colonies and almost no antibacterial performance. Figure 2 The adhesion of microalgae on the surfaces of different samples is shown. A large amount of microalgae adhere to the surface of the bare board, and there is almost no anti-fouling effect. Although the surface of Example 4 can partially inhibit the adhesion of microalgae, a certain amount of microalgae adhesion can still be observed. In contrast, the coating of Example 5 has almost no microalgae adhesion, which further confirms its excellent anti-diatom performance, indicating that the coating has excellent comprehensive performance in anti-fouling performance and is suitable for application in environments that require long-term resistance to microorganisms and microalgae adhesion, such as ships, marine structures, etc.

[0163] The antifouling coatings prepared by this method have good surface morphology. After testing, their antibacterial adhesion rate is above 85%, and their anti-diatom adhesion rate is about 90%. No corrosion occurs or the corrosion area is less than 3% during the neutral salt spray resistance test for 2000 hours. They have excellent antifouling and anti-corrosion properties (in the test results of salt spray resistance, "excellent" means no corrosion occurs, and "good" means the corrosion area is less than 3%).

[0164] Table 1 Coating performance test results

[0165]

Claims

1. A method for preparing a polymer antifouling coating, characterized in that: The steps include: S1) Surface cleaning: Clean the surface of the steel plate to ensure that there is no oil stain, rust or other impurities; S2) preparing a monomer solution: mixing a monomer solution of carboxylic acid betaine methyl methacrylate, perfluoropolyether urethane and ethylene glycol diacrylate in trifluoroethanol and perfluorooctane to form a uniform mixture; S3) adding a photoinitiator: adding ethylene glycol diacrylate and 2,2-dimethoxy-2-phenylacetophenone to the mixed solution, and dissolving these substances in acetonitrile; S4) degassing: degassing the prepared mixed solution to remove oxygen in the solution; S5) Spraying: pour the degassed solution into the container of the spray gun, and use compressed air to evenly spray the polymer solution on the surface of the steel plate; S6) UV irradiation: in a closed, oxygen-free sealed chamber, UV light is used for irradiation for different time periods to induce polymerization reaction; S7) leaching: after the reaction is completed, the obtained polymer coating is immersed in trifluoroethanol to remove unreacted monomers; S8) Surface modification: a) Plasma treatment: The steel plate coated with the polymer coating is subjected to plasma treatment for a certain period of time; b) Chemical modification: The steel plate after plasma treatment is treated with a modification solution for a certain period of time, and after the steel plate is taken out, the excess modification solution is rinsed off; c) Drying: The steel plate is dried to ensure that the chemical modification layer is evenly covered and firmly attached.

2. The preparation method according to claim 1, characterized in that: In the surface modification of step S8), the chemical modification solution in b) is 3-mercaptopropyltrimethoxysilane, and the cleaning solution is ethanol; the drying temperature in c) is 60-65° C., and the drying time is 2-2.25 h.

3. The preparation method according to claim 2, characterized in that: In the step S2, the content of carboxylic acid betaine methyl methacrylate is 15-30 wt.%, the content of perfluoropolyether urethane is 40-60 wt.%, and the content of ethylene glycol diacrylate is 10-20 wt.%.

4. The preparation method according to claim 3, characterized in that: The step S2 is specifically as follows: S2.1) Solution preparation: Add trifluoroethanol to a glass beaker, then add perfluorooctane with a pipette and stir well; S2.2) Dissolution of carboxylic acid betaine methyl methacrylate: Weigh carboxylic acid betaine methyl methacrylate and slowly add it to the above mixed solvent, stirring until completely dissolved; S2.3) Dissolution of perfluoropolyether urethane: Weigh high-viscosity perfluoropolyether urethane and add it to the solution in which carboxylic acid betaine methyl methacrylate has been dissolved, stir, heat to 40°C and continue stirring and heating until completely dissolved; S2.4) Addition of ethylene glycol diacrylate: Weigh ethylene glycol diacrylate and add it to the solution, stirring until evenly mixed; S2.5) Solution post-treatment: After the mixed solution is filtered through a 0.22μm filter membrane, it is transferred to a brown glass bottle, sealed and refrigerated and stored away from light to prevent photo-oxidation or polymerization.

5. The preparation method according to claim 4, characterized in that: The mass percentages of ethylene glycol diacrylate and 2,2-dimethoxy-2-phenylacetophenone in step S2 are 2-5% and 0.5-1.5% respectively.

6. The preparation method according to claim 5, characterized in that: The degassing treatment time in step S4 is 40-60 minutes.

7. The preparation method according to claim 6, characterized in that: The ultraviolet light irradiation time in step S6 is 5-30 minutes.

8. The preparation method according to claim 7, characterized in that: The plasma treatment and 3-mercaptopropyltrimethoxysilane solution treatment in step S8 last for 5-15 minutes and 20-40 minutes respectively.

9. An antifouling coating obtained by the preparation method according to claim 8, characterized in that: The components of the antifouling coating are as follows: carboxylic acid betaine methyl methacrylate: 15-30wt.%; perfluoropolyether urethane: 40-60wt.%; ethylene glycol diacrylate: 10-20wt.%; the mass percentages of ethylene glycol diacrylate and 2,2-dimethoxy-2-phenylacetophenone are 2-5% and 0.5-1.5% respectively. The antifouling coating has excellent corrosion resistance and antifouling performance.

10. Use of the antifouling coating according to claim 9, characterized in that: Anti-fouling applications in shipbuilding and marine engineering, medical devices, flexible electronic devices, biomedical equipment, environmental monitoring equipment, and energy facilities.

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