A fluorescent acrylic acid hydrogel antifouling coating and its preparation method and use

Abstract

The present invention relates to a fluorescent acrylic hydrogel antifouling coating, its preparation method, and its use. The preparation method comprises the steps of preparing a monomer mixture, synthesizing a fluorescent acrylic hydrogel antifouling coating prepolymer, and preparing the fluorescent acrylic hydrogel antifouling coating. The preparation method of the present invention produces a hydrogel antifouling coating with fluorescent properties without using a fluorescent agent, making it an environmentally friendly antifouling coating. The fluorescent acrylic hydrogel antifouling coating of the present invention exhibits excellent adhesion, anti-algae adhesion, and marine antifouling capabilities, demonstrating its potential for marine antifouling applications.

Description

Technical Field

[0001] The present invention belongs to the technical field of marine fouling control. More specifically, the present invention relates to a fluorescent acrylic hydrogel antifouling coating, a method for preparing the fluorescent acrylic hydrogel antifouling coating, and a use of the fluorescent acrylic hydrogel antifouling coating. Background Art

[0002] Fouling such as molecules, algae, and bacteria attached to the surface of equipment and ships used in marine operations can cause serious economic losses and environmental damage. Therefore, it is crucial to study marine antifouling materials that can prevent biofouling. It has been found that hydrogels, as a typical environmentally friendly antifouling material, have great application potential in the field of marine antifouling. However, due to the wide variety of fouling in the ocean, the antifouling strategy of relying solely on the original properties of hydrogels is simple and difficult to achieve broad-spectrum and long-term antifouling properties. Therefore, giving hydrogels more antifouling strategies is an effective means to enhance antifouling performance.

[0003] Inspired by the antifouling mechanism of corals, corals emit fluorescence, providing weak light for algae to photosynthesize, which can inhibit the sedimentation and adhesion of algae. Therefore, a large number of fluorescent agents are combined with various coatings to give the coatings fluorescent properties, thereby enhancing the antifouling performance of the coatings. For example, Xiong et al. described in the document "Effect of the properties of long afterglowphosphors on the antifouling performance of silicone fouling-release coating", "Progress in Organic Coatings", Vol. 170, 2022, p. 106965, that adding fluorescent agents to polydimethylsiloxane coatings gives them fluorescent properties, but the introduction of fluorescent agents makes the coating surface rougher, which is not conducive to improving the antifouling performance. Mao et al. described in the document “Advanced Marine Antifouling Hydrogels Based on 7-Amino-4-methylcoumarin Fluorescence Driven by Rare-Earth Phosphorescence”, ACS Applied Materials & Interfaces, Vol. 15, 2023, pp. 57582-57592, the preparation of a fluorescent agent that can emit light, and complexing it with polyvinyl alcohol to prepare a fluorescent polyvinyl alcohol hydrogel. However, compared with the polyvinyl alcohol hydrogel without the addition of a fluorescent agent, its water content is reduced, which has a certain effect on the antifouling effect of the hydrogel hydration layer. Therefore, the current method of using a fluorescent agent to impart fluorescent properties to the coating will destroy the original properties of the coating, and cannot achieve a better synergistic antifouling effect of the coating properties and fluorescent properties. At the same time, the combination of the above-mentioned fluorescent agent and the coating will cause the fluorescent agent in the coating to be released into the seawater, which has a certain impact on the ecological environment. In addition, the steps of preparing the fluorescent agent first in order to impart fluorescent properties to the coating are cumbersome, which is not conducive to the process of industrial application. In summary, imparting fluorescent properties to antifouling coatings without using fluorescent agents is a technical challenge in imparting fluorescent properties to antifouling coatings.

[0004] Based on this, the inventors proposed to prepare a fluorescent acrylic hydrogel antifouling coating by utilizing the aggregation effect between polymer molecules through a simple polymerization reaction without using a fluorescent agent. The fluorescent acrylic hydrogel antifouling coating can emit fluorescence at multiple wavelengths, thereby achieving synergistic antifouling properties of fluorescence and acrylic hydrogel antifouling coating. Summary of the Invention

[0005] [Technical problems to be solved]

[0006] The purpose of the present invention is to provide a fluorescent acrylic acid hydrogel antifouling coating.

[0007] Another object of the present invention is to provide a method for preparing the fluorescent acrylic hydrogel antifouling coating.

[0008] Another object of the present invention is to provide a use of the fluorescent acrylic hydrogel antifouling coating obtained by the preparation method.

[0009] [Technical solution]

[0010] The present invention is achieved through the following technical solutions.

[0011] The invention also relates to a method for preparing the fluorescent acrylic acid hydrogel antifouling coating.

[0012] The preparation steps of the preparation method are as follows:

[0013] A. Preparation of Monomer Mixture

[0014] The oily acrylate monomer, acrylic acid monomer, acrylamide monomer, amino acrylate monomer and water-based acrylate monomer are mixed uniformly in a molar ratio of 20-85:5-20:0-20:0-50:0-40, and then 0.4-2.0% of an initiator based on the total weight of the monomers is added and mixed uniformly to obtain the monomer mixture;

[0015] B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer

[0016] Under nitrogen protection, a mixed organic solvent (50-200% by weight of the total weight of the monomer mixture obtained in step A) and 5-15% by weight of the monomer mixture are added to a four-necked flask equipped with a stirrer, a condenser, and a thermometer. The reaction system is then heated to 65-95° C., maintained at this temperature for 10-30 minutes, and the remaining monomer mixture is then divided into 3-10 equal portions, with one portion added every 10-30 minutes. After the monomer mixture is added, the temperature is maintained for 1 hour, and then 0.01-0.1% by weight of the initiator is added, based on the total weight of the monomer mixture. The reaction is continued for 1-3 hours to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer.

[0017] C. Preparation of fluorescent acrylic hydrogel antifouling coating

[0018] The fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B is mixed evenly with the crosslinking agent at a temperature of 10 to 40° C., according to the crosslinking agent being 5 to 50% of the molar amount of the acrylic monomer, and then coated on a substrate for full crosslinking and drying to obtain the fluorescent acrylic hydrogel antifouling coating.

[0019] According to a preferred embodiment of the present invention, in step A, the oily acrylate monomer is one or more oily acrylate monomers selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, dodecyl methacrylate, myristyl acrylate, myristyl methacrylate, hexadecyl acrylate, octadecyl acrylate or octadecyl methacrylate.

[0020] According to another preferred embodiment of the present invention, in step A and step C, the acrylic acid monomer is one or more acrylic acid monomers selected from acrylic acid, methacrylic acid or itaconic acid.

[0021] According to another preferred embodiment of the present invention, in step A, the acrylamide monomer is one or more acrylamide monomers selected from acrylamide, N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N,N-methylenebisacrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-isopropyl acrylamide or N-tert-butyl acrylamide; the amino acrylate monomer is one or more amino acrylate monomers selected from dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or 3-(dimethylamino)propyl acrylate; and the water-based acrylate monomer is one or more water-based acrylate monomers selected from hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-(hydroxymethyl)methyl acrylate or 2-(hydroxymethyl)ethyl acrylate.

[0022] According to another preferred embodiment of the present invention, in step A, the initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, di(2-ethylhexyl) peroxydicarbonate, di-tert-butyl peroxide, dodecyl peroxide, tert-butyl perbenzoate, potassium persulfate or ammonium persulfate.

[0023] According to another preferred embodiment of the present invention, in step B, the organic solvent is one or more organic solvents selected from xylene, methyl isobutyl ketone, butyl acetate, n-butanol, ethanol or cyclohexanone.

[0024] According to another preferred embodiment of the present invention, in step B, the fluorescent acrylic hydrogel antifouling coating prepolymer has the following chemical structural formula (I):

[0025]

[0026] Where:

[0027] R1, R5 and R8 represent H or CH3;

[0028] R2 represents CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CH2CH(CH3)2, C(CH3)3, CH2CH(CH2CH3)(CH2)3CH3, (CH2)7CH3, (CH2) 11 CH3, (CH2) 13 CH3, (CH2) 15 CH3 or (CH2) 17 CH3;

[0029] R3 represents H, CH3 or CH2COOH;

[0030] R4 represents H, CH2OH, (CH2)2OH, CH2NHCOCHCH2, (CH3)2, (CH2CH3)2, CH(CH3)2 or C(CH3)3;

[0031] R6 represents CH2CH2 or CH2CH2CH2;

[0032] R7 and R 10 represents CH3 or CH2CH3;

[0033] R9 represents CH2, CH2CH2, CH2CH2CH2, CH2CHCH3 or CH2CH2CH2CH2;

[0034] a and b are positive integers, i, o, u, and n are 0 or positive integers, and i and o cannot be 0 at the same time;

[0035] Its number average molecular weight is 10,000 to 1,000,000, and its molecular weight distribution is 1.0 to 3.5.

[0036] According to another preferred embodiment of the present invention, in step C, the crosslinking agent is one or more crosslinking agents selected from aziridine crosslinker XR-100, aziridine crosslinker CX-100, aziridine crosslinker CX-300, aziridine crosslinker XC-103, acrylic acid crosslinker CX-A10 or silicone crosslinker Silicone-9301.

[0037] The invention also relates to a fluorescent acrylic acid hydrogel antifouling coating prepared by the preparation method.

[0038] The present invention also relates to the use of the fluorescent acrylic hydrogel antifouling coating in preventing the formation of marine biofouling.

[0039] The present invention will be described in more detail below.

[0040] Acrylic hydrogel is a typical environmentally friendly antifouling material. Modifications to incorporate other antifouling structures can enhance its antifouling properties, giving it significant potential for preventing the formation of marine biofouling. Therefore, the present invention introduces hydrophilic groups to construct a water-absorbing acrylic hydrogel antifouling coating. Furthermore, by constructing a different monomer composition, the polymer achieves clustered fluorescence through intermolecular interactions within the polymer without the introduction of a fluorescent agent, thus achieving a multi-faceted antifouling mechanism combining hydrophilicity and fluorescence in the acrylic hydrogel antifouling coating.

[0041] The invention relates to a method for preparing a fluorescent acrylic acid hydrogel antifouling coating.

[0042] A. Preparation of Monomer Mixture

[0043] The oily acrylate monomer, acrylic acid monomer, acrylamide monomer, amino acrylate monomer and water-based acrylate monomer are mixed uniformly in a molar ratio of 20-85:5-20:0-20:0-50:0-40, and then 0.4-2.0% of an initiator based on the total weight of the monomers is added and mixed uniformly to obtain the monomer mixture;

[0044] In the present invention, the oily acrylate monomer should be understood as an acrylate monomer that does not contain a hydrophilic group. Its main function in preparing the fluorescent acrylic hydrogel antifouling coating is to improve the solubility of the prepolymer in the organic solvent system to obtain a uniform fluorescent acrylic antifouling coating prepolymer.

[0045] The oily acrylate monomers used in the present invention are one or more oily acrylate monomers selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, octadecyl acrylate or octadecyl methacrylate, all of which are products currently sold on the market, such as the butyl acrylate sold by Tianjin Tianjiao Chemical Co., Ltd. under the trade name butyl acrylate.

[0046] The main role of acrylic monomers in the preparation of fluorescent acrylic hydrogel antifouling coatings is to provide cross-linking groups that can react with cross-linking agents, construct cross-linking networks, and promote the formation of fluorescent acrylic hydrogel antifouling coatings from fluorescent acrylic hydrogel antifouling coating prepolymers.

[0047] The acrylic acid monomers used in the present invention are one or more acrylic acid monomers selected from acrylic acid, methacrylic acid or itaconic acid, which are all products currently sold on the market, such as acrylic acid sold by Tianjin Damao Chemical Reagent Company under the trade name acrylic acid.

[0048] The main function of acrylamide monomer in the preparation of fluorescent acrylic hydrogel antifouling coating is to provide fluorescent chromophores and hydrophilic groups, so that the fluorescent acrylic hydrogel antifouling coating emits fluorescence and absorbs water to form a hydrogel.

[0049] The acrylamide monomers used in the present invention are one or more acrylamide monomers selected from acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, N,N-methylenebisacrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-isopropyl acrylamide or N-tert-butyl acrylamide, all of which are currently available on the market, for example, acrylamide sold under the trade name acrylamide by Jiangxi Jiuchang Agricultural Science and Chemical Co., Ltd.

[0050] The main function of the acrylic acid amino ester monomer in the preparation of the fluorescent acrylic hydrogel antifouling coating is to provide the fluorescent chromophore and hydrophilic group of the fluorescent acrylic hydrogel antifouling coating, thereby promoting the coating to emit fluorescence and absorb water.

[0051] The amino acrylate used in the present invention is one or more amino acrylate monomers selected from dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or 3-(dimethylamino)propyl acrylate, all of which are products currently sold on the market, such as the dimethylaminoethyl methacrylate sold by Aladdin Reagent Co., Ltd. under the trade name dimethylaminoethyl methacrylate.

[0052] In the present invention, the water-based acrylate monomer should be understood as an acrylate monomer with a hydrophilic group. Its main function in preparing the fluorescent acrylic hydrogel antifouling coating is to provide a hydrophilic group that binds to water molecules and promote the hydrogel to play the antifouling role of the hydration layer.

[0053] The aqueous acrylate monomers used in the present invention are one or more aqueous acrylate monomers selected from hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-(hydroxymethyl)methyl acrylate or 2-(hydroxymethyl)ethyl acrylate, all of which are products currently sold on the market, such as the hydroxypropyl acrylate sold by Aladdin Reagent Co., Ltd. under the trade name hydroxypropyl acrylate.

[0054] In this step, when the amounts of acrylic acid monomer, acrylamide monomer, amino acrylate monomer, and aqueous acrylate monomer are within the stated ranges, if the amount of the oily acrylate monomer is less than 20%, phase separation between the prepolymer and the solvent is likely to occur, hindering the formation of a uniform prepolymer and solvent system. If the amount of the oily acrylate monomer is greater than 85%, insufficient fluorescent chromophores and hydrophilic groups are provided, hindering the formation of a fluorescent acrylic hydrogel antifouling coating. Therefore, a reasonable amount of the oily acrylate monomer is 20-85, preferably 30-70, and more preferably 35-60.

[0055] When the amounts of the oil-based acrylate monomer, acrylamide monomer, amino acrylate monomer, and water-based acrylate monomer are within the stated ranges, if the amount of the acrylate monomer is less than 5, it will not react with the crosslinker to form a sufficient crosslinking structure, thus reducing the hydrogel properties. If the amount of the acrylate monomer is greater than 20, the prepolymer will likely gel, hindering the polymerization reaction and causing the crosslinking structure to be too tight, leading to cracking of the coating. Therefore, an appropriate amount of the acrylate monomer is 5-20, preferably 8-18, and more preferably 10-15.

[0056] When the amounts of the oily acrylate monomer, acrylic acid monomer, amino acrylate monomer, and water-based acrylate monomer are within the stated ranges, and the amount of the amino acrylate monomer is not zero, and the fluorescent acrylic hydrogel antifouling coating can emit fluorescence and absorb water, the amount of the acrylamide monomer can be zero. If the amount of the acrylamide monomer exceeds 20, gelation may occur during the polymerization reaction, hindering the smooth progress of the polymerization reaction and preventing the formation of a uniform prepolymer and solvent system. Therefore, an acrylamide monomer amount of 0 to 20 is appropriate, preferably 5 to 15, and more preferably 8 to 12.

[0057] When the amounts of the oily acrylate monomer, acrylic acid monomer, acrylamide monomer, and water-based acrylate monomer are within the stated ranges, and the amount of the acrylamide monomer is not zero, and the fluorescent acrylic hydrogel antifouling coating can emit fluorescence and bind to water molecules, the amount of the amino acrylate monomer can be zero. If the amount of the amino acrylate monomer exceeds 50, the viscosity of the prepolymer and solvent system will be too high, hindering subsequent processing and easily causing the fluorescent acrylic hydrogel antifouling coating to absorb too much water, resulting in excessive swelling and destruction. Therefore, an amount of the amino acrylate monomer of 0 to 50 is suitable, preferably 10 to 40, and more preferably 12 to 30.

[0058] When the amounts of oily acrylate monomer, acrylic acid monomer, acrylamide monomer, and amino acrylate monomer are within the stated ranges, the amount of water-based acrylate monomer can be 0, provided the fluorescent acrylic hydrogel antifouling coating can combine with sufficient water molecules to form a hydration layer and exert its antifouling effect. However, if the amount of water-based acrylate monomer exceeds 40, a large number of hydroxyl groups will form hydrogen bonds between the polymers, leading to gelation and phase separation during the polymerization reaction, which is detrimental to subsequent reactions. Therefore, a reasonable amount of water-based acrylate monomer is 0-40, preferably 10-30, and more preferably 12-25.

[0059] Preferably, the molar ratio of oily acrylate monomer, acrylic acid monomer, acrylamide monomer, amino acrylate monomer and water-based acrylate monomer is 30-70:8-18:5-15:10-40:10-30, more preferably 35-60:10-15:8-12:12-30:12-25.

[0060] According to the present invention, the main function of the initiator in preparing the fluorescent acrylic hydrogel antifouling coating is that the initiator decomposes into free radicals, thereby initiating the polymerization reaction of the monomers to generate polymers.

[0061] The initiator used in the present invention is an initiator selected from azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, di(2-ethylhexyl) peroxydicarbonate, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, potassium persulfate or ammonium persulfate, all of which are products currently sold on the market, such as the azobisisobutyronitrile sold under the trade name azobisisobutyronitrile by Tianjin Damao Chemical Reagent Factory.

[0062] The same initiator is used in the subsequent steps of preparing the fluorescent acrylic hydrogel antifouling coating of the present invention, so it will not be described in detail.

[0063] In this step, if the initiator dosage exceeds 2.0%, the molecular weight of the fluorescent acrylic hydrogel antifouling coating will be too low, which is not conducive to improving its mechanical properties. It will also result in an excessively large molecular weight dispersion coefficient, which is not conducive to process stability. If the initiator dosage is less than 0.4%, the polymerization reaction will be unstable or even non-initiated, and the molecular weight of the prepolymer may be too high, preventing the polymerization reaction from proceeding smoothly. Therefore, an initiator dosage of 0.4-2.0% is reasonable, and preferably 0.6-1.5%.

[0064] B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer

[0065] Under nitrogen protection, 50-200% of a mixed organic solvent and 5-15% of the monomer mixture obtained in step A, based on the total mass of the monomer mixture, are added to a four-necked flask equipped with a stirrer, a condenser, and a thermometer. The reaction system is then heated to 65-95° C., maintained at this temperature for 10-30 minutes, and the remaining monomer mixture is then divided into 3-10 equal portions, with one portion added every 10-30 minutes. After the monomer mixture is added, the temperature is maintained for 1 hour, and then 0.01-0.1% of the initiator, based on the total mass of the monomer mixture, is added, and the reaction is continued for 1-3 hours to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer.

[0066] The organic solvent used in this step is one or more organic solvents selected from xylene, methyl isobutyl ketone, butyl acetate, n-butanol, ethanol or cyclohexanone, which are all products currently sold on the market, such as the xylene sold by Qingdao Datang Chemical Co., Ltd. under the trade name xylene.

[0067] The mixed organic solvent used in this step should be understood to be a solvent formed by mixing one or more of the above-mentioned organic solvents in any proportion.

[0068] In this step, 50-200% of the mixed organic solvent and 5-15% of the monomer mixture are maintained at a temperature of 65° C. to 95° C. for 10-30 minutes.

[0069] When the amount of the monomer mixture is within the stated range, if the amount of the mixed organic solvent is less than 50%, the prepolymer will have high viscosity in the later stages of the reaction, resulting in an uneven reaction and hindering subsequent use. If the amount of the mixed organic solvent is greater than 200%, a large amount of volatile organic compounds will be released during later use, polluting the environment and wasting resources. Therefore, an amount of the mixed organic solvent of 50-200% is appropriate, preferably 80-150%. When the amount of the mixed organic solvent is within the stated range, if the amount of the monomer mixture is less than 5%, the initial reaction will be insufficient, hindering the stable progress of the later reaction. If the amount of the monomer mixture is greater than 15%, the reaction will be violent in the initial stage, making it difficult to control the temperature of the reaction system and posing a safety hazard. Therefore, an amount of the monomer mixture of 5-15% is appropriate, preferably 8-12%.

[0070] In this step, when the holding time is within the range, if the temperature is lower than 65°C, it is not conducive to the decomposition of the initiator and the smooth progress of the reaction; if the temperature is higher than 95°C, the reaction will be too violent, posing a safety hazard, and the distribution coefficient of the polymer molecular weight will be too large, resulting in process instability. Therefore, a temperature of 65 to 95°C is suitable, preferably 70 to 90°C. When the temperature is within the range, if the holding time is shorter than 10 minutes, the initiation reaction is insufficient, which is not conducive to the stable progress of the subsequent reaction; if the holding time is longer than 30 minutes, it is easy to cause dead-end polymerization and is not conducive to improving process efficiency. Therefore, a holding time of 10 to 30 minutes is suitable, preferably 15 to 25 minutes.

[0071] In this step, the remaining monomer mixture is divided into 3 to 10 portions, and one portion is added every 10 to 30 minutes. The main purpose is to avoid adding too much monomer mixture at a time, which cannot be dispersed into the reaction system in time. It can also avoid the reaction being too violent, causing the reaction temperature to be too high, causing safety problems and unstable reaction.

[0072] In this step, the purpose of adding initiator after keeping the temperature for 1 hour is to allow unreacted monomers in the system to participate in the polymerization reaction. The reaction is continued for 1 to 3 hours after adding initiator, its basic function is to ensure that unreacted monomers are fully reacted and polymerized.

[0073] The product obtained in this step was determined by conventional analytical methods using a Fourier transform infrared spectrometer manufactured by Bruker, Germany, to be a fluorescent acrylic hydrogel antifouling coating prepolymer, and its chemical structure is:

[0074]

[0075] Where:

[0076] R1, R3, R5 and R8 represent H or CH3;

[0077] R2 represents CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CH2CH(CH3)2, C(CH3)3, CH2CH(CH2CH3)(CH2)3CH3, (CH2)7CH3, (CH2) 11 CH3, (CH2) 13 CH3, (CH2) 15 CH3 or (CH2) 17 CH3;

[0078] R4 represents H, CH2OH, (CH2)2OH, CH2NHCOCHCH2, (CH3)2, (CH2CH3)2, CH(CH3)2 or C(CH3)3;

[0079] R6 represents CH2CH2 or CH2CH2CH2;

[0080] R7 and R 10 represents CH3 or CH2CH3;

[0081] R9 represents CH2, CH2CH2, CH2CH2CH2 or CH2CH2CH2CH2

[0082] a and b are positive integers, i, o, u, and n are 0 or positive integers, and i and o cannot be 0 at the same time;

[0083] Its number average molecular weight is 10,000 to 1,000,000, and its molecular weight distribution is 1.0 to 3.5.

[0084] C. Preparation of fluorescent acrylic hydrogel antifouling coating

[0085] The fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B is mixed evenly with the crosslinking agent at a temperature of 10 to 40° C., according to the crosslinking agent being 5 to 50% of the molar amount of the acrylic monomer, and then coated on a substrate for full crosslinking and drying to obtain the fluorescent acrylic hydrogel antifouling coating.

[0086] According to the present invention, the main function of the crosslinking agent in the preparation of the fluorescent acrylic hydrogel antifouling coating is to react with the carboxyl groups in the fluorescent acrylic hydrogel antifouling coating prepolymer to form a crosslinked network structure. When the coating comes into contact with water, the hydrophilic groups in the coating combine with water molecules and absorb water molecules, so that the water molecules fill the three-dimensional network and form a hydrogel coating with a three-dimensional structure.

[0087] The crosslinking agent used in the present invention is one or more crosslinking agents selected from aziridine crosslinker XR-100, aziridine crosslinker CX-100, aziridine crosslinker CX-300, aziridine crosslinker XC-103, acrylic acid crosslinker CX-A10 or silicone crosslinker Silicone-9301.

[0088] In this step, the crosslinking agent is used in an amount of 5-50% of the molar weight of the acrylic acid monomer. If the crosslinking agent amount exceeds 50%, uncrosslinked crosslinking agent will be present in the system, resulting in waste. If the crosslinking agent amount is less than 5%, the crosslinked structure of the hydrogel coating will be insufficient, easily destroyed after water absorption, and the mechanical properties will be poor. Therefore, a crosslinking agent amount of 5-50% is desirable, preferably 10-40%.

[0089] The fluorescent acrylic hydrogel antifouling coating prepolymer and the crosslinking agent are mixed uniformly at a temperature of 10-40°C. If the temperature of the fluorescent acrylic hydrogel antifouling coating prepolymer and the crosslinking agent is lower than 10°C, the crosslinking activity is reduced, requiring longer time to fully complete the crosslinking, which is not conducive to the efficient construction process and increases production costs. If the temperature of the fluorescent acrylic hydrogel antifouling coating prepolymer and the crosslinking agent is higher than 40°C, the activity of the crosslinking agent is increased, causing excessive bubbles to appear in the coating, affecting the coating's performance. Therefore, the ideal temperature for mixing the fluorescent acrylic hydrogel antifouling coating prepolymer and the crosslinking agent is 10-40°C, preferably 15-35°C.

[0090] The reaction vessel, electric stirring device, oil bath pot, drying device, etc. used in the present invention are all chemical equipment or devices commonly used in the field of chemical technology.

[0091] The fluorescent acrylic acid hydrogel antifouling coating prepared by the present invention was analyzed by conventional infrared spectroscopy, and the analysis results are listed in the attached Figure 1 middle.

[0092] The invention relates to a fluorescent acrylic acid hydrogel antifouling coating prepared by a preparation method.

[0093] The present invention also relates to the use of the fluorescent acrylic hydrogel antifouling coating in preventing marine biofouling. The adhesion properties of the fluorescent acrylic hydrogel antifouling coating were tested using a static bubble board; the coating's fluorescence was observed using a fluorescence microscope; its indoor antifouling performance was tested using an algae growth inhibition experiment; and its outdoor antifouling performance was tested using a live ocean hanging board experiment. Detailed test results are described in the detailed description of the embodiments.

[0094] [Beneficial Effects]

[0095] The beneficial technical effects of the present invention are:

[0096] (1) The present invention does not require the separate preparation of fluorescent compounds or fluorescent agents having a fluorescent effect, which can shorten the process flow and time.

[0097] (2) The fluorescent acrylic hydrogel antifouling coating prepared by the preparation method of the present invention can emit fluorescence in multiple excitation wavelength ranges, combining the hydrogel properties and multiple antifouling mechanisms of fluorescence.

[0098] (3) The method of imparting fluorescent properties to the hydrogel does not involve the introduction of a fluorescent agent. The original properties of the hydrogel will not be affected, such as its water absorption properties. The two antifouling mechanisms can achieve a mutually reinforcing synergistic effect, which is beneficial for preventing the formation of marine biofouling and will not cause the release of fluorescent agents into the environment and cause environmental impact. This coating exhibits good adhesion properties and has both indoor and outdoor antifouling effects.

[0099] (4) The fluorescent acrylic hydrogel antifouling coating has good film-forming properties, storage stability, and construction performance. Its preparation method is simple, and the raw materials are cheap and easily available, so it can be used for large-scale production of antifouling applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] Attachment Figure 1 is an infrared spectrum of the fluorescent acrylic hydrogel antifouling coating prepared in Example 1-5;

[0101] Attachment Figure 2 This is a fluorescent imaging image of the fluorescent acrylic hydrogel antifouling coating prepared in Example 1-5;

[0102] Attachment Figure 3 1 is a graph showing the adhesion performance test results of the fluorescent acrylic hydrogel antifouling coating prepared in Examples 1-5;

[0103] Attachment Figure 4 1. The anti-algae adhesion test results of the fluorescent acrylic hydrogel antifouling coating prepared in Example 1-5;

[0104] Attachment Figure 5 This is a picture of the actual sea hanging board results of preparing the fluorescent acrylic hydrogel antifouling coating in Example 1-5; DETAILED DESCRIPTION

[0105] The present invention is described in detail below with reference to the embodiments.

[0106] Example 1: Preparation of the fluorescent acrylic hydrogel antifouling coating of the present invention

[0107] The implementation steps of this embodiment are as follows:

[0108] A. Preparation of Monomer Mixture

[0109] Butyl acrylate oily acrylate monomer, acrylic acid acrylic acid monomer, acrylamide acrylamide monomer, dimethylaminoethyl methacrylate acrylate amino ester monomer and hydroxypropyl acrylate water-based acrylate monomer are mixed uniformly in a molar ratio of 85:20:20:50:40, and then 1.2% of initiator based on the total mass of the monomer initiator is added and mixed uniformly to obtain the monomer mixture;

[0110] B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer

[0111] Under nitrogen protection, a four-necked flask equipped with a stirrer, a condenser, and a thermometer was added with 200% of a mixed organic solvent of xylene, n-butanol, and ethanol (mass ratio 2:1.5:1) based on the total mass of the monomer mixture obtained in step A and 10% of the monomer mixture. The reaction system was then heated to 80° C.; at the same time, the temperature was maintained for 20 minutes, and the remaining monomer mixture was then divided into 7 equal parts, with one part added every 15 minutes. After the monomer mixture was added, the temperature was continued to be maintained for 1 hour, and then 0.01% of the above-mentioned initiator based on the total mass of the monomer mixture was added, and the reaction was continued for 2 hours to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer.

[0112] C. Preparation of fluorescent acrylic hydrogel antifouling coating

[0113] The fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B was mixed uniformly with the aziridine CX-100 crosslinker at a temperature of 20° C., with the crosslinker accounting for 25% of the molar amount of the acrylic monomer. The mixture was then coated on a substrate, fully crosslinked, and dried to obtain the fluorescent acrylic hydrogel antifouling coating Y1.

[0114] Conventional infrared spectroscopy analysis confirmed that the product prepared in this example is the fluorescent acrylic hydrogel antifouling coating. The results are shown in the attached Figure 1 The fluorescent microscope was used to take fluorescence images of the coating at different excitation wavelengths. The photos clearly show that the fluorescent acrylic hydrogel coating can exhibit different colors of fluorescence at different excitation wavelengths. The photos are shown in the attached Figure 2 .

[0115] Example 2: Preparation of the fluorescent acrylic hydrogel antifouling coating of the present invention

[0116] The implementation steps of this embodiment are as follows:

[0117] A. Preparation of Monomer Mixture

[0118] Butyl acrylate oily acrylate monomer, itaconic acid acrylic acid monomer and acrylamide acrylamide monomer are mixed uniformly in a molar ratio of 20:5:5, and then 2.0% of initiator based on the total mass of the monomer initiator is added and mixed uniformly to obtain the monomer mixture;

[0119] B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer

[0120] Under nitrogen protection, a four-necked flask equipped with a stirrer, a condenser, and a thermometer was added with 150% of a mixed organic solvent of xylene, n-butanol, and ethanol (mass ratio 3:1.5:1) based on the total mass of the monomer mixture obtained in step A and 5% of the monomer mixture. The reaction system was then heated to 65° C.; at the same time, the temperature was maintained for 30 minutes, and the remaining monomer mixture was then divided into 10 equal parts, with one part added every 10 minutes. After the monomer mixture was added, the temperature was continued to be maintained for 1 hour, and then 0.05% of the above-mentioned initiator based on the total mass of the monomer mixture was added, and the reaction was continued for 3 hours to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer.

[0121] C. Preparation of fluorescent acrylic hydrogel antifouling coating

[0122] The fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B was mixed uniformly with an aziridine crosslinker XR-100 at a temperature of 10° C., with the crosslinker accounting for 50% of the molar amount of the acrylic monomer. The mixture was then coated on a substrate, fully crosslinked, and dried to obtain the fluorescent acrylic hydrogel antifouling coating Y2.

[0123] Conventional infrared spectroscopy analysis confirmed that the product prepared in this example is the fluorescent acrylic hydrogel antifouling coating. The results are shown in the attached Figure 1 The fluorescent microscope was used to take fluorescence images of the coating at different excitation wavelengths. The photos clearly show that the fluorescent acrylic hydrogel coating can exhibit different colors of fluorescence at different excitation wavelengths. The photos are shown in the attached Figure 2 .

[0124] Example 3: Preparation of the fluorescent acrylic hydrogel antifouling coating of the present invention

[0125] The implementation steps of this embodiment are as follows:

[0126] A. Preparation of Monomer Mixture

[0127] n-Butyl methacrylate oily acrylate monomer, acrylic acid acrylate monomer, dimethylaminoethyl methacrylate amino acrylate monomer and hydroxyethyl acrylate water-based acrylate monomer are mixed uniformly in a molar ratio of 50:15:15:20, and then 0.4% of an initiator based on the total weight of the monomers is added and mixed uniformly to obtain the monomer mixture;

[0128] B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer

[0129] Under nitrogen protection, 120% of a mixed organic solvent, based on the total weight of the monomer mixture obtained in step A, and 15% of the monomer mixture were added to a four-necked flask equipped with a stirrer, a condenser, and a thermometer. The reaction system was then heated to 95° C., maintained at this temperature for 10 minutes, and the remaining monomer mixture was then divided into 8 equal portions, with one portion added every 12 minutes. After the monomer mixture was added, the temperature was maintained for another hour, and then 0.1% of the initiator, based on the total weight of the monomer mixture, was added. The reaction was continued for another hour to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer.

[0130] C. Preparation of fluorescent acrylic hydrogel antifouling coating

[0131] The fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B was mixed uniformly with an aziridine crosslinker XR-100 at a temperature of 40° C., with the crosslinker accounting for 15% of the molar amount of the acrylic monomer. The mixture was then coated on a substrate, fully crosslinked, and dried to obtain the fluorescent acrylic hydrogel antifouling coating Y3.

[0132] Conventional infrared spectroscopy analysis confirmed that the product prepared in this example is the fluorescent acrylic hydrogel antifouling coating. The results are shown in the attached Figure 1 The fluorescent microscope was used to take fluorescence images of the coating at different excitation wavelengths. The photos clearly show that the fluorescent acrylic hydrogel coating can exhibit different colors of fluorescence at different excitation wavelengths. The photos are shown in the attached Figure 2 .

[0133] Example 4: Preparation of the fluorescent acrylic hydrogel antifouling coating of the present invention

[0134] The implementation steps of this embodiment are as follows:

[0135] A. Preparation of Monomer Mixture

[0136] Lauryl acrylate oily acrylate monomer, acrylic acid acrylic acid monomer, acrylamide acrylamide monomer, dimethylaminoethyl methacrylate acrylate amino ester monomer and 4-hydroxybutyl acrylate water-based acrylate monomer are mixed uniformly in a molar ratio of 60:10:5:15:10, and then 1.0% of an initiator based on the total weight of the monomers is added and mixed uniformly to obtain the monomer mixture;

[0137] B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer

[0138] Under nitrogen protection, 50% of the mixed organic solvent and 12% of the monomer mixture, based on the total weight of the monomer mixture obtained in step A, were added to a four-necked flask equipped with a stirrer, a condenser, and a thermometer. The reaction system was then heated to 85° C. and maintained at this temperature for 15 minutes. The remaining monomer mixture was then divided into five equal portions and added one portion every 15 minutes. After the monomer mixture was added, the temperature was maintained for another hour. 0.06% of the initiator, based on the total weight of the monomer mixture, was then added, and the reaction was continued for 1.5 hours to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer.

[0139] C. Preparation of fluorescent acrylic hydrogel antifouling coating

[0140] The fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B was mixed uniformly with an aziridine crosslinker CX-300 at a temperature of 15° C., with the crosslinker accounting for 30% of the molar amount of the acrylic monomer. The mixture was then coated on a substrate, fully crosslinked, and dried to obtain the fluorescent acrylic hydrogel antifouling coating Y4.

[0141] Conventional infrared spectroscopy analysis confirmed that the product prepared in this example is the fluorescent acrylic hydrogel antifouling coating. The results are shown in the attached Figure 1 The fluorescent microscope was used to take fluorescence images of the coating at different excitation wavelengths. The photos clearly show that the fluorescent acrylic hydrogel coating can exhibit different colors of fluorescence at different excitation wavelengths. The photos are shown in the attached Figure 2 .

[0142] Example 5: Preparation of the fluorescent acrylic hydrogel antifouling coating of the present invention

[0143] The implementation steps of this embodiment are as follows:

[0144] A. Preparation of Monomer Mixture

[0145] n-Butyl methacrylate oily acrylate monomer, methacrylate acrylic acid monomer, N-hydroxymethyl acrylamide acrylamide monomer, dimethylamino acrylate acrylate amino ester monomer and hydroxypropyl methacrylate water-based acrylate monomer are mixed uniformly in a molar ratio of 35:18:10:20:12, and then 0.8% of an initiator based on the total weight of the monomers is added and mixed uniformly to obtain the monomer mixture;

[0146] B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer

[0147] Under nitrogen protection, a four-necked flask equipped with a stirrer, a condenser, and a thermometer was added with 180% of the mixed organic solvent, based on the total weight of the monomer mixture obtained in step A, and 0.8% of the monomer mixture. The reaction system was then heated to 75° C. and maintained at this temperature for 12 minutes. The remaining monomer mixture was then divided into three equal portions, with one portion added every 30 minutes. After the monomer mixture was added, the temperature was maintained for another hour. The initiator was then added at a level of 0.06% of the total weight of the monomer mixture, and the reaction was continued for 2.5 hours to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer.

[0148] C. Preparation of fluorescent acrylic hydrogel antifouling coating

[0149] The fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B was mixed uniformly with an acrylic crosslinker CX-A10 crosslinker at a temperature of 22° C., according to a crosslinker ratio of 5% by molar amount of the acrylic monomer. The mixture was then coated on a substrate, fully crosslinked, and dried to obtain the fluorescent acrylic hydrogel antifouling coating Y5.

[0150] Conventional infrared spectroscopy analysis confirmed that the product prepared in this example is the fluorescent acrylic hydrogel antifouling coating. The results are shown in the attached Figure 1 The fluorescent microscope was used to take fluorescence images of the coating at different excitation wavelengths. The photos clearly show that the fluorescent acrylic hydrogel coating can exhibit different colors of fluorescence at different excitation wavelengths. The photos are shown in the attached Figure 2 .

[0151] Application Example 1: Adhesion Performance Test of the Fluorescent Acrylic Hydrogel Antifouling Coating of the Present Invention The implementation of this application example is as follows:

[0152] Test samples: fluorescent acrylic hydrogel antifouling coatings Y1, Y2, Y3, Y4, and Y5 prepared in Examples 1-5;

[0153] Test substrate: Acrylonitrile / butadiene / styrene copolymer (ABS) board, ABS board size is 100×80×1mm 3 ;

[0154] Pretreatment of the test substrate: The ABS plate was evenly polished with 80-grit sandpaper, then cleaned with ethanol and purified water, and dried at room temperature to constant weight.

[0155] Coating method: Use conventional coating method

[0156] Adhesion performance test is based on: "Determination of Salt Water Resistance of Marine Coatings - Salt Water and Hot Salt Water Immersion Method" (GB / T10834-2008);

[0157] Specifically, the static seawater bubble board method was used to test the adhesion performance of the fluorescent acrylic hydrogel antifouling coating of the present invention, and the test results are listed in the attached Figure 3 middle.

[0158] By the attached Figure 3 It can be seen that the fluorescent acrylic hydrogel antifouling coatings prepared in Examples 1-5 did not fall off during the 50-day static bubble board test, and had good adhesion performance.

[0159] Application Example 2: Anti-algae adhesion performance test of the fluorescent acrylic acid hydrogel antifouling coating of the present invention The implementation method of this application example is as follows:

[0160] Test samples: fluorescent acrylic hydrogel antifouling coatings Y1, Y2, Y3, Y4, and Y5 prepared in Examples 1-5;

[0161] The non-fluorescent acrylic hydrogel coating Y01 was prepared by our laboratory according to the existing conventional preparation method;

[0162] The blank sample Y0 is a substrate without any coating on the surface;

[0163] Test substrate: Acrylonitrile / butadiene / styrene copolymer (ABS) board, ABS board size is 50×50×1mm 3 ;

[0164] Pretreatment of the test substrate: The ABS plate was evenly polished with 80-grit sandpaper, then cleaned with ethanol and purified water, and dried at room temperature to constant weight.

[0165] Coating method: Use conventional coating method;

[0166] The anti-algae adhesion test was based on the method described in the literature by Feng Kang et al., “Synthesis and antifouling evaluation of indole derivatives”, Ecotoxicology and Environmental Safety, Vol. 182, p. 109423.

[0167] The anti-algae adhesion test test steps are as follows: according to the method described in the literature on the comparison of algal cell counting methods in algal growth inhibition experiments, a nutrient solution is prepared with vitamins, sodium nitrate, sodium phosphate, sodium silicate and trace elements at a ratio of 50:100:100:100:50 (μL / 100mL seawater). This nutrient solution is then mixed with crescent-shaped Nitzschia closterium cultured to the exponential growth period to prepare an algal solution with an absorbance value of 0.09 at an ultraviolet absorption wavelength of 680nm.

[0168] A fluorescent acrylic hydrogel antifouling coating sample was placed face-up in a weighing bottle. 40 mL of the algae solution was added, and the Petri dish was placed in an incubator set at 4000 lux, a light-to-dark ratio of 14:10, and a temperature of 21°C. After 7 days, the coated sample was removed and rinsed with the algae solution in the Petri dish to remove any attached algae. Subsequently, 20 mL of nutrient solution was used to rinse all algae attached to the coating surface into another Petri dish. The absorbance of the rinse solution at 680 nm was measured using a UV spectrophotometer. Algae concentration was calculated using a standard working curve for algal growth, and the number of algae per unit area was calculated based on the coating area. Seawater was filtered through a sand-core funnel and sterilized in an autoclave (121°C).

[0169] The results of the anti-algae adhesion test are listed in the attached Figure 4 In the attached Figure 4 As can be seen, compared to the blank sample Y0 and the acrylic hydrogel coating without fluorescent properties, Y01, the fluorescent acrylic hydrogel antifouling coatings prepared in Examples 1-5 had significantly less algae attached to their surfaces. This demonstrates that the fluorescent acrylic hydrogel antifouling coatings of the present invention have excellent algae resistance and are significantly superior to acrylic hydrogel antifouling coatings without fluorescent properties.

[0170] Application Example 3: Performance Test of the Fluorescent Acrylic Hydrogel Antifouling Coating of the Present Invention on a Real Sea Board This application example is implemented as follows:

[0171] Test samples: fluorescent acrylic hydrogel antifouling coatings Y1, Y2, Y3, Y4, and Y5 prepared in Examples 1-5;

[0172] The blank sample is a control PVC substrate without any coating on the surface;

[0173] Test substrate: PVC, size 900×300×3mm 3

[0174] Pretreatment of the test substrate: The PVC board was evenly polished with 80-grit sandpaper, then cleaned with ethanol and purified water, and dried at room temperature to constant weight.

[0175] Coating method: conventional coating method;

[0176] Antifouling performance test is based on the national standard "Antifouling Paint Sample Shallow Sea Immersion Test Method" (GB / T 5370-2007);

[0177] Testing time: October 2023;

[0178] Antifouling performance test results:

[0179] The test results are shown in the attached Figure 5, where blank represents the results of the biofouling test on a control plate without any coating, and Y1, Y2, Y3, Y4 and Y5 represent the results of the biofouling adhesion test on the fluorescent acrylic hydrogel antifouling coatings prepared in Examples 1-5 for 35 days.

[0180] By the attached Figure 5 As can be seen, the blank plate had a thick biofilm and some algae attached to its surface after 35 days, while the surfaces of the Y1, Y2, Y3, Y4, and Y5 coatings were essentially free of biofilm and algae. These results fully demonstrate that the fluorescent acrylic hydrogel antifouling coating prepared in this invention has excellent antifouling capabilities in real marine environments.

Claims

1. A method for preparing a fluorescent acrylic hydrogel antifouling coating, characterized in that The preparation steps of this preparation method are as follows: A. Preparation of Monomer Mixture The oily acrylate monomer, acrylic acid monomer, acrylamide monomer, amino acrylate monomer and water-based acrylate monomer are mixed uniformly in a molar ratio of 20-85:5-20:0-20:10-50:10-40, and then 0.4-2.0% of an initiator based on the total weight of the monomers is added and mixed uniformly to obtain the monomer mixture; The oily acrylic acid ester monomer is one or more oily acrylic acid ester monomers selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, dodecyl methacrylate, myristyl acrylate, myristyl methacrylate, hexadecyl acrylate, octadecyl acrylate or octadecyl methacrylate; The acrylic acid monomer is one or more acrylic acid monomers selected from acrylic acid, methacrylic acid or itaconic acid; The acrylamide monomers are one or more acrylamide monomers selected from acrylamide, N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N,N-methylenebisacrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-isopropyl acrylamide or N-tert-butyl acrylamide; the amino acrylate monomers are one or more amino acrylate monomers selected from dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or 3-(dimethylamino)propyl acrylate; the water-based acrylate monomers are one or more water-based acrylate monomers selected from hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-(hydroxymethyl)methyl acrylate or 2-(hydroxymethyl)ethyl acrylate; B. Synthesis of fluorescent acrylic hydrogel antifouling coating prepolymer Under nitrogen protection, a four-necked flask equipped with a stirrer, a condenser, and a thermometer is added with 50-200% of a mixed organic solvent and 5-15% of the monomer mixture obtained in step A, based on the total mass of the monomer mixture. The reaction system is then heated to 65-95° C., maintained at this temperature for 10-30 minutes, and the remaining monomer mixture is then divided into 3-10 equal portions, with one portion added every 10-30 minutes. After the monomer mixture is added, the temperature is maintained for 1 hour, and then 0.01-0.1% of the initiator is added, based on the total mass of the monomer mixture, and the reaction is continued for 1-3 hours to obtain the fluorescent acrylic hydrogel antifouling coating prepolymer. C. Preparation of fluorescent acrylic hydrogel antifouling coating According to the crosslinking agent being 5-50% of the molar amount of the acrylic acid monomer, the fluorescent acrylic hydrogel antifouling coating prepolymer obtained in step B is mixed with the crosslinking agent at a temperature of 10-40° C., and then coated on a substrate, fully crosslinked, and dried to obtain the fluorescent acrylic hydrogel antifouling coating.

2. The preparation method according to claim 1, wherein In step A, the initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, di(2-ethylhexyl) peroxydicarbonate, di-tert-butyl peroxide, dodecyl peroxide, tert-butyl perbenzoate, potassium persulfate or ammonium persulfate.

3. The preparation method according to claim 1, wherein In step B, the mixed organic solvent is a plurality of organic solvents selected from xylene, methyl isobutyl ketone, butyl acetate, n-butanol, ethanol or cyclohexanone.

4. The preparation method according to claim 1, characterized in that In step B, the fluorescent acrylic hydrogel antifouling coating prepolymer has the following chemical structural formula (I): Where: R1, R5 and R8 represent H or CH3; R2 represents CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CH2CH(CH3)2, C(CH3)3, CH2CH(CH2CH3)(CH2)3CH3, (CH2)7CH3, (CH2) 11 CH3, (CH2) 13 CH3, (CH2) 15 CH3 or (CH2) 17 CH3; R3 represents H, CH3 or CH2COOH; R4 represents H, CH2OH, (CH2)2OH, CH2NHCOCHCH2, (CH3)2, (CH2CH3)2, CH(CH3)2 or C(CH3)3; R6 represents CH2CH2 or CH2CH2CH2; R7 and R 10 represents CH3 or CH2CH3; R9 represents CH2, CH2CH2, CH2CH2CH2, CH2CHCH3 or CH2CH2CH2CH2; a and b are positive integers, i and n are 0 or positive integers, and o and u are positive integers; Its number average molecular weight is 10,000 to 1,000,000, and its molecular weight distribution is 1.0 to 3.

5.

5. The preparation method according to claim 1, characterized in that In step C, the crosslinking agent is one or more crosslinking agents selected from aziridine crosslinker XR-100, aziridine crosslinker CX-100, aziridine crosslinker CX-300, aziridine crosslinker XC-103 or silicone crosslinker Silicone-9301.

6. The fluorescent acrylic hydrogel antifouling coating prepared according to the preparation method according to any one of claims 1 to 5.

7. Use of the fluorescent acrylic hydrogel antifouling coating according to claim 6 in preventing the formation of marine biofouling.

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