Acrylic acid metal salt resin containing coumarin structure as well as preparation method and application of acrylic acid metal salt resin

Abstract

The invention relates to acrylic acid metal salt resin containing a coumarin structure as well as a preparation method and application of the acrylic acid metal salt resin. The acrylic acid metal salt resin has the following chemical structural formula (I): # imgabs0 #, the acrylic acid metal salt resin containing the coumarin structure has the antifouling effect of integrating antibacterial, fluorescent antifouling and self-polishing antifouling functions, the antifouling performance of the resin is enhanced, and a real sea antifouling test result shows that the coating has the static real sea antifouling effect for more than 110 days. The anti-fouling resin is environment-friendly, the preparation process is simple, and the raw materials are easy to obtain.

Description

[Technical field]

[0001] The present invention belongs to the technical field of functional polymer materials. More specifically, the present invention relates to a metal acrylate resin containing a coumarin structure, a preparation method of the metal acrylate resin, and a use of the metal acrylate resin. [Background technology]

[0002] Instruments and equipment in the marine environment are inevitably faced with the trouble of marine biofouling. Marine biofouling not only brings economic losses, but also threatens life. The prevention and control of biofouling has become a marine environmental issue of common concern to all countries. At present, the application of antifouling coatings is the most economical and effective method to prevent marine biofouling. Among them, self-polishing antifouling coatings are widely used at home and abroad due to their strong surface self-renewal ability, long antifouling period and high antifouling performance. The representative tributyltin (TBT) self-polishing coating in the 19th century was widely used on ships due to its excellent antifouling performance. However, since tributyltin compounds are not friendly to the marine environment, the International Maritime Organization and the Marine Environment Protection Committee have announced a ban on the use of tributyltin compounds in the marine environment before 2008. At the same time, many countries strictly monitor the harm of antifouling coatings to the marine environment. For this reason, the development of environmentally friendly antifouling coatings has become a research focus, and countries have proposed the development of environmentally friendly Wuxi self-polishing antifouling coatings.

[0003] With the continuous enhancement of environmental awareness, the application of natural antifouling agents in the field of marine antifouling has received more and more attention. Natural antifouling agents usually come from natural resources such as plants, seaweed and microorganisms, and have the characteristics of biocompatibility, non-toxicity / low toxicity and environmental protection, which can effectively reduce the impact on the marine ecosystem. However, although natural antifouling agents have good antifouling properties, their large-scale application is limited due to the complexity of their separation and extraction processes. Therefore, how to synthesize marine antifouling coatings containing environmentally friendly antifouling agents by simple and easy methods has become a problem that technicians in this field urgently need to solve.

[0004] Aiming at the technical defects of current environmentally friendly marine antifouling coatings, the inventors have finally completed the present invention through a large number of experimental studies and analytical summaries based on the summary of the prior art. [Summary of the invention]

[0005] The purpose of the present invention is to provide a metal acrylate resin containing a coumarin structure.

[0006] Another object of the present invention is to provide a method for preparing the coumarin structure-containing acrylic acid metal salt resin.

[0007] Another object of the present invention is to provide the use of the coumarin structure-containing acrylic acid metal salt resin.

[0008] The present invention is achieved through the following technical solutions.

[0009] The invention relates to an acrylic acid metal salt resin containing a coumarin structure.

[0010] The metal acrylate resin has the following chemical structural formula (I):

[0011]

[0012] In the formula: R1 is H, R2 is H; or R1 is CH3, R2 is H; or R1 is H, R2 is Cl;

[0013] R3 is H, -OCH3, -OH or -Et2N;

[0014] X is Zn 2+ or Cu 2+ Metal ions;

[0015] n is a positive integer; m is 0 or a positive integer; x is 0 or a positive integer; y is a positive integer;

[0016] The number average molecular weight of the above-mentioned metal acrylate resin containing coumarin structure is 2000-60000, and its molecular weight distribution is 1.0-2.5.

[0017] The invention also relates to a method for preparing the acrylic acid metal salt resin containing the coumarin structure.

[0018] The preparation steps of the preparation method are as follows:

[0019] A. Preparation of hydroxycoumarin compounds

[0020] In a round-bottom flask, resorcinol or 2-methylresorcinol and ethyl acetoacetate are stirred and dissolved in a molar ratio of 1:0.8-2.0 to obtain a mixture solution, and then ZrCl4 is slowly added to the mixture solution according to 15%-25% of their total molar amount, and the mixture is vigorously stirred and reacted for 20-40 minutes at room temperature, and then ice water is slowly added to precipitate, and the precipitate is filtered by suction, and the obtained filter cake is recrystallized in an ethanol solution with a concentration of more than 90% by volume, filtered, and dried to obtain 7-hydroxy-4-methylcoumarin or 7-hydroxy-4,8-dimethylcoumarin;

[0021] B. Preparation of coumarin compounds containing C=C double bond structure

[0022] The hydroxy coumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask in a molar ratio of 30-40:40-55:40-55:0.7-1.0, and then acetone solvent is added to the reactants in a ratio of 10-20:150-200 of the total mass of the reactants in grams to acetone in milliliters, and then heated under reflux at a temperature of 50°C to 70°C for 15-24h, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 40°C to 50°C and a vacuum degree of -0.07 to -0.1kPa to obtain a coumarin compound containing a C=C double bond structure;

[0023] C. Preparation of coumarin acid compounds

[0024] The salicylaldehyde compound and the Michaelis acid are added to a round-bottom flask in a molar ratio of 20:20-25, and then 350%-500% of a water solvent based on the total mass of the salicylaldehyde compound and the Michaelis acid is added, stirred and mixed evenly, and then reacted at a temperature of 100-120° C. for 2-6 hours, filtered, and dried to obtain the coumarin acid compound;

[0025] D. Synthesis of acrylic prepolymer containing coumarin structure

[0026] Ethyl acrylate, butyl acrylate, acrylic acid and a coumarin compound containing a C=C double bond structure are mixed uniformly in a molar ratio of 6:2:2:0.05-2.5 to obtain a monomer mixture, and then 0.5%-3.2% of an initiator is added based on the weight of the monomer mixture, and the mixture is mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 100-230% of a solvent, 10%-20% of a monomer mixture containing an initiator and 0.3%-2.0% of a chain transfer agent are added based on the weight of the monomer mixture, and the mixture is stirred uniformly, and the reaction temperature of the reaction mixture is controlled at 75°C-110°C, and then the remaining monomer mixture containing an initiator is evenly divided into 9-15 portions, and one portion is added every 10-20 minutes, and the mixture is reacted for 4-8 hours to obtain a viscous acrylic acid prepolymer containing a coumarin structure;

[0027] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0028] The coumarin structure-containing acrylic prepolymer obtained in step D is cooled to a temperature below 70° C., and then a metal oxide or hydroxide and a coumarin acid compound obtained in step C are added, wherein the added amounts are 0.8 to 1.5 times the molar amount of acrylic acid in the coumarin structure-containing acrylic prepolymer, and the molar ratio of the metal oxide or hydroxide to the coumarin acid compound is 1:0.8 to 1.5. The mixture is mixed evenly, and then 150% to 200% of a solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 100° C. to 130° C. for 3 to 5 days to obtain a coumarin structure-containing acrylic metal salt resin.

[0029] According to a preferred embodiment of the present invention, in step A, 4-chlororesorcinol and ethyl acetoacetate are stirred and mixed in a molar ratio of 1:0.8-2.0 to obtain a mixture solution. At the same time, 100%-200% concentrated sulfuric acid based on the total volume of the mixture solution is cooled to a temperature of -10°C-5°C using an ice-salt bath, and the mixture solution is added to the concentrated sulfuric acid under stirring for reaction for 3-7h, and then ice water is slowly added under stirring to precipitate, and the filter cake is dissolved in a NaOH solution with a concentration of 5%-10% by weight, and the obtained solution is then extracted 2-5 times with ethyl acetate at a volume ratio of 1:1.5-3.0 between the solution and ethyl acetate, and the obtained aqueous phase is acidified to pH=5 with sulfuric acid with a concentration of 10%-20% by weight under ice bath cooling, and the precipitate is precipitated, and the filter cake is recrystallized in an ethanol solution with a concentration of more than 75% by volume, filtered, and dried to obtain 6-chloro-7-hydroxy-4-methylcoumarin.

[0030] According to another preferred embodiment of the present invention, in step C, the salicylaldehyde compound is salicylaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 4-(diethylamino) salicylaldehyde or 2,4-dihydroxybenzaldehyde.

[0031] According to another preferred embodiment of the present invention, in step C, the coumarin acid compound is coumarin-3-carboxylic acid, 7-methoxycoumarin-3-carboxylic acid, 7-diethylaminocoumarin-3-carboxylic acid or 7-hydroxycoumarin-3-carboxylic acid.

[0032] According to another preferred embodiment of the present invention, in step D, the initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate or potassium persulfate.

[0033] According to another preferred embodiment of the present invention, in step D, the solvent is one or more solvents selected from toluene, xylene, n-butanol, butyl acetate or ethyl acetate.

[0034] According to another preferred embodiment of the present invention, in step D, the chain transfer agent is n-dodecyl mercaptan, tert-dodecyl mercaptan or an aliphatic mercaptan chain transfer agent.

[0035] According to another preferred embodiment of the present invention, in step E, the divalent metal oxide is zinc oxide or copper oxide; the divalent metal hydroxide is zinc hydroxide or copper hydroxide; and the solvent is N,N-dimethylformamide or dimethyl sulfoxide solvent.

[0036] The present invention also relates to the use of the coumarin structure-containing acrylic acid metal salt resin or the coumarin structure-containing acrylic acid metal salt resin prepared according to the preparation method in marine antifouling coatings.

[0037] The present invention will be described in more detail below.

[0038] The invention relates to an acrylic acid metal salt resin containing a coumarin structure.

[0039] Coumarin is a typical natural compound widely found in fruits, vegetables and grasses. Existing studies have found that benzopyrone of coumarin has a wide range of bioinhibitory properties, including antibacterial, antioxidant, antiviral and other effects. Among them, coumarin-3-carboxylic acid compounds have good inhibitory effects on almost all tested bacteria (plant pathogens), with an inhibition rate of up to 93.11%, and have potential prospects in marine antifouling. For details, see the document "Antibacterial activities of coumarin-3-carboxylic acid against Acidovorax citrulli", journal name "Frontiers in Microbiology", Volume 14, Issue 2023. Recent research results show that the fluorescent properties of the compound can give the material good antifouling properties. Therefore, it is possible to achieve excellent antifouling performance through the synergistic effect of fluorescent properties and self-antibacterial properties. Introducing coumarin structures with bioinhibitory properties and fluorescent properties into acrylic resins can develop new environmentally friendly self-polishing antifouling resins with multifunctional synergistic effects.

[0040] According to the present invention, the acrylic acid metal salt resin has the following chemical structural formula (I):

[0041]

[0042] In the formula: R1 is H, R2 is H; or R1 is CH3, R2 is H; or R1 is H, R2 is Cl;

[0043] R3 is H, -OCH3, -OH or -Et2N;

[0044] X is Zn 2+ Cu 2+ Metal ions;

[0045] n is a positive integer; m is 0 or a positive integer; x is 0 or a positive integer; y is a positive integer;

[0046] The number average molecular weight of the above-mentioned metal acrylate resin containing coumarin structure is 2000-60000, and its molecular weight distribution is 1.0-2.5.

[0047] The number average molecular weight and molecular weight distribution of the acrylic acid metal salt resin are measured by conventional gel permeation chromatography.

[0048] The invention also relates to a method for preparing the acrylic acid metal salt resin containing the coumarin structure.

[0049] The preparation steps of the preparation method are as follows:

[0050] A. Preparation of hydroxycoumarin compounds

[0051] In this step, the basic reaction for preparing hydroxyl coumarin compounds is as follows:

[0052]

[0053] In the formula: R1 is H, R2 is H; or R1 is CH3, R2 is H; or R1 is H, R2 is Cl;

[0054] In the present invention, the hydroxyl-containing coumarin is 7-hydroxy-4-methylcoumarin, 7-hydroxy-4,8-dimethylcoumarin or 6-chloro-7-hydroxy-4-methylcoumarin.

[0055] For 7-hydroxy-4-methylcoumarin or 7-hydroxy-4,8-dimethylcoumarin, the specific preparation method is as follows:

[0056] In a round-bottom flask, resorcinol or 2-methylresorcinol and ethyl acetoacetate are stirred and dissolved in a molar ratio of 1:0.8-2.0 to obtain a mixture solution, and then ZrCl4 is slowly added to the mixture solution according to 15%-25% of their total molar amount, and the mixture is vigorously stirred and reacted for 20-40 minutes at room temperature, and then ice water is slowly added to precipitate, and the precipitate is filtered by suction, and the obtained filter cake is recrystallized in an ethanol solution with a concentration of more than 90% by volume, filtered, and dried to obtain 7-hydroxy-4-methylcoumarin or 7-hydroxy-4,8-dimethylcoumarin;

[0057] In the present invention, the molar ratio of resorcinol or 2-methylresorcinol to ethyl acetoacetate is 1:0.8-2.0. If the molar ratio of resorcinol or 2-methylresorcinol to ethyl acetoacetate is greater than 1:0.8, the reaction is not carried out completely and the reaction yield is low; if the molar ratio of resorcinol or 2-methylresorcinol to ethyl acetoacetate is less than 1:2.0, the excess ethyl acetoacetate does not participate in the reaction, resulting in a waste of resources; therefore, the molar ratio of resorcinol or 2-methylresorcinol to ethyl acetoacetate is 1:0.8-2.0, which is reasonable, preferably 1:1.0-1.8; more preferably 1:1.2-1.6;

[0058] The resorcinol, 2-methylresorcinol and ethyl acetoacetate used in the present invention are all products currently sold on the market, such as products sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name of resorcinol and 2-methylresorcinol, and products sold by Sinopharm Chemical Reagent Co., Ltd. under the trade name of ethyl acetoacetate.

[0059] The main function of adding ZrCl4 to the mixture solution is to act as a catalyst for the reaction, thereby increasing the chemical reaction rate and the reaction yield.

[0060] After adding ZrCl4 to the mixture solution, a common stirrer is required to stir the reaction at a stirring speed of 300-600rpm for 20-40min. When the stirring reaction time is within the range, if the stirring speed of the stirrer is lower than 300rpm, the reactants will settle and the reaction will be incomplete; if the stirring speed of the stirrer is higher than 600rpm, the reaction will be very intense; therefore, a stirring speed of 300-600rpm is appropriate, preferably 400-500rpm; when the stirring speed of the stirrer is within the range, if the stirring time is shorter than 20min, the reaction will not be thorough and the reaction yield will be low; if the stirring time is longer than 40min, the reaction cost will increase, resulting in waste of resources; therefore, a stirring time of 20-40min is appropriate;

[0061] In this step, ice water is added to the reaction solution to allow the reactants to precipitate out in the form of precipitation, wherein the volume ratio of the reaction solution to ice water is generally 1:3-6; the reaction solution and ice water mixture is allowed to stand at room temperature until the precipitate no longer increases. The separated precipitate is filtered using a suction filtration device sold by Shanghai Ailang Instrument Co., Ltd. under the trade name of a water flow vacuum pump, and the obtained filter cake is recrystallized in an ethanol solution with a concentration of more than 90% by volume. The main purpose is to obtain a high-purity compound. During recrystallization, the ratio of the weight of the filter cake in grams to the volume of the ethanol solution in milliliters is generally 1:10-20; after recrystallization, the filter cake is filtered using a filtration device sold by Shanghai Ailang Instrument Co., Ltd. under the trade name of a water flow vacuum pump, and the obtained filter cake is then dried to constant weight at a temperature of 65°C using a drying device sold by Shanghai Yiheng Instrument Co., Ltd. under the trade name of a constant temperature blast dryer, and the obtained dried product is tested by nuclear magnetic resonance hydrogen spectrum analysis, and the test results are listed in the attached Figure 1 With attached Figure 2 In, by the attached Figure 1 With attached Figure 2 The listed results indicate that the dried product is 7-hydroxy-4-methylcoumarin or 7-hydroxy-4,8-dimethylcoumarin compound;

[0062] For the 6-chloro-7-hydroxy-4-methylcoumarin compound, the specific preparation method is as follows:

[0063] 4-Chlororesorcinol and ethyl acetoacetate are stirred and mixed in a molar ratio of 1:0.8-2.0 to obtain a mixture solution. Meanwhile, concentrated sulfuric acid of 100%-200% based on the total volume of the mixture solution is cooled to a temperature of -10°C-5°C using an ice-salt bath. The mixture solution is added to the concentrated sulfuric acid under stirring to react for 3-7 hours. Then, ice water is slowly added under stirring to precipitate a precipitate, and the precipitate is filtered. The obtained filter cake is dissolved in a NaOH solution of 5%-10% by weight. The obtained solution is extracted 2-5 times with ethyl acetate under the condition that the volume ratio of the solution to ethyl acetate is 1:1.5-3.0. The obtained aqueous phase is acidified to pH=5 with sulfuric acid of 10%-20% by weight under ice bath cooling, a precipitate is precipitated, and the precipitate is filtered. The obtained filter cake is recrystallized in an ethanol solution of 75% or more by volume, filtered, and dried to obtain a 6-chloro-7-hydroxy-4-methylcoumarin compound.

[0064] In the preparation method, the molar ratio of 4-chlororesorcinol to ethyl acetoacetate is the same as the molar ratio of resorcinol or 2-methylresorcinol to ethyl acetoacetate mentioned above, so it is not repeated here.

[0065] The concentrated sulfuric acid used in the preparation method should be understood as a sulfuric acid solution with a concentration of 98% by weight.

[0066] In the preparation method, the amount of concentrated sulfuric acid used is 100% to 200% of the total volume of the mixture solution. If the amount of concentrated sulfuric acid used is less than 100% of the total volume of the mixture solution, the reaction is slow and incomplete, and the reaction yield is also low; if the amount of concentrated sulfuric acid used is higher than 200% of the total volume of the mixture solution, the reaction cost increases and resources are wasted; therefore, it is appropriate that the amount of concentrated sulfuric acid used is 100% to 200% of the total volume of the mixture solution;

[0067] The mixture solution is reacted with concentrated sulfuric acid at a temperature of -10°C to 5°C under stirring for 3 to 7 hours. If the reaction time of the mixture solution and the concentrated sulfuric acid is shorter than 3 hours, the reaction is not thorough and the reaction yield is low; if the reaction time of the mixture solution and the concentrated sulfuric acid is longer than 7 hours, the side reactions increase and the yield of the target product decreases; therefore, the reaction time of the mixture solution and the concentrated sulfuric acid is appropriately 3 to 7 hours, preferably 4 to 6 hours;

[0068] The main purpose of precipitating the reaction product of the mixture solution and concentrated sulfuric acid in ice water is to terminate the reaction.

[0069] The filter cake obtained by filtration is dissolved in a NaOH solution with a concentration of 5% to 10% by weight, and the obtained solution is then extracted 2 to 5 times with ethyl acetate under the condition that the volume ratio of the NaOH solution to ethyl acetate is 1:1.5 to 3.0. The basic function of this extraction step is to transfer NaOH to the ethyl acetate solution, and the product is directly retained in the aqueous solution. When the number of extractions is 2 to 5 times, if the volume ratio of the NaOH solution to ethyl acetate is greater than 1:1.5, the reaction product is not completely extracted; if the volume ratio of the NaOH solution to ethyl acetate is less than 1:3.0, it will cause a waste of resources; therefore, a volume ratio of the NaOH solution to ethyl acetate of 1:1.5 to 3.0 is desirable; when the volume ratio of the NaOH solution to ethyl acetate is 1:1.5 to 3.0, if the number of extractions is less than 2 times, the product is not completely extracted; if the number of extractions is more than 5 times, it is time-consuming and labor-intensive, resulting in a waste of resources; therefore, an extraction number of 2 to 5 times is appropriate;

[0070] The aqueous phase obtained by extraction is acidified to pH=5 using sulfuric acid having a concentration of 10% to 20% by weight under ice bath cooling, a precipitate is precipitated, suction filtered, and the filter cake obtained is recrystallized in an ethanol solution having a concentration of more than 75% by volume, filtered, and dried to obtain a 6-chloro-7-hydroxy-4-methylcoumarin compound. The recrystallization, filtration, drying and the equipment involved in the implementation process of this step are as described above, so they are not repeated here.

[0071] The obtained dried product was tested by the above analytical method, and the test results are listed in the attached Figure 3 , by the attached Figure 3The results listed indicate that the dried product is 6-chloro-7-hydroxy-4-methylcoumarin compound.

[0072] B. Preparation of coumarin compounds containing C=C double bond structure

[0073] The hydroxy coumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask in a molar ratio of 30-40:40-55:40-55:0.7-1.0, and then acetone solvent is added to the reactants in a ratio of 10-20:150-200 of the total mass of the reactants in grams to acetone in milliliters, and then heated to reflux for reaction at a temperature of 50°C to 70°C for 15-24h, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 40°C to 50°C and a vacuum degree of -0.07 to -0.10kPa to obtain a coumarin compound containing a C=C double bond structure;

[0074] In this step, the basic reaction for preparing coumarin compounds containing a C=C double bond structure is as follows:

[0075]

[0076] In the formula: R1 is H, R2 is H; or R1 is CH3, R2 is H; or R1 is H, R2 is Cl;

[0077] Among them, the main role of K2CO3 in this basic reaction is to increase the leaving ability of the leaving group in the substrate and enhance the nucleophilic ability of the nucleophilic reagent; the main role of 3-bromopropylene in this basic reaction is to act as a reactant and provide a double bond; the main role of KI in this basic reaction is to act as a catalyst to change the transition state of the reaction, reduce the activation energy of the reaction, and enable the reaction to proceed smoothly.

[0078] The molar ratio of the hydroxy coumarin compound, K2CO3, 3-bromopropylene and KI reactant is 30-40: 40-55: 40-55: 0.7-1.0. When the amount of K2CO3, 3-bromopropylene and KI reactants is within the range, if the amount of the hydroxy coumarin compound is less than 30, the reaction yield is low due to the low content of the reactant; if the amount of the hydroxy coumarin compound is higher than 40, the amount of the reactant is too large, resulting in a waste of resources; therefore, it is reasonable to use 30-40 hydroxy coumarin compounds, preferably 32-38;

[0079] When the amount of the hydroxy coumarin compound, 3-bromopropylene and KI reactants is within the above range, if the amount of K2CO3 is less than 40, the reaction is not completely carried out due to the small amount of alkali and the reaction cannot be well promoted, resulting in a low reaction yield; if the amount of K2CO3 is higher than 55, some side reactions increase, resulting in a decrease in the reaction yield; therefore, the amount of K2CO3 is suitable to be 40-55, preferably 44-52;

[0080] When the amount of the hydroxyl coumarin compound, K2CO3 and KI reactants is within the range, if the amount of 3-bromopropylene is less than 40, the reaction yield is low due to the low content of the reactants; if the amount of 3-bromopropylene is more than 55, the reactants are excessive and the resources are wasted; therefore, the amount of 3-bromopropylene is appropriately 40-55, preferably 42-48;

[0081] When the amount of the hydroxy coumarin compound, K2CO3 and 3-bromopropylene reactants is within the range, if the amount of KI is less than 0.7, the catalyst will not have a good catalytic effect when the amount is small, so that the reaction cannot proceed smoothly, resulting in an incomplete reaction and a low reaction yield; if the amount of KI is higher than 1.0, some side reactions will occur, thereby affecting the yield of the reaction; therefore, the amount of KI is appropriately 0.7-1.0, preferably 0.8-0.9.

[0082] Preferably, the molar ratio of the hydroxyl coumarin compound, K2CO3, 3-bromopropylene and KI reactants is 32-38: 44-52: 42-48: 0.8-0.9.

[0083] In this step, the ratio of the total mass of the hydroxycoumarin compound, K2CO3, 3-bromopropylene and KI reactants in grams to the acetone in milliliters is 10-20:150-200. When the total mass of the hydroxycoumarin compound, K2CO3, 3-bromopropylene and KI reactants is 10-20, if the amount of acetone is less than 150, these reactants cannot be completely dissolved, resulting in a low reaction yield; if the amount of acetone is higher than 200, the concentration of these reactants is low, which also leads to a decrease in the reaction yield and a waste of resources; therefore, the amount of acetone is appropriately 150-200, preferably 160-190;

[0084] When the amount of acetone is 150-200, if the total mass of the hydroxycoumarin compound, K2CO3, 3-bromopropylene and KI reactants is less than 10, the concentration of these reactants is significantly reduced, resulting in a significant decrease in the yield of the reaction; if the total mass of the hydroxycoumarin compound, K2CO3, 3-bromopropylene and KI reactants is greater than 20, these reactants cannot be fully dissolved, resulting in a low yield of the reaction; therefore, the total mass of the hydroxycoumarin compound, K2CO3, 3-bromopropylene and KI reactants is appropriately 10-20, preferably 12-18;

[0085] The hydroxy coumarin compound, K2CO3, 3-bromopropylene and KI reactants are heated to reflux in an acetone solvent at a temperature of 50°C to 70°C for 15 to 24 hours. In this step, when the heating reflux reaction time is within the range, if the reaction temperature is lower than 50°C, the reaction is not thorough and the yield of the reaction product is significantly reduced; if the reaction temperature is higher than 70°C, some side reactions occur due to the high reaction temperature, and the yield of the target product is reduced; therefore, the reaction temperature of 50°C to 70°C is feasible, preferably 56°C to 65°C; when the heating reflux reaction temperature is within the range, if the reaction time is shorter than 15h, the reaction is not thorough, resulting in a significant reduction in the yield of the product; if the reaction time is longer than 24h, some side reactions occur, resulting in a waste of resources; therefore, the reaction time of 15 to 24h is reasonable, preferably 18 to 22h;

[0086] After the heating reflux reaction is completed, suction filtration is performed using a suction filtration device sold by Shanghai Ailang Instrument Co., Ltd. under the trade name of water flow vacuum pump, and the collected filtrate is vacuum evaporated using a vacuum rotary evaporator sold by Zhengzhou Keda Mechanical Instrument Equipment Co., Ltd. under the trade name of rotary evaporator at a temperature of 40°C to 50°C and a vacuum degree of -0.07 to -0.10 kPa.

[0087] The dried product was dried at 65°C until constant weight using a drying device sold by Shanghai Yiheng Instrument Co., Ltd. under the trade name Constant Temperature Blower Dryer. The dried product was tested using conventional nuclear magnetic resonance hydrogen spectrum analysis, and the test results are listed in the attached Figure 4-6 , by the attached Figure 4-6 The listed results showed that the dried products were 7-allyloxy-4-methylcoumarin, 7-allyloxy-4,8-dimethylcoumarin and 6-chloro-7-allyloxy-4-methylcoumarin.

[0088] C. Preparation of coumarin acid compounds

[0089] The salicylaldehyde compound and the Michaelis acid are added to a round-bottom flask in a molar ratio of 20:20-25, and then 350%-500% of a water solvent based on the total mass of the salicylaldehyde compound and the Michaelis acid is added, stirred and mixed evenly, and then reacted at a temperature of 100-120° C. for 2-6 hours, filtered, and dried to obtain the coumarin acid compound;

[0090] In this step, the basic reaction for preparing the coumarin acid compound is as follows:

[0091]

[0092] Wherein: R3 is H, -OCH3, -OH or -Et2N;

[0093] According to the present invention, the salicylaldehyde compound is salicylaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 4-(diethylamino) salicylaldehyde or 2,4-dihydroxybenzaldehyde, which are all products currently sold on the market, such as products sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name salicylaldehyde, products sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name 2-hydroxy-4-methoxybenzaldehyde, products sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name 4-(diethylamino) salicylaldehyde, and products sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name 2,4-dihydroxybenzaldehyde. The Michaelis acid used in the present invention is a product currently sold on the market, such as a product sold by Shanghai MacLean Biochemical Technology Co., Ltd. under the trade name Michaelis acid.

[0094] In this step, the molar ratio of salicylaldehyde compound to Michael's acid is 20:20 to 25. If the molar ratio of salicylaldehyde compound to Michael's acid is greater than 20:20, the reaction is not thorough and the yield of the reaction product is significantly reduced; if the molar ratio of salicylaldehyde compound to Michael's acid is less than 20:25, Michael's acid is used in excessive amounts, resulting in a waste of resources; therefore, a molar ratio of salicylaldehyde compound to Michael's acid of 20:20 to 25 is appropriate;

[0095] The mass of the water solvent is 350% to 500% of the total mass of the salicylaldehyde compound and the Michaelis acid. If the mass of the water solvent is lower than 350%, the concentration of these reactants is too high, and the reaction is not thorough, so the yield of the reaction product is significantly reduced; if the mass of the water solvent is higher than 500%, the concentration of these reactants is too low, so the yield of the reaction product is also significantly low; therefore, the mass of the water solvent is 350% to 500% is appropriate;

[0096] The salicylaldehyde compound and the Michaelis acid are reacted in an aqueous solvent at a temperature of 100 to 120° C. for 2 to 6 hours. When the reaction time is within the range, if the reaction temperature is lower than 100° C., the reactants cannot fully react, and the yield of the reaction product will naturally decrease; if the reaction temperature is higher than 120° C., some side reactions will occur, which will significantly affect the yield of the target product; therefore, a reaction temperature of 100 to 120° C. is appropriate; when the reaction temperature is within the range, if the reaction time is shorter than 2 hours, the reactants do not fully react, and the yield of the reaction product will also decrease; if the reaction time is longer than 6 hours, some side reactions will occur, which will significantly affect the yield of the target product; therefore, a reaction time of 2 to 6 hours is appropriate, preferably 2.8 to 5.1 hours;

[0097] After the reaction of salicylaldehyde compound and Michaelis acid in water solvent is completed, it is necessary to filter and dry until constant weight. The obtained dry product is detected by conventional nuclear magnetic resonance hydrogen spectrum analysis method, and the detection results are listed in the attached Figure 7-10 , by the attached Figure 7-10 The results listed indicate that the dry product is coumarin-3-carboxylic acid, 7-methoxycoumarin-3-carboxylic acid, 7-diethylaminocoumarin-3-carboxylic acid or 7-hydroxycoumarin-3-carboxylic acid.

[0098] The filtration equipment used in this step is a product currently sold on the market, such as the product sold by Shanghai Ailang Instrument Co., Ltd. under the trade name Water Flow Aspirator.

[0099] The drying equipment used in this step is a product currently sold on the market, such as a product sold by Shanghai Yiheng Instrument Co., Ltd. under the trade name of Constant Temperature Blower Dryer.

[0100] D. Synthesis of acrylic prepolymer containing coumarin structure

[0101] Ethyl acrylate, butyl acrylate, acrylic acid and a coumarin compound containing a C=C double bond structure are mixed uniformly in a molar ratio of 6:2:2:0.05-2.5 to obtain a monomer mixture, and then 0.5%-3.2% of an initiator is added based on the weight of the monomer mixture, and the mixture is mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 100-230% of a solvent, 10%-20% of a monomer mixture containing an initiator and 0.3%-2.0% of a chain transfer agent are added based on the weight of the monomer mixture, and the mixture is stirred uniformly, and the reaction temperature of the reaction mixture is controlled at 75°C-110°C, and then the remaining monomer mixture containing an initiator is evenly divided into 9-15 portions, and one portion is added every 10-20 minutes, and the mixture is reacted for 4-8 hours to obtain a viscous acrylic acid prepolymer containing a coumarin structure;

[0102] In this step, the basic reaction for preparing the coumarin-containing acrylic prepolymer is as follows:

[0103]

[0104] In the formula: R1 is H, R2 is H; or R1 is CH3, R2 is H; or R1 is H, R2 is Cl;

[0105] R3 is H, -OCH3, -OH or -Et2N;

[0106] n is a positive integer; m is 0 or a positive integer; x is 0 or a positive integer; y is a positive integer;

[0107] The molar ratio of ethyl acrylate, butyl acrylate, acrylic acid and coumarin compound containing C=C double bond structure in the monomer mixture is 6:2:2:0.05-2.5. Ethyl acrylate, butyl acrylate and acrylic acid used in the present invention are all products currently sold on the market, and they are all products sold by Datang Chemical Reagent Co., Ltd.

[0108] According to the present invention, the main purpose of adding an initiator to the monomer mixture is that it decomposes the acrylate basic monomer, the acrylic acid monomer and the functional monomer containing the coumarin structure into active particles, and initiates these monomers to carry out free radical polymerization. The initiator used in the present invention is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate or potassium persulfate, which are all products currently sold on the market, for example, they are all products sold by Tianjin Damao Chemical Reagent Factory or Tianjin Hedong Hongyan Reagent Factory.

[0109] The amount of the initiator added is 0.5% to 3.2% by weight of the monomer mixture. If the amount of the initiator added is less than 0.5%, it is difficult for these monomers to polymerize to obtain an acrylic prepolymer; if the amount of the initiator added is more than 3.2%, the acrylic prepolymer will have a higher viscosity and a shorter molecular chain, which is not conducive to the subsequent acrylic resin film formation; therefore, the amount of the initiator added is appropriately 0.5% to 3.2%, preferably 0.9% to 2.5%;

[0110] Then, 100-230% of the solvent, 10%-20% of the monomer mixture containing the initiator and 0.3%-2.0% of the chain transfer agent are stirred and mixed uniformly according to the weight of the monomer mixture to obtain a reaction mixture, wherein: the solvent is one or more solvents selected from toluene, xylene, n-butanol, butyl acetate or ethyl acetate, which are all products currently sold on the market, such as products sold by Datang Chemical Reagent Co., Ltd.;

[0111] The chain transfer agent is n-dodecyl mercaptan, tert-dodecyl mercaptan or aliphatic mercaptan chain transfer agent, which are products currently sold on the market, such as products sold by Shanghai Aladdin Biochemical Technology Co., Ltd.

[0112] The reaction temperature of the reaction mixture is controlled at 75°C to 110°C so that the polymerization reaction can proceed smoothly and fully. Then the remaining monomer mixture containing the initiator is evenly divided into 9 to 15 portions, and one portion is added every 10 to 20 minutes. The purpose is to avoid agglomeration caused by excessive single addition or explosion caused by excessive local temperature.

[0113] After the remaining monomer mixture containing the initiator is added, the reaction needs to be continued for 4 to 8 hours. If the reaction time is shorter than 4 hours, the prepolymerization reaction is not complete and the yield of the prepolymerization product is reduced; if the reaction time is longer than 8 hours, some side reactions will increase significantly, thereby reducing the yield of the target product; therefore, the reaction time is suitable for 4 to 8 hours, preferably 4.6 to 7.2 hours.

[0114] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0115] The coumarin structure-containing acrylic prepolymer obtained in step D is cooled to a temperature below 70° C., and then a metal oxide or hydroxide and a coumarin acid compound obtained in step C are added, wherein the added amounts are 0.8 to 1.5 times the molar amount of acrylic acid in the coumarin structure-containing acrylic prepolymer, and the molar ratio of the metal oxide or hydroxide to the coumarin acid compound is 1:0.8 to 1.5. The mixture is mixed evenly, and then 150% to 200% of a solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 100° C. to 130° C. for 3 to 5 days to obtain a coumarin structure-containing acrylic metal salt resin.

[0116] In this step, the basic reaction for preparing the coumarin structure-containing acrylic acid metal salt resin is as follows:

[0117]

[0118] Where:

[0119] R1 is H, R2 is H; or R1 is CH3, R2 is H; or R1 is H, R2 is Cl;

[0120] R3 is H, -OCH3, -OH or -Et2N;

[0121] X is Zn 2+ Cu 2+ Metal ions;

[0122] n is a positive integer; m is 0 or a positive integer; x is 0 or a positive integer; y is a positive integer;

[0123] According to the present invention, the divalent metal oxide is zinc oxide or copper oxide; the divalent metal hydroxide is zinc hydroxide or copper hydroxide; and the solvent is N,N-dimethylformamide or dimethyl sulfoxide solvent.

[0124] The coumarin acid compound prepared in step C of the preparation method of the present invention is coumarin-3-carboxylic acid, 7-methoxycoumarin-3-carboxylic acid, 7-diethylaminocoumarin-3-carboxylic acid or 7-hydroxycoumarin-3-carboxylic acid;

[0125] In this step, the amount of the metal oxide, the metal hydroxide and the coumarin acid compound is 0.8 to 1.5 times the molar amount of acrylic acid in the coumarin structure-containing acrylic prepolymer. If the amount of any one of the metal oxide, the metal hydroxide and the coumarin acid compound is less than 0.8 times, a large amount of prepolymer will remain in the acrylic metal salt resin; if the amount of any one of the metal oxide, the metal hydroxide and the coumarin acid compound is more than 1.5 times, a large amount of side reaction products will exist in the acrylic metal salt resin; therefore, it is feasible to use 0.8 to 1.5 times any one of the metal oxide, the metal hydroxide and the coumarin acid compound;

[0126] In addition, the molar ratio of the metal oxide or metal hydroxide to the coumarin acid compound is 1:0.8 to 1.5. If the molar ratio of the metal oxide or metal hydroxide to the coumarin acid compound is greater than 1:0.8, the polymerization reaction will not be carried out completely; if the molar ratio of the metal oxide or metal hydroxide to the coumarin acid compound is less than 1:1.5, a large amount of organic acid monomer substances will remain in the polymer solution; therefore, the molar ratio of the metal oxide or metal hydroxide to the coumarin acid compound is 1:0.8 to 1.5, which is reasonable;

[0127] The amount of the solvent used is 150% to 200% of the weight of the mixture obtained in this step. If the amount of the solvent used is less than 150% of the weight of the mixture obtained in this step, it is not conducive to the heat transfer in the system, thereby affecting the smooth progress of the reaction; if the amount of the solvent used is more than 200% of the weight of the mixture obtained in this step, the viscosity of the acrylic acid metal salt resin is too low, affecting its film-forming properties, and excessive organic solvents will affect the environment and cause waste of resources; therefore, it is feasible that the amount of the solvent used is 150% to 200% of the weight of the mixture obtained in this step;

[0128] The metal oxide, metal hydroxide and coumarin acid compound are reacted in the solvent at a temperature of 100°C to 130°C for 3 to 5 days to obtain the coumarin structure-containing acrylic acid metal salt resin. When the reaction time is within the range, if the reaction temperature is lower than 100°C, the reaction rate is low and it is difficult to proceed thoroughly, so the reaction yield is significantly reduced; if the reaction temperature is higher than 130°C, the product obtained by the reaction has a low molecular weight, and the side reactions increase, resulting in a waste of resources; therefore, the reaction temperature of 100°C to 130°C is reasonable, preferably 108°C to 122°C; when the reaction temperature is within the range, if the reaction time is shorter than 3 days, the polymerization degree of the reactant is low; if the reaction time is longer than 5 days, the side reactions increase; therefore, the reaction time of 3 to 5 days is appropriate, preferably 3.5 to 4.5 days.

[0129] The product obtained in this preparation step was detected by conventional nuclear magnetic resonance hydrogen spectrum and conventional Fourier transform infrared analysis method, and the detection results are listed in the attached Figure 11-12 , by the attached Fig.11 With attached Fig.12 The listed results show that the product is a metal acrylate resin containing a coumarin structure.

[0130] The present invention also relates to the use of the coumarin structure-containing acrylic acid metal salt resin or the coumarin structure-containing acrylic acid metal salt resin prepared according to the preparation method in marine antifouling coatings.

[0131] According to the national standard "Antifouling paint sample shallow sea immersion test method" (GB / T 5370-2007), the antifouling performance test of the coumarin structure-containing acrylic acid metal salt resin of the present invention was carried out in Qingdao, Shandong. The specific test results are shown in the following specific implementation method section. These test results clearly show that the coumarin structure-containing acrylic acid metal salt resin of the present invention has an antifouling period of at least 110 days in the marine environment.

[0132] The beneficial effects of the present invention are:

[0133] The coumarin structure-containing acrylic metal salt resin synthesized by the present invention is an environmentally friendly antifouling resin, with a simple preparation process and readily available raw materials. At the same time, a natural antifouling agent is grafted into the acrylic metal salt resin to prepare an acrylic metal salt resin containing a coumarin structure, which has the antifouling effects of antibacterial, fluorescent antifouling and self-polishing antifouling, and enhances the antifouling performance of the resin. Through a real sea antifouling test, the coating has a static real sea antifouling effect of more than 110 days.

Brief Description of the Drawings

[0134] Figure 1 is the nuclear magnetic hydrogen resonance spectrum of 7-hydroxy-4-methylcoumarin;

[0135] Figure 2 It is the hydrogen nuclear magnetic resonance spectrum of 7-hydroxy-4,8-dimethylcoumarin;

[0136] Figure 3 It is the hydrogen nuclear magnetic resonance spectrum of 6-chloro-7-hydroxy-4-methylcoumarin;

[0137] Figure 4 is the H NMR spectrum of 7-allyloxy-4-methylcoumarin;

[0138] Figure 5 It is the hydrogen nuclear magnetic resonance spectrum of 7-allyloxy-4,8-dimethylcoumarin;

[0139] Figure 6 It is the hydrogen nuclear magnetic resonance spectrum of 6-chloro-7-allyloxy-4-methylcoumarin;

[0140] Figure 7 is the hydrogen nuclear magnetic resonance spectrum of coumarin-3-carboxylic acid;

[0141] Figure 8 It is the hydrogen nuclear magnetic resonance spectrum of 7-methoxycoumarin-3-carboxylic acid;

[0142] Fig. 9 It is the hydrogen nuclear magnetic resonance spectrum of 7-diethylaminocoumarin-3-carboxylic acid;

[0143] Fig.10 It is the hydrogen nuclear magnetic resonance spectrum of 7-hydroxycoumarin-3-carboxylic acid;

[0144] Fig.11 is the hydrogen nuclear magnetic resonance spectrum of metal salt of acrylic acid;

[0145] Fig.12 This is the Fourier transform infrared spectrum of acrylic acid metal salt.

[0146] Fig.13 This is a real sea effect picture of acrylic acid metal salt. [Specific implementation method]

[0147] The present invention will be better understood through the following examples.

[0148] Example 1: Preparation of metal acrylate resin containing coumarin structure of the present invention

[0149] The implementation steps of this embodiment are as follows:

[0150] A. Preparation of hydroxycoumarin compounds

[0151] In a round-bottom flask, resorcinol and ethyl acetoacetate are stirred and dissolved in a molar ratio of 1:1:1.2 to obtain a mixture solution, and then ZrCl4 is slowly added to the mixture solution according to 18% of their total molar amount, and the mixture is vigorously stirred and reacted for 35 minutes at room temperature, and then ice water is slowly added to precipitate, and the precipitate is filtered by suction. The filter cake obtained is recrystallized in an ethanol solution with a concentration of 90% by volume, filtered, and dried to obtain 7-hydroxy-4-methylcoumarin;

[0152] B. Preparation of coumarin compounds containing C=C double bond structure

[0153] The 7-hydroxy-4-methylcoumarin, K2CO3, 3-bromopropylene and KI reactants prepared in step A are added to a round-bottom flask in a molar ratio of 35:48:48:0.9, and then an acetone solvent is added to the reactants in a ratio of 15:180 of the total mass of the reactants in grams to the acetone in milliliters, and then heated under reflux at a temperature of 60° C. for 20 hours, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 50° C. and a vacuum degree of -0.07 kPa to obtain 7-allyloxy-4-methylcoumarin;

[0154] C. Preparation of coumarin acid compounds

[0155] Salicylaldehyde and Michaelis' acid are added to a round-bottom flask in a molar ratio of 20:22, and then 400% of a water solvent based on the total mass of the salicylaldehyde compound and Michaelis' acid is added, stirred and mixed evenly, and then reacted at a temperature of 112° C. for 4 hours, filtered, and dried to obtain a coumarin-3-carboxylic acid compound;

[0156] D. Synthesis of acrylic prepolymer containing coumarin structure

[0157] Ethyl acrylate, butyl acrylate, acrylic acid and the prepared 7-allyloxy-4-methylcoumarin are mixed uniformly in a molar ratio of 6:2:2:1.0 to obtain a monomer mixture, and then 1.1% of azobisisobutyronitrile initiator is added to the monomer mixture by weight, and mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 150% of toluene solvent, 14% of the monomer mixture containing an initiator and 1.3% of n-dodecyl mercaptan chain transfer agent are added to the monomer mixture by weight, and stirred uniformly, and the reaction temperature of the reaction mixture is controlled at 96° C., and then the remaining monomer mixture containing an initiator is evenly divided into 10 parts, and one part is added every 20 minutes, and the reaction is carried out for 6 hours to obtain a viscous acrylic acid prepolymer containing a 7-allyloxy-4-methylcoumarin structure;

[0158] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0159] The coumarin-containing acrylic prepolymer obtained in step D is cooled to a temperature of 60° C., and then zinc oxide and the coumarin-3-carboxylic acid compound obtained in step C are added, wherein the added amounts are 1.0 times the molar amount of acrylic acid in the coumarin-containing acrylic prepolymer, and the molar ratio of zinc oxide to the coumarin acid compound is 1:1.3. The mixture is mixed evenly, and then 150% of N,N-dimethylformamide solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 100° C. for 4 days to obtain the acrylic metal salt resin containing a coumarin structure.

[0160] The antifouling performance of the coumarin-containing acrylic acid metal salt resin prepared in this example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , it has an antifouling period of more than 110 days in marine environments.

[0161] Example 2: Preparation of metal acrylate resin containing coumarin structure of the present invention

[0162] The implementation steps of this embodiment are as follows:

[0163] A. Preparation of hydroxycoumarin compounds

[0164] In a round-bottom flask, 2-methylresorcinol and ethyl acetoacetate are stirred and dissolved in a molar ratio of 1:0.8 to obtain a mixture solution, and then ZrCl4 is slowly added to the mixture solution according to 22% of their total molar amount, and the mixture is vigorously stirred and reacted for 20 minutes at room temperature, and then ice water is slowly added to precipitate, and the precipitate is filtered by suction. The filter cake obtained is recrystallized in an ethanol solution with a concentration of 92% by volume, filtered, and dried to obtain a 7-hydroxy-4,8-dimethylcoumarin compound;

[0165] B. Preparation of coumarin compounds containing C=C double bond structure

[0166] The 7-hydroxy-4,8-dimethylcoumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask in a molar ratio of 30:52:43:0.7, and then acetone solvent is added to the reactants in a ratio of 18:200 of the total mass of the reactants in grams to acetone in milliliters, and then heated under reflux at a temperature of 54° C. for 24 hours, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 44 and a vacuum degree of -0.09 kPa to obtain a 7-allyloxy-4,8-dimethylcoumarin compound;

[0167] C. Preparation of coumarin acid compounds

[0168] 2-Hydroxy-4-methoxybenzaldehyde salicylaldehyde compound and Michaelis acid are added into a round-bottom flask in a molar ratio of 20:24, and then 360% of a water solvent based on the total mass of the salicylaldehyde compound and Michaelis acid is added, stirred and mixed evenly, and then reacted at a temperature of 116° C. for 3 h, filtered, and dried to obtain a 7-methoxycoumarin-3-carboxylic acid compound;

[0169] D. Synthesis of acrylic prepolymer containing coumarin structure

[0170] Ethyl acrylate, butyl acrylate, acrylic acid and the prepared 7-allyloxy-4,8-dimethylcoumarin compound are mixed uniformly in a molar ratio of 6:2:2:1.5 to obtain a monomer mixture, and then 0.5% of azobisisoheptanenitrile initiator based on the weight of the monomer mixture is added and mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 230% of a xylene solvent, 10% of a monomer mixture containing an initiator and 0.5% of a tert-dodecyl mercaptan chain transfer agent are added based on the weight of the monomer mixture, and stirred uniformly, the reaction temperature of the reaction mixture is controlled at 75° C., and then the remaining monomer mixture containing an initiator is evenly divided into 9 parts, one part is added every 15 minutes, and the reaction is carried out for 4 hours to obtain a viscous acrylic acid prepolymer containing a 7-allyloxy-4,8-dimethylcoumarin structure;

[0171] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0172] The coumarin structure-containing acrylic prepolymer obtained in step D is cooled to a temperature of 68° C., and then copper oxide and the 7-methoxycoumarin-3-carboxylic acid compound obtained in step C are added, wherein the added amounts are 0.8 times the molar amount of acrylic acid in the coumarin structure-containing acrylic prepolymer, and the molar ratio of copper oxide to the coumarin acid compound is 1:1.0. The mixture is mixed evenly, and then 180% of dimethyl sulfoxide solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 105° C. for 3 days to obtain the coumarin structure-containing acrylic metal salt resin.

[0173] The antifouling performance of the coumarin-containing acrylic acid metal salt resin prepared in this example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , it has an antifouling period of more than 110 days in marine environments.

[0174] Example 3: Preparation of metal acrylate resin containing coumarin structure of the present invention

[0175] The implementation steps of this embodiment are as follows:

[0176] A. Preparation of hydroxycoumarin compounds

[0177] In a round-bottom flask, resorcinol and ethyl acetoacetate are stirred and dissolved in a molar ratio of 1:1.6 to obtain a mixture solution, and then ZrCl4 is slowly added to the mixture solution according to 25% of their total molar amount, and the mixture is vigorously stirred and reacted for 28 minutes at room temperature, and then ice water is slowly added to precipitate, and the precipitate is filtered by suction. The filter cake obtained is recrystallized in an ethanol solution with a concentration of 94% by volume, filtered, and dried to obtain a 7-hydroxy-4-methylcoumarin compound;

[0178] B. Preparation of coumarin compounds containing C=C double bond structure

[0179] The 7-hydroxy-4-methylcoumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask in a molar ratio of 32:55:46:0.8, and then an acetone solvent is added to the reactants in a ratio of 20:190 of the total mass of the reactants in grams to the acetone in milliliters, and then heated under reflux at a temperature of 58° C. for 22 hours, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 42° C. and a vacuum degree of -0.10 kPa to obtain a 7-allyloxy-4-methylcoumarin compound;

[0180] C. Preparation of coumarin acid compounds

[0181] 4-(Diethylamino) salicylaldehyde compound and Michaelis acid were added into a round-bottom flask at a molar ratio of 20:20, and then 350% of water solvent based on the total mass of salicylaldehyde compound and Michaelis acid was added, stirred and mixed evenly, and then reacted at a temperature of 108° C. for 4 hours, filtered and dried to obtain 7-diethylaminocoumarin-3-carboxylic acid compound;

[0182] D. Synthesis of acrylic prepolymer containing coumarin structure

[0183] Ethyl acrylate, butyl acrylate, acrylic acid and the prepared 7-allyloxy-4-methylcoumarin compound are mixed uniformly in a molar ratio of 6:2:2:0.1 to obtain a monomer mixture, and then 1.6% of dimethyl azobisisobutyrate initiator based on the weight of the monomer mixture is added and mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 100% of n-butanol solvent, 16% of the monomer mixture containing the initiator and 2.0% of an aliphatic thiol chain transfer agent are added based on the weight of the monomer mixture, and stirred uniformly, the reaction temperature of the reaction mixture is controlled at 82° C., and then the remaining monomer mixture containing the initiator is evenly divided into 12 parts, one part is added every 10 minutes, and the reaction is carried out for 5 hours to obtain a viscous acrylic acid prepolymer containing a 7-allyloxy-4-methylcoumarin structure;

[0184] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0185] The coumarin structure-containing acrylic prepolymer obtained in step D is cooled to a temperature of 65° C., and then zinc hydroxide and the 7-diethylaminocoumarin-3-carboxylic acid coumarin acid compound obtained in step C are added, wherein the added amounts are 1.2 times the molar amount of acrylic acid in the coumarin structure-containing acrylic prepolymer, and the molar ratio of zinc hydroxide to the coumarin acid compound is 1:0.8. The mixture is mixed evenly, and then 200% of N,N-dimethylformamide solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 110° C. for 5 days, thereby obtaining the coumarin structure-containing acrylic metal salt resin.

[0186] The antifouling performance of the coumarin-containing acrylic acid metal salt resin prepared in this example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , it has an antifouling period of more than 110 days in marine environments.

[0187] Example 4: Preparation of Metal Acrylate Resin Containing Coumarin Structure of the Present Invention

[0188] The implementation steps of this embodiment are as follows:

[0189] A. Preparation of hydroxycoumarin compounds

[0190] In a round-bottom flask, resorcinol and ethyl acetoacetate are stirred and dissolved in a molar ratio of 1:2.0 to obtain a mixture solution, and then ZrCl4 is slowly added to the mixture solution according to 15% of their total molar amount, and the mixture is vigorously stirred and reacted for 40 minutes at room temperature, and then ice water is slowly added to precipitate, and the precipitate is filtered by suction. The filter cake obtained is recrystallized in an ethanol solution with a concentration of 92% by volume, filtered, and dried to obtain a 7-hydroxy-4,8-dimethylcoumarin compound;

[0191] B. Preparation of coumarin compounds containing C=C double bond structure

[0192] The 7-hydroxy-4,8-dimethylcoumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask at a molar ratio of 36:40:52:1.0, and then an acetone solvent is added to the reactants at a ratio of 10:150 of the total mass of the reactants in grams to the acetone in milliliters, and then heated under reflux at a temperature of 64° C. for 20 hours, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 48° C. and a vacuum degree of -0.08 kPa to obtain a 7-allyloxy-4,8-dimethylcoumarin compound;

[0193] C. Preparation of coumarin acid compounds

[0194] 2,4-dihydroxybenzaldehyde salicylaldehyde compound and Michaelis acid are added into a round-bottom flask in a molar ratio of 20:25, and then 490% of a water solvent based on the total mass of the salicylaldehyde compound and Michaelis acid is added, stirred and mixed evenly, and then reacted at a temperature of 104° C. for 5 hours, filtered, and dried to obtain a 7-hydroxycoumarin-3-carboxylic acid compound;

[0195] D. Synthesis of acrylic prepolymer containing coumarin structure

[0196] Ethyl acrylate, butyl acrylate, acrylic acid and the prepared 7-allyloxy-4,8-dimethylcoumarin compound are mixed uniformly in a molar ratio of 6:2:2:0.5 to obtain a monomer mixture, and then 2.2% of benzoyl peroxide initiator is added to the monomer mixture by weight, and mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 125% of butyl acetate solvent, 12% of the monomer mixture containing an initiator and 0.8% of n-dodecyl mercaptan chain transfer agent are added to the monomer mixture by weight, and stirred uniformly, and the reaction temperature of the reaction mixture is controlled at 104° C., and then the remaining monomer mixture containing an initiator is evenly divided into 15 parts, and one part is added every 12 minutes, and the reaction is carried out for 8 hours to obtain a viscous acrylic acid prepolymer containing a 7-allyloxy-4,8-dimethylcoumarin structure;

[0197] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0198] The coumarin-containing acrylic prepolymer obtained in step D is cooled to a temperature of 62° C., and then copper hydroxide and the 7-hydroxycoumarin-3-carboxylic acid compound obtained in step C are added, wherein the added amounts are 1.5 times the molar amount of acrylic acid in the coumarin-containing acrylic prepolymer, and the molar ratio of copper hydroxide to the coumarin acid compound is 1:1.2. The mixture is mixed evenly, and then 190% of a dimethyl sulfoxide solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 116° C. for 3 days to obtain the acrylic metal salt resin containing a coumarin structure.

[0199] The antifouling performance of the coumarin-containing acrylic acid metal salt resin prepared in this example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , it has an antifouling period of more than 110 days in marine environments.

[0200] Example 5: Preparation of metal acrylate resin containing coumarin structure of the present invention

[0201] The implementation steps of this embodiment are as follows:

[0202] A. Preparation of hydroxycoumarin compounds

[0203] In a round-bottom flask, 4-chlororesorcinol and ethyl acetoacetate are stirred and mixed in a molar ratio of 1:2.0 to obtain a mixture solution. At the same time, concentrated sulfuric acid of 100% of the total volume of the mixture solution is cooled to a temperature of -10°C using an ice-salt bath. The mixture solution is added to concentrated sulfuric acid under stirring for reaction for 7 hours. Then, ice water is slowly added under stirring to precipitate a precipitate, and the precipitate is filtered. The obtained filter cake is dissolved in a 5% by weight NaOH solution. The obtained solution is then extracted twice with ethyl acetate at a volume ratio of 1:1.5 between the solution and ethyl acetate. The obtained aqueous phase is acidified to pH=5 using sulfuric acid of 20% by weight under ice bath cooling, a precipitate is precipitated, and the precipitate is filtered. The obtained filter cake is recrystallized in an 80% by volume ethanol solution, filtered, and dried to obtain a 6-chloro-7-hydroxy-4-methylcoumarin compound.

[0204] B. Preparation of coumarin compounds containing C=C double bond structure

[0205] The 6-chloro-7-hydroxy-4-methylcoumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask in a molar ratio of 40:43:55:0.8, and then an acetone solvent is added to the reactants in a ratio of 12:160 of the total mass of the reactants in grams to the acetone in milliliters, and then heated under reflux at a temperature of 70° C. for 15 hours, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 46° C. and a vacuum degree of -0.09 kPa to obtain a 6-chloro-7-allyloxy-4-methylcoumarin compound;

[0206] C. Preparation of coumarin acid compounds

[0207] 2-Hydroxy-4-methoxybenzaldehyde salicylaldehyde compound and Michaelis acid are added into a round-bottom flask in a molar ratio of 20:23, and then 500% of a water solvent based on the total mass of the salicylaldehyde compound and Michaelis acid is added, stirred and mixed evenly, and then reacted at a temperature of 120° C. for 2 h, filtered, and dried to obtain a 7-hydroxycoumarin-3-carboxylic acid compound;

[0208] D. Synthesis of acrylic prepolymer containing coumarin structure

[0209] Ethyl acrylate, butyl acrylate, acrylic acid and the prepared 6-chloro-7-allyloxy-4-methylcoumarin compound are mixed uniformly in a molar ratio of 6:2:2:2.5 to obtain a monomer mixture, and then 2.7% of tert-butyl peroxide benzoyl initiator based on the weight of the monomer mixture is added and mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 180% of ethyl acetate solvent, 18% of the monomer mixture containing an initiator and 1.0% of tert-dodecyl mercaptan chain transfer agent are added based on the weight of the monomer mixture, and stirred uniformly, the reaction temperature of the reaction mixture is controlled at 110° C., and then the remaining monomer mixture containing an initiator is evenly divided into 14 parts, one part is added every 18 minutes, and the reaction is carried out for 6 hours to obtain a viscous acrylic acid prepolymer containing a 6-chloro-7-allyloxy-4-methylcoumarin structure;

[0210] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0211] The coumarin-containing acrylic prepolymer obtained in step D is cooled to a temperature of 70° C., and then copper oxide and the 7-methoxycoumarin-3-carboxylic acid compound obtained in step C are added, wherein the added amounts are 1.3 times the molar amount of acrylic acid in the coumarin-containing acrylic prepolymer, and the molar ratio of copper oxide to the coumarin acid compound is 1:1.5. The mixture is mixed evenly, and then 170% of dimethyl sulfoxide solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 124° C. for 4 days to obtain the acrylic metal salt resin containing a coumarin structure.

[0212] The antifouling performance of the coumarin-containing acrylic acid metal salt resin prepared in this example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , it has an antifouling period of more than 110 days in marine environments.

[0213] Example 6: Preparation of Metal Acrylate Resin Containing Coumarin Structure of the Present Invention

[0214] The implementation steps of this embodiment are as follows:

[0215] A. Preparation of hydroxycoumarin compounds

[0216] In a round-bottom flask, 4-chlororesorcinol and ethyl acetoacetate are stirred and mixed in a molar ratio of 1:1.2 to obtain a mixture solution. At the same time, 200% concentrated sulfuric acid based on the total volume of the mixture solution is cooled to a temperature of -5°C using an ice-salt bath. The mixture solution is added to the concentrated sulfuric acid under stirring for reaction for 7 hours. Then, ice water is slowly added under stirring to precipitate a precipitate, and the precipitate is filtered. The obtained filter cake is dissolved in a 10% by weight NaOH solution. The obtained solution is then extracted 5 times with ethyl acetate at a volume ratio of 1:3.0 between the solution and ethyl acetate. The obtained aqueous phase is acidified to pH=5 using 10% by weight sulfuric acid under ice bath cooling, a precipitate is precipitated, and the precipitate is filtered. The obtained filter cake is recrystallized in a 75% by volume ethanol solution, filtered, and dried to obtain a 6-chloro-7-hydroxy-4-methylcoumarin compound.

[0217] B. Preparation of coumarin compounds containing C=C double bond structure

[0218] The 6-chloro-7-hydroxy-4-methylcoumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask in a molar ratio of 38:46:55:0.9, and then acetone solvent is added to the reactants in a ratio of 14:170 of the total mass of the reactants in grams to acetone in milliliters, and then heated under reflux at a temperature of 68° C. for 18 hours, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 40° C. and a vacuum degree of -0.07 kPa to obtain a 6-chloro-7-allyloxy-4-methylcoumarin compound;

[0219] C. Preparation of coumarin acid compounds

[0220] 2,4-dihydroxybenzaldehyde salicylaldehyde compound and Michaelis acid are added into a round-bottom flask in a molar ratio of 20:21, and then 480% of a water solvent based on the total mass of the salicylaldehyde compound and Michaelis acid is added, stirred and mixed evenly, and then reacted at a temperature of 100° C. for 6 hours, filtered, and dried to obtain a 7-methoxycoumarin-3-carboxylic acid compound;

[0221] D. Synthesis of acrylic prepolymer containing coumarin structure

[0222] Ethyl acrylate, butyl acrylate, acrylic acid and the prepared 6-chloro-7-allyloxy-4-methylcoumarin compound are mixed uniformly in a molar ratio of 6:2:2:2.0 to obtain a monomer mixture, and then 3.2% of ammonium persulfate initiator based on the weight of the monomer mixture is added and mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 205% of a toluene and n-butanol mixture (weight ratio 4:1) solvent, 20% of the monomer mixture containing an initiator and 1.6% of a n-dodecyl mercaptan chain transfer agent are added based on the weight of the monomer mixture, and stirred uniformly, the reaction temperature of the reaction mixture is controlled at 90° C., and then the remaining monomer mixture containing an initiator is evenly divided into 13 parts, one part is added every 14 minutes, and the reaction is carried out for 7 hours to obtain a viscous 6-chloro-7-allyloxy-4-methylcoumarin structure acrylic acid prepolymer;

[0223] E. Synthesis of metal salt acrylic acid resin containing coumarin structure

[0224] The coumarin-containing acrylic prepolymer obtained in step D is cooled to a temperature of 66° C., and then zinc hydroxide and the 7-hydroxycoumarin-3-carboxylic acid compound obtained in step C are added, wherein the added amounts are 1.4 times the molar amount of acrylic acid in the coumarin-containing acrylic prepolymer, and the molar ratio of the metal zinc hydroxide to the coumarin acid compound is 1:1.4. The mixture is mixed evenly, and then 160% of N,N-dimethylformamide solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 130° C. for 5 days, thereby obtaining the acrylic metal salt resin containing a coumarin structure.

[0225] The antifouling performance of the coumarin-containing acrylic acid metal salt resin prepared in this example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , it has an antifouling period of more than 110 days in marine environments.

[0226] Comparative Example 1: Preparation of Metal Acrylate Resin

[0227] The implementation method of this comparative example is the same as the implementation step D and the implementation step E of Example 1, except that the 7-allyloxy-4-methylcoumarin compound is not used in the implementation step D, and the coumarin-3-carboxylic acid compound is not used in the implementation step E.

[0228] The antifouling performance of the acrylic acid metal salt resin prepared in this comparative example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , its antifouling period in the marine environment is much less than 110 days.

[0229] Comparative Example 2: Preparation of Metal Acrylate Resin

[0230] The implementation method of this comparative example is the same as implementation step D and implementation step E of Example 3, except that 7-allyloxy-4-methylcoumarin compound is not used in implementation step D, and 7-diethylaminocoumarin-3-carboxylic acid compound is not used in implementation step E.

[0231] The antifouling performance of the acrylic acid metal salt resin prepared in this comparative example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , its antifouling period in the marine environment is much less than 110 days.

[0232] Comparative Example 3: Preparation of Metal Acrylate Resin

[0233] The implementation method of this comparative example is the same as the implementation step D and the implementation step E of Example 5, except that the 6-chloro-7-allyloxy-4-methyl aromatic compound is not used in the implementation step D, and the 7-hydroxycoumarin-3-carboxylic acid compound is not used in the implementation step E.

[0234] The antifouling performance of the acrylic acid metal salt resin prepared in this comparative example was tested according to the method described in the specification of this application. Its actual marine antifouling effect is shown in the attached Fig.13 , its antifouling period in the marine environment is much less than 110 days.

[0235] Attached Fig.13 This is the actual marine antifouling effect of acrylic acid metal salt resin, which is attached Fig.13 It can be seen that the actual marine antifouling conditions of Examples 1-6 and Comparative Examples 1-3 show that the antifouling period of the metal acrylate resin containing coumarin structure in the actual marine environment exceeds 110 days, which is much higher than that of the metal acrylate resin without coumarin structure.

Claims

1. A metal acrylate resin containing a coumarin structure, characterized in that The metal acrylate resin has the following chemical structural formula (I): Where: R1 is H, R2 is H; or R1 is CH3, R2 is H; or R1 is H, R2 is Cl; R3 is H, -OCH3, -OH or -Et2N; X is Zn 2+ Cu 2+ Metal ions; n is a positive integer; m is 0 or a positive integer; x is 0 or a positive integer; y is a positive integer; The number average molecular weight of the above-mentioned metal acrylate resin containing coumarin structure is 2000-60000, and its molecular weight distribution is 1.0-2.

5.

2. The method for preparing the acrylic acid metal salt resin according to claim 1, characterized in that The preparation steps of the preparation method are as follows: A. Preparation of hydroxycoumarin compounds In a round-bottom flask, resorcinol or 2-methylresorcinol and ethyl acetoacetate are stirred and dissolved in a molar ratio of 1:0.8-2.0 to obtain a mixture solution, and then ZrCl4 is slowly added to the mixture solution according to 15%-25% of their total molar amount, and the mixture is vigorously stirred and reacted for 20-40 minutes at room temperature, and then ice water is slowly added to precipitate, and the precipitate is filtered by suction, and the obtained filter cake is recrystallized in an ethanol solution with a concentration of more than 90% by volume, filtered, and dried to obtain 7-hydroxy-4-methylcoumarin or 7-hydroxy-4,8-dimethylcoumarin; B. Preparation of coumarin compounds containing C=C double bond structure The hydroxy coumarin compound prepared in step A, K2CO3, 3-bromopropylene and KI reactants are added to a round-bottom flask in a molar ratio of 30-40:40-55:40-55:0.7-1.0, and then acetone solvent is added to the reactants in a ratio of 10-20:150-200 of the total mass of the reactants in grams to acetone in milliliters, and then heated to reflux for reaction at a temperature of 50°C to 70°C for 15-24h, filtered, and the collected filtrate is vacuum-rotated and dried at a temperature of 40°C to 50°C and a vacuum degree of -0.07 to -0.10kPa to obtain a coumarin compound containing a C=C double bond structure; C. Preparation of coumarin acid compounds The salicylaldehyde compound and the Michaelis acid are added to a round-bottom flask in a molar ratio of 20:20-25, and then 350%-500% of a water solvent based on the total mass of the salicylaldehyde compound and the Michaelis acid is added, stirred and mixed evenly, and then reacted at a temperature of 100-120° C. for 2-6 hours, filtered, and dried to obtain the coumarin acid compound; D. Synthesis of acrylic prepolymer containing coumarin structure Ethyl acrylate, butyl acrylate, acrylic acid and a coumarin compound containing a C=C double bond structure are mixed uniformly in a molar ratio of 6:2:2:0.05-2.5 to obtain a monomer mixture, and then 0.5%-3.2% of an initiator is added based on the weight of the monomer mixture, and the mixture is mixed uniformly to obtain a monomer mixture containing an initiator; in a round-bottom flask, 100-230% of a solvent, 10%-20% of a monomer mixture containing an initiator and 0.3%-2.0% of a chain transfer agent are added based on the weight of the monomer mixture, and the mixture is stirred uniformly, and the reaction temperature of the reaction mixture is controlled at 75°C-110°C, and then the remaining monomer mixture containing an initiator is evenly divided into 9-15 portions, and one portion is added every 10-20 minutes, and the mixture is reacted for 4-8 hours to obtain a viscous acrylic acid prepolymer containing a coumarin structure; E. Synthesis of metal salt acrylic acid resin containing coumarin structure The coumarin structure-containing acrylic prepolymer obtained in step D is cooled to a temperature below 70° C., and then a metal oxide or hydroxide and a coumarin acid compound obtained in step C are added, wherein the added amounts are 0.8 to 1.5 times the molar amount of acrylic acid in the coumarin structure-containing acrylic prepolymer, and the molar ratio of the metal oxide or hydroxide to the coumarin acid compound is 1:0.8 to 1.

5. The mixture is mixed evenly, and then 150% to 200% of a solvent based on the weight of the mixture is added to the obtained mixture, followed by reaction at a temperature of 100° C. to 130° C. for 3 to 5 days to obtain a coumarin structure-containing acrylic metal salt resin.

3. The preparation method according to claim 2, characterized in that In step A, 4-chlororesorcinol and ethyl acetoacetate are stirred and mixed in a molar ratio of 1:0.8-2.0 to obtain a mixture solution. At the same time, concentrated sulfuric acid of 100%-200% of the total volume of the mixture solution is cooled to a temperature of -10°C-5°C using an ice-salt bath. The mixture solution is added to the concentrated sulfuric acid under stirring for reaction for 3-7 hours. Then, ice water is slowly added under stirring to precipitate a precipitate, and the precipitate is filtered. The obtained filter cake is dissolved in a NaOH solution with a concentration of 5%-10% by weight. The obtained solution is then extracted 2-5 times with ethyl acetate at a volume ratio of the solution to ethyl acetate of 1:1.5-3.

0. The obtained aqueous phase is acidified to pH=5 with sulfuric acid with a concentration of 10%-20% by weight under ice bath cooling, a precipitate is precipitated, and the precipitate is filtered. The obtained filter cake is recrystallized in an ethanol solution with a concentration of more than 75% by volume, filtered, and dried to obtain 6-chloro-7-hydroxy-4-methylcoumarin.

4. The preparation method according to claim 2, characterized in that In step C, the salicylaldehyde compound is salicylaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 4-(diethylamino)salicylaldehyde or 2,4-dihydroxybenzaldehyde.

5. The preparation method according to claim 2, characterized in that In step C, the coumarin acid compound is coumarin-3-carboxylic acid, 7-methoxycoumarin-3-carboxylic acid, 7-diethylaminocoumarin-3-carboxylic acid or 7-hydroxycoumarin-3-carboxylic acid.

6. The preparation method according to claim 2, characterized in that In step D, the initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate or potassium persulfate.

7. The preparation method according to claim 2, characterized in that In step D, the solvent is one or more solvents selected from toluene, xylene, n-butanol, butyl acetate or ethyl acetate.

8. The preparation method according to claim 2, characterized in that In step D, the chain transfer agent is n-dodecyl mercaptan, tert-dodecyl mercaptan or an aliphatic mercaptan chain transfer agent.

9. The preparation method according to claim 2, characterized in that In step E, the divalent metal oxide is zinc oxide or copper oxide; the divalent metal hydroxide is zinc hydroxide or copper hydroxide; and the solvent is N,N-dimethylformamide or dimethyl sulfoxide solvent.

10. Use of the coumarin structure-containing metal acrylate resin according to claim 1 or the coumarin structure-containing metal acrylate resin prepared by the preparation method according to any one of claims 2 to 9 in marine antifouling coatings.

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