Acrylic acid self-polishing antifouling resin capable of being stripped in seawater in layered manner as well as preparation method and application of acrylic acid self-polishing antifouling resin

Abstract

The invention relates to acrylic acid self-polishing antifouling resin capable of being stripped in a layered manner in seawater as well as a preparation method and application of the acrylic acid self-polishing antifouling resin. The preparation method of the antifouling resin comprises the steps of preparing a macromolecular acrylic acid organosilicon monomer, preparing a monomer mixture containing an initiator and the like. The acrylic acid self-polishing antifouling resin capable of being stripped in the seawater in a layered manner, which is prepared by the preparation method disclosed by the invention, shows good protein adsorption resistance and antibacterial growth resistance, and can be stripped in the seawater in a layered manner, so that stains adhered to the surface of a coating are released into a marine environment along with stripping of the coating; the surface of the new coating still can show an antifouling behavior, so that the new coating shows excellent antifouling capacity in actual ocean. The self-polishing antifouling resin is simple in preparation process and low in raw material cost, and has large-scale production and application prospects.

Description

[Technical Field]

[0001] This invention belongs to the field of marine fouling biofouling control technology. More specifically, this invention relates to a self-polishing antifouling resin of acrylic acid that can be peeled off in seawater, a method for preparing the self-polishing antifouling resin of acrylic acid that can be peeled off in seawater, and the uses of the self-polishing antifouling resin of acrylic acid that can be peeled off in seawater. [Background Technology]

[0002] To reduce the harm of antifouling coatings to the marine environment, self-polishing antifouling resins, as film-forming materials in self-polishing antifouling coatings, are increasingly being used independently as a self-polishing antifouling coating. In seawater, with prolonged immersion, some polymers in the self-polishing antifouling coating gradually hydrolyze, achieving a polishing effect, typically through a structure containing metal ions. Therefore, while releasing metal ions to kill fouling organisms, the self-polishing coating also releases fouling adhering to its surface into the marine environment through polishing. However, this localized polishing has limited effectiveness in releasing fouling adhering to the coating; therefore, it is necessary to develop self-polishing antifouling coatings with suitable polishing properties.

[0003] The inventors have developed a self-polishing antifouling coating that can be completely peeled off layer by layer in seawater. Through the complete peeling off of the surface layer, it can release metal ions to kill fouling organisms and also completely release the fouling adhering to the coating surface.

[0004] Based on a summary of existing technologies, the inventors completed this invention through extensive experimental research and analysis. [Summary of the Invention]

[0005] [Technical problem to be solved]

[0006] The purpose of this invention is to provide an acrylic self-polishing antifouling resin that can be peeled off in seawater in layers.

[0007] Another object of the present invention is to provide a method for preparing the acrylic self-polishing antifouling resin that can be peeled off in seawater.

[0008] Another object of the present invention is to provide the use of the described layered peelable acrylic self-polishing antifouling resin in seawater.

[0009] [Technical Solution]

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

[0011] The present invention also relates to a method for preparing an acrylic self-polishing antifouling resin that can be peeled off in seawater.

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

[0013] A. Preparation of macromolecular acrylic acid organosilicon monomers

[0014] The hydroxy acrylate and organosilicon monomer are mixed evenly at a molar ratio of 1:0.5-5.0. Then, 0.5-1.5% catalyst and 30-300% organic solvent (based on the mass of organosilicon monomer) are added and mixed evenly. The mixture is then reacted at 125-135°C for 3.5-5.0 hours to obtain the macromolecular acrylic organosilicon monomer.

[0015] B. Preparation of monomer mixtures

[0016] Oily acrylate monomers, acrylic monomers, acrylamide monomers, water-based acrylate monomers, and macromolecular acrylic organosilicon monomers obtained in step A are mixed evenly in a molar ratio of 25-65:5-25:5-15:10-40:3-20. Then, 0.2-1.5% of initiator based on the total mass of monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0017] C. Preparation of acrylic acid prepolymer

[0018] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 100-300% of the total mass of the initiator-containing monomer mixture obtained in step B and 5-15% of the initiator-containing monomer mixture were added and mixed thoroughly. The mixture was then heated to 65-95°C and maintained at this temperature for 12-45 minutes. The remaining initiator-containing monomer mixture was then divided into 3-10 equal portions, with one portion added every 15-35 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for 1 hour. Then, 0.05-0.15% of the initiator was added based on the total mass of the initiator-containing monomer mixture, and the reaction was continued for 1-4 hours to obtain the acrylic acid prepolymer.

[0019] D. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0020] Under nitrogen protection, metal oxides or hydroxides and organic acids are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of metal oxides or hydroxides to the acrylic acid monomers is 0.5-1.5:1.0, and the molar ratio of metal oxides or hydroxides to organic acids is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the total mass ratio of mixed organic solvent to metal oxides or hydroxides and organic acids of 0-10:1.0, mixed evenly, and then reacted at a temperature of 85-100°C for 3-6 hours to obtain the acrylic acid self-polishing antifouling resin prepolymer.

[0021] E. Preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater.

[0022] The crosslinking agent is 10-80% of the molar amount of carboxyl, hydroxyl or amino groups of the acrylic self-polishing antifouling resin prepolymer. The hydrogel acrylic self-polishing antifouling resin prepolymer obtained in step D is mixed with the crosslinking agent at a temperature of 15-40°C. Under these conditions, it is dried until the solvent content of the dried product is less than 1% by weight, thus obtaining an acrylic self-polishing antifouling resin that can be peeled off in seawater.

[0023] According to a preferred embodiment of the present invention, in step A, the hydroxy acrylate is one or more hydroxy acrylates selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or hydroxybutyl 4-acrylate; the catalyst is one or more catalysts selected from tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, or dibutyltin dilaurate; and the organosilicon monomer is one or more catalysts selected from DOWSIL. TM RSN-6018Resin Intermediate, DOWSIL TM RSN-0249Flake Resin, DOWSIL TM RSN-0806Resin,DOWSIL TM RSN-0804Resin or DOWSIL TM RSN-0805Resin is an organosilicon monomer.

[0024] According to another preferred embodiment of the present invention, in step B, the oily acrylate monomer is one or more of the following oily acrylate monomers: 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; the acrylic monomer is one or more acrylic monomers selected from acrylic acid, methacrylic acid, or itaconic acid; the acrylamide monomer is one or more acrylamide monomers selected from acrylamide, N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, N,N-methylenebisacrylamide, or N,N-dimethylacrylamide; the watery acrylate monomer is one or more watery acrylic monomers selected from hydroxy acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or 3-(dimethylamino)propyl acrylate.

[0025] According to another preferred embodiment of the present invention, in steps B and C, the initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, potassium persulfate, or ammonium persulfate.

[0026] According to another preferred embodiment of the present invention, in step AD, the organic solvent is one or more solvents selected from n-butanol, ethanol, toluene, xylene, butyl acetate, cyclohexanone or methyl isobutyl ketone.

[0027] According to another preferred embodiment of the present invention, in step D, the metal oxide is zinc oxide, copper oxide, magnesium oxide or calcium oxide; the metal hydroxide is magnesium hydroxide, calcium hydroxide, zinc hydroxide or copper hydroxide; and the organic acid is benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, lactic acid, polylactic acid, rosin acid, amino acid, salicylic acid or furoic acid.

[0028] According to another preferred embodiment of the present invention, in step E, the crosslinking agent is glutaraldehyde, succinaldehyde, aziridine CX100, aziridine CX300, aziridine XR100, epoxy silane crosslinking agent XR-500, or glycidyl ether.

[0029] The present invention also relates to an acrylic self-polishing antifouling resin that can be delaminated in seawater by the preparation method described above.

[0030] The present invention also relates to the use of the aforementioned self-polishing antifouling acrylic resin that can be peeled off in seawater in preventing marine fouling.

[0031] The invention will now be described in more detail.

[0032] This invention relates to a method for preparing an acrylic self-polishing antifouling resin that can be peeled off in seawater.

[0033] Currently available self-polishing antifouling resin coatings achieve their antifouling purpose through partial hydrolysis of the resin polymer chains. This localized polishing results in incomplete removal of surface-adhered contaminants. To address the shortcomings of existing technologies, the inventors propose introducing monomers with significantly different molecular weights and hydrophilic / hydrophobic properties, resulting in different polymer distributions across different layers of the coating. This causes a noticeable difference in water absorption between the surface and underlying layers of the self-polishing antifouling resin coating in seawater. Over time, the excessively absorbent surface layer becomes fragile and eventually breaks down, polishing the coating. The exposed underlying layer then exhibits the same result with prolonged immersion, thus achieving layered peeling of the coating in seawater.

[0034] This invention relates to a method for preparing an acrylic self-polishing antifouling resin that can be peeled off in seawater.

[0035] The preparation steps of this method are as follows:

[0036] A. Preparation of macromolecular acrylic acid organosilicon monomers

[0037] The hydroxy acrylate and organosilicon monomer are mixed evenly at a molar ratio of 1:0.5-5.0. Then, 0.5-1.5% catalyst and 30-300% organic solvent (based on the mass of organosilicon monomer) are added and mixed evenly. The mixture is then reacted at 125-135°C for 3.5-5.0 hours to obtain the macromolecular acrylic organosilicon monomer.

[0038] In this invention, the role of hydroxyl acrylate in the preparation of macromolecular acrylic organosilicon monomers is to provide hydroxyl groups that undergo dehydration condensation reactions with the hydroxyl groups in the organosilicon monomers, thereby endowing the organosilicon monomers with double bonds that can participate in free radical polymerization.

[0039] The hydroxy acrylates used in this invention are one or more hydroxy acrylates selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or hydroxybutyl 4-acrylate. These are all products currently sold on the market, such as those sold by McLean under the trade name hydroxypropyl acrylate, and those sold by Shanghai Aladdin under the trade name hydroxypropyl methacrylate.

[0040] In this invention, the organosilicon monomer should be understood as an organosilicon resin. Its main role in preparing a self-polishing antifouling acrylic resin that can be peeled off in seawater is that, as a high molecular weight reactive monomer, it exhibits different aggregation capabilities compared to low molecular weight monomers during the polymerization process, causing the resin polymer to produce different aggregations. At the same time, it can improve the hardness of the antifouling resin and improve its mechanical properties.

[0041] The organosilicon monomers used in this invention are one or more selected from DOWSIL. TM RSN-6018ResinIntermediate, DOWSIL TM RSN-0249Flake Resin, DOWSIL TM RSN-0806Resin,DOWSIL TM RSN-0804Resin or DOWSIL TM RSN-0805Resin's organosilicon monomers are all commercially available products, such as those marketed by Dow Chemical Company under the trade name DOWSIL. TM RSN-6018ResinIntermediate sells products under the trade name DOWSILTM RSN-0249Flake Resin sells products under the trade name DOWSIL TM RSN-0806Resin sells products under the trade name DOWSIL TM RSN-0804Resin sells products under the trade name DOWSIL TM RSN-0805 is a product sold by Resin.

[0042] In this step, the molar ratio of hydroxy acrylate to organosilicon monomer is 1:0.5–5.0. If the molar ratio is greater than 1:0.5, there will be excessive hydroxy acrylate residue, resulting in waste, and it is prone to self-polymerization, affecting the next step of the reaction. If the molar ratio is less than 1:5.0, there will be too much organosilicon monomer residue, resulting in waste. Therefore, a molar ratio of hydroxy acrylate to organosilicon monomer of 1:0.5–5.0 is appropriate, preferably 1:1.0–4.4, and more preferably 1.6–3.8.

[0043] In this invention, the catalyst plays a role in the preparation of acrylic organosilicon monomers by promoting the reaction between hydroxyl acrylates and organosilicon resins.

[0044] The catalyst used in this invention is one or more catalysts selected from tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, or dibutyltin dilaurate. These are all commercially available products, such as tetrabutyl titanate sold by Maclean Company under the trade name tetrabutyl titanate, stannous octoate sold by Maclean Company under the trade name stannous isooctanoate, and dibutyltin dilaurate sold by Sinopharm Chemical Reagent Co., Ltd. under the trade name dibutyltin dilaurate.

[0045] In this step, if the amount of catalyst used is less than 0.5%, the reaction will not be catalyzed; if the amount of catalyst used is more than 1.5%, it may be excessive, resulting in catalyst waste and being economically disadvantageous. Therefore, a catalyst amount of 0.5% to 1.5% is appropriate, preferably 0.7% to 1.3%, and more preferably 0.8% to 1.2%.

[0046] The organic solvent used in this step is one or more solvents selected from n-butanol, ethanol, toluene, xylene, butyl acetate, cyclohexanone, or methyl isobutyl ketone. These are all commercially available products, such as xylene sold by Qingdao Datang Chemical Co., Ltd. under the trade name xylene, cyclohexanone sold by Qingdao Datang Chemical Co., Ltd. under the trade name cyclohexanone, and methyl isobutyl ketone sold by Qingdao Datang Chemical Co., Ltd. under the trade name methyl isobutyl ketone. The solvents used in subsequent steps are the same as those mentioned above, and therefore will not be described again.

[0047] Then, 0.5–1.5% catalyst and 30–300% organic solvent (based on the mass of the organosilicon monomer) are added to the above-mentioned mixture of hydroxyl acrylate and organosilicon monomer. When the amount of organic solvent is within the aforementioned range, if the amount of catalyst is less than 0.5%, the reaction will not be catalyzed; if the amount of catalyst is greater than 1.5%, the amount of catalyst may be excessive, resulting in catalyst waste, which is economically disadvantageous. Therefore, an amount of catalyst of 0.5–1.5% is reasonable, preferably 0.8–1.3%, and more preferably 0.9–1.1%.

[0048] When the amount of catalyst is within the aforementioned range, if the amount of organic solvent is less than 30%, the viscosity of the mixed solution of hydroxyl acrylate and organosilicon monomer will be too high, resulting in an uneven reaction. If the amount of organic solvent is greater than 300%, it will result in a large amount of volatile organic compounds in the subsequent preparation process, polluting the environment and wasting resources. Therefore, an amount of organic solvent of 30-300% is appropriate, preferably 80-220%, and more preferably 120-180%.

[0049] Hydroxy acrylate and organosilicon monomer organic solution are reacted in the presence of a catalyst at a temperature of 125–135°C for 3.5–5.0 hours to obtain the macromolecular acrylic organosilicon monomer.

[0050] When the reaction time is within the specified range, if the reaction temperature is below 125°C, the reaction will be difficult to occur or proceed slowly, which is not conducive to improving efficiency; if the reaction temperature is above 135°C, the side reactions will increase, which is not conducive to obtaining the target product; therefore, a reaction temperature of 125-135°C is desirable, preferably 127-133°C, and more preferably 128-132°C.

[0051] When the reaction temperature is within the specified range, if the reaction time is less than 3.5 hours, the reaction will be incomplete; if the reaction time is more than 5.0 hours, there will be too much remaining time after the reaction is completed, which is detrimental to the efficiency of the process. Therefore, a reaction time of 3.5 to 5.0 hours is appropriate, preferably 3.7 to 4.8 hours, and more preferably 4.0 to 4.6 hours.

[0052] According to the standard analytical method of Fourier transform attenuated total reflectance infrared spectroscopy, the product obtained in this step is a macromolecular acrylic organosilicon monomer.

[0053] B. Preparation of monomer mixtures

[0054] Oily acrylate monomers, acrylic monomers, acrylamide monomers, water-based acrylate monomers, and macromolecular acrylic silicone monomers obtained in step A are mixed evenly in a molar ratio of 25-65:5-25:5-15:10-40:3-20. Then, 0.2-1.5% of initiator based on the total mass of the above monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0055] In this invention, the oily acrylate monomer should be understood as an acrylate monomer without hydrophilic groups. Its main role in the self-polishing antifouling acrylic resin that can be peeled off in seawater is to provide a large number of hydrophobic groups, which can exert a hydrophobic association effect and give the coating good adhesion.

[0056] The oily acrylate monomers used in this invention are one or more 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. These are all products currently sold on the market, such as methyl acrylate sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name methyl acrylate, butyl methacrylate sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name butyl methacrylate, tetradecyl methacrylate sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name tetradecyl methacrylate, and octadecyl acrylate sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name octadecyl acrylate.

[0057] In this invention, the main role of acrylic monomers in the preparation of acrylic self-polishing antifouling resins that can be peeled off in seawater is that they undergo dehydration condensation reactions with metal oxides or hydroxides to graft metal ions, and they form cross-linked structures with cross-linking agents to provide a three-dimensional network structure.

[0058] The acrylic monomer used in this invention is one or more acrylic monomers selected from acrylic acid, methacrylic acid or itaconic acid. These are all products currently sold on the market, such as acrylic acid sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name acrylic acid, and itaconic acid sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name itaconic acid.

[0059] In this invention, the main role of acrylamide monomer in the preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater is to maintain sufficient hardness in the resin and give it good mechanical properties.

[0060] The acrylamide monomer used in this invention is one or more acrylamide monomers selected from acrylamide, N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, N,N-methylenebisacrylamide or N,N-dimethylacrylamide. These are all products currently sold on the market, such as acrylamide sold by Jiangxi Jiuchang Agricultural Science and Technology Chemical Co., Ltd. under the trade name acrylamide, N-hydroxymethylacrylamide sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name N-hydroxymethylacrylamide, and N,N-methylenebisacrylamide sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name N,N-methylenebisacrylamide.

[0061] In this invention, the waterborne acrylate monomer should be understood as a monomer containing hydrophilic groups and having an affinity for water. Its main function in preparing a self-polishing antifouling acrylic resin that can be peeled off in seawater is that it can provide water-absorbing hydrophilic groups, which is beneficial for the resin surface to absorb water and swell, thereby promoting surface peeling.

[0062] The aqueous acrylate monomers used in this invention are one or more aqueous acrylate monomers selected from hydroxy acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or propyl 3-(dimethylamino)acrylate. These are all products currently sold on the market, such as hydroxyethyl acrylate sold by Sinopharm Chemical Reagent Co., Ltd. under the trade name hydroxyethyl acrylate, dimethylaminoethyl acrylate sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name dimethylaminoethyl acrylate, and dimethylaminoethyl methacrylate sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name dimethylaminoethyl methacrylate.

[0063] In this step, when the amounts of acrylic monomer, acrylamide monomer, waterborne acrylate monomer, and macromolecular acrylic silicone monomer are within the specified range, if the amount of oily acrylate monomer is less than 25%, the hydrophobic structure content in the acrylic self-polishing antifouling resin will be too low, which is not conducive to the resin adhering to the substrate. If the amount of oily acrylate monomer is higher than 65%, the content of oily structural units will be too high, and the content of structural units with other properties will be too low, which is not conducive to the formation of a layered structure and the delamination of the acrylic self-polishing antifouling resin in seawater. Therefore, an amount of oily acrylate monomer of 25-65% is reasonable, preferably 32-58%, and more preferably 36-54%.

[0064] When the amounts of oil-based acrylate monomers, acrylamide monomers, water-based acrylate monomers, and macromolecular acrylic silicone monomers are within the aforementioned range, if the amount of acrylic monomer is less than 5%, the amount of metal ions and molecular acids grafted onto the coating will be too low, reducing the coating's antifouling ability. If the amount of acrylic monomer is greater than 25%, the prepolymer will easily gel, and after subsequent grafting of metal ions, the viscosity of the resin system will be too high, which is not conducive to subsequent construction. Therefore, an amount of acrylic monomer of 5–25% is appropriate, preferably 8–22%, and more preferably 10–20%.

[0065] When the amounts of oil-based acrylate monomers, acrylic monomers, water-based acrylate monomers, and macromolecular acrylic silicone monomers are within the aforementioned range, if the amount of acrylamide monomer is less than 5%, the hardness of the self-polishing antifouling resin coating will be too low, which is not conducive to maintaining its shape in practical applications; if the amount of acrylamide monomer is more than 15%, the viscosity will be too high or even gel during the reaction, which is not conducive to the normal progress of the reaction. Therefore, an amount of acrylamide monomer of 5 to 15% is suitable, preferably 7 to 13%, and more preferably 9 to 11%.

[0066] When the amounts of oil-based acrylate monomers, acrylic monomers, acrylamide monomers, and macromolecular acrylic silicone monomers are within the aforementioned range, if the amount of water-based acrylate monomer is less than 10, it is not conducive to the formation of a surface water layer by the self-polishing and antifouling resin coating, and it is not conducive to coating peeling; if the amount of water-based acrylate monomer is more than 40, it will lead to an excessively high content of hydrophilic groups in the resin coating, resulting in excessive water absorption by the coating, thereby greatly reducing the coating's adhesion. Therefore, an amount of water-based acrylate monomer of 10-40 is appropriate, preferably 15-35, and more preferably 18-32.

[0067] When the amounts of oil-based acrylate monomers, acrylic monomers, acrylamide monomers, and water-based acrylate monomers are within the aforementioned range, if the amount of macromolecular acrylic silicone monomer is less than 3%, it is not conducive to the formation of a significantly uneven polymer in the self-polishing antifouling resin, resulting in the inability to peel off the subsequent self-polishing resin coating in layers. If the amount of macromolecular acrylic silicone monomer is greater than 20%, it results in excessive viscosity of the resin polymer system, which is not conducive to subsequent construction. Therefore, an amount of macromolecular acrylic silicone monomer of 3 to 20% is appropriate, preferably 5 to 18%, and more preferably 8 to 15%.

[0068] Preferably, the molar ratio of oily acrylate monomer, acrylic monomer, acrylamide monomer, water-based acrylate monomer to macromolecular acrylic silicone monomer is 32-58:8-22:7-13:15-35:5-18.

[0069] More preferably, the molar ratio of oily acrylate monomer, acrylic monomer, acrylamide monomer, watery acrylate monomer to macromolecular acrylic silicone monomer is 36-54:10-20:9-11:18-32:8-15.

[0070] According to the present invention, the main role of the initiator in the preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater is that it decomposes into active free radicals, thereby initiating the polymerization reaction of the monomers to generate a polymer.

[0071] The initiator used in this invention is one or more selected from azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, potassium persulfate, or ammonium persulfate. These are all products currently sold on the market, such as azobisisobutyronitrile sold by Tianjin Damao Chemical Reagent Factory under the trade name azobisisobutyronitrile, benzoyl tert-butyl peroxide sold by Tianjin Hedong Hongyan Reagent Factory under the trade name benzoyl tert-butyl peroxide, and methyl ethyl ketone peroxide sold by Wuhan Jiyesheng Chemical Co., Ltd. under the trade name methyl ethyl ketone peroxide.

[0072] The same initiator is used in the subsequent steps of preparing the self-polishing antifouling acrylic resin that can be peeled off in seawater in this invention, so it will not be described again.

[0073] Next, 0.2% to 1.5% initiator, based on the total mass of the monomers, is added to the above monomer mixture. If the amount of initiator is higher than 1.5%, it will lead to a decrease in the molecular weight of the acrylic self-polishing antifouling resin that can be delaminated in seawater, which is detrimental to the improvement of its mechanical properties; if the amount of initiator is lower than 0.2%, it will lead to unstable polymerization reaction initiated by it, or even make it difficult to initiate polymerization reaction; therefore, an initiator amount of 0.2% to 1.5% is reasonable, preferably 0.4% to 1.2%, and more preferably 0.6% to 1.0%.

[0074] C. Preparation of acrylic acid prepolymer

[0075] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 100-300% of the mixed organic solvent and 5-15% of the initiator-containing monomer mixture obtained in step B were added and mixed thoroughly. The mixture was then heated to 65-95°C and maintained at this temperature for 12-45 minutes. The remaining initiator-containing monomer mixture was then divided into 3-10 equal portions, with one portion added every 15-35 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for 1 hour. Then, 0.05-0.15% of the initiator was added based on the total mass of the initiator-containing monomer mixture, and the reaction was continued for 1-4 hours to obtain the acrylic acid prepolymer.

[0076] In this step, the mixture obtained by mixing 100-300% of the mixed organic solvent with 5-15% of the monomer mixture containing the initiator is kept at a temperature of 65-95°C for 12-45 minutes. The purpose is to allow the initiation to occur fully, which helps to stabilize the initiation of subsequent reactions.

[0077] When the amount of the initiator monomer mixture, reaction temperature, and reaction time are within the aforementioned range, if the amount of mixed organic solvent is less than 100%, it will lead to high viscosity of the prepolymer in the later stage of the reaction, uneven reaction, and uneven molecular weight distribution of the obtained prepolymer, affecting the performance of the coating. If the amount of mixed organic solvent is greater than 300%, it will result in more volatile organic compounds during later use, polluting the environment and wasting resources. Therefore, a mixed organic solvent amount of 100% to 300% is suitable, preferably 140% to 250%, and more preferably 160% to 220%.

[0078] When the amount of mixed organic solvent, reaction temperature, and reaction time are within the aforementioned ranges, if the amount of the monomer mixture containing the initiator is less than 5%, it is easy to cause subsequent accumulation of the monomer mixture, leading to instability in the subsequent reaction; if the amount of the monomer mixture is greater than 15%, it will cause violent reaction in the initial stage, making it difficult to control the temperature of the reaction system and posing safety hazards. Therefore, an amount of 5-15% of the monomer mixture is appropriate, preferably 7-13%, and more preferably 9-11%.

[0079] When the amounts of mixed organic solvent, initiator-containing monomer mixture, and reaction time are within the aforementioned ranges, if the reaction temperature is below 65°C, it is not conducive to initiator decomposition, thus making it difficult for the polymerization reaction to proceed stably. If the reaction temperature is above 95°C, the reaction will be too vigorous, posing some safety hazards and causing uneven reaction, affecting coating performance. Therefore, a reaction temperature of 65–95°C is suitable, preferably 70–90°C, and more preferably 72–88°C.

[0080] When the amount of mixed organic solvent, the amount of initiator-containing monomer mixture, and the reaction temperature are within the ranges described, if the reaction time is less than 12 minutes, the reaction cannot be fully initiated, leading to instability in subsequent reactions; if the reaction time is longer than 45 minutes, dead-end polymerization is likely to occur, which is not conducive to improving process efficiency; therefore, a reaction time of 12 to 45 minutes is appropriate, preferably 18 to 38 minutes, and more preferably 22 to 34 minutes.

[0081] In this step, the remaining monomer mixture containing the initiator is divided into 3 to 10 equal parts, and one part is added every 15 to 35 minutes. The main purpose is to avoid adding too much monomer mixture at once, which would prevent it from being dispersed into the reaction system in time. It also avoids the reaction from being too violent, causing the temperature to rise, the reaction to be unstable, and the risk of danger.

[0082] The purpose of continuing the reaction at a constant temperature for 1 hour after adding the initiator-containing monomer mixture is to ensure that the unreacted monomers in the system react and polymerize completely. Continuing the reaction for 1–4 hours after adding the initiator is primarily to guarantee that the unreacted monomers fully react and polymerize.

[0083] D. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0084] Under nitrogen protection, metal oxides or hydroxides and organic acids are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of metal oxides or hydroxides to the acrylic acid monomers is 0.5-1.5:1.0, and the molar ratio of metal oxides or hydroxides to organic acids is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the total mass ratio of mixed organic solvent to metal oxides or hydroxides and organic acids of 0-10:1.0, mixed evenly, and then reacted at a temperature of 85-100°C for 3-6 hours to obtain the acrylic acid self-polishing antifouling resin prepolymer.

[0085] In this invention, the main role of metal oxides or hydroxides in the preparation of acrylic self-polishing antifouling resins that can be peeled off in seawater is to provide metal ions that can undergo ion exchange in seawater to enable the coating to achieve self-polishing.

[0086] The metal oxides used in this invention are zinc oxide, copper oxide, magnesium oxide, or calcium oxide; the metal hydroxides used in this invention are magnesium hydroxide, calcium hydroxide, zinc hydroxide, or copper hydroxide, all of which are currently commercially available products, such as zinc oxide sold by Tianjin Tianjiao Chemical Co., Ltd. under the trade name zinc oxide.

[0087] The molar ratio of the metal oxide or hydroxide to the acrylic monomer used in step B is 0.5–1.5:1.0. Exceeding this range is undesirable, as it ensures sufficient reaction within this range; otherwise, excessive residues of metal oxide, hydroxide, or acrylic monomer may result.

[0088] The molar ratio of the metal oxide or hydroxide to the organic acid is 1.0:1.0. A molar ratio higher than 1.0:1.0 is undesirable because some metal oxides or hydroxides will not participate in the reaction, resulting in waste.

[0089] In this invention, the main role of organic acids in the preparation of acrylic self-polishing antifouling resin that can be peeled off in seawater is to undergo a dehydration condensation reaction with metal oxides or metal hydroxides.

[0090] The organic acids used in this invention are benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, lactic acid, polylactic acid, rosin acid, amino acids, salicylic acid, or furoic acid. These are all products currently sold on the market, such as benzoic acid sold by Tianjin Damao Chemical Reagent Co., Ltd. under the trade name benzoic acid, and lauric acid sold by Nantong Zhonghe Chemical New Materials Co., Ltd. under the trade name lauric acid.

[0091] The mass ratio of organic solvent to the total mass of metal oxide or hydroxide and organic acid is 0–10:1.0. If the viscosity of the acrylic prepolymer prepared in step C is less than 2000 cp, the amount of organic solvent can be 0; if the mass ratio of organic solvent to the total mass of metal oxide or hydroxide and organic acid is greater than 10:1.0, the resin viscosity will be too low and solvent will be wasted; therefore, a mass ratio of organic solvent to the total mass of metal oxide or hydroxide and organic acid of 0–10:1.0 is appropriate, preferably 1.0–8.0:1.0, and more preferably 2.0–7.0:1.0.

[0092] After adding an organic solvent, the acrylic prepolymer, metal oxide, or hydroxide reacts with the organic acid at a temperature of 85–100°C for 3–6 hours. Within this range, if the reaction temperature is below 85°C, the reaction is not conducive to its proper progress; if the reaction temperature is above 100°C, the reaction becomes too vigorous, which is not conducive to the formation of the acrylic self-polishing antifouling resin prepolymer. Therefore, a reaction temperature of 85–100°C is reasonable, preferably 88–96°C, and more preferably 90–94°C.

[0093] When the reaction temperature is within the specified range, if the reaction time is less than 3 hours, the reaction will be incomplete, leaving a large amount of unreacted compounds; if the reaction time is longer than 6 hours, the reaction effect will not be significantly improved, but its efficiency will be significantly reduced. Therefore, a reaction time of 3 to 6 hours is suitable, preferably 3.6 to 5.4 hours, and more preferably 4.0 to 5.0 hours.

[0094] E. Preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater.

[0095] The crosslinking agent is 10-80% of the molar amount of carboxyl, hydroxyl or amino groups of the acrylic self-polishing antifouling resin prepolymer. The hydrogel acrylic self-polishing antifouling resin prepolymer obtained in step D is mixed with the crosslinking agent at a temperature of 15-40°C. Under these conditions, it is dried until the solvent content of the dried product is less than 1% by weight, thus obtaining an acrylic self-polishing antifouling resin that can be peeled off in seawater.

[0096] According to the present invention, the main role of the crosslinking agent in the preparation of the acrylic self-polishing antifouling resin that can be peeled off in seawater is that it reacts with the carboxyl, hydroxyl or amine groups of the acrylic self-polishing antifouling resin prepolymer to form a three-dimensional network structure of the acrylic self-polishing antifouling resin prepolymer.

[0097] The crosslinking agents used in this invention are glutaraldehyde, succinaldehyde, aziridine CX100, aziridine CX300, aziridine XR100, epoxy silane crosslinking agent XR-500, or glycidyl ether. These are all products currently available on the market. For example, aziridine CX300 crosslinking agent sold by Shanghai Chemical Reagent Research Institute under the trade name aziridine crosslinking agent (TTMAP), and epoxy silane crosslinking agent XR-500 sold by Shanghai Xirun Chemical Technology Co., Ltd. under the trade name epoxy silane crosslinking agent XR-500.

[0098] In this step, the amount of crosslinking agent is 10-80% of the molar amount of carboxyl, hydroxyl, or amino groups in the acrylic self-polishing antifouling resin prepolymer. If the amount of crosslinking agent is higher than 80%, the cohesive force of the acrylic self-polishing antifouling resin that can be peeled off in seawater will be too large, causing the coating to crack during use, which is not conducive to application. If the amount of crosslinking agent is lower than 10%, the crosslinking will be incomplete, and a sufficient crosslinking network cannot be formed in the acrylic self-polishing antifouling resin. Therefore, a crosslinking agent amount of 10-80% is desirable, preferably 18-72%, and more preferably 22-68%.

[0099] The acrylic self-polishing antifouling resin prepolymer and crosslinking agent are mixed uniformly at a temperature of 15–40°C. If the mixing temperature of the acrylic self-polishing antifouling resin prepolymer and crosslinking agent is below 15°C, the activity of the crosslinking agent will decrease, and it will not be able to undergo a sufficient crosslinking reaction with the acrylic self-polishing antifouling resin prepolymer, thereby reducing the degree of crosslinking of the acrylic self-polishing antifouling resin of the present invention. If the mixing temperature of the acrylic self-polishing antifouling resin and crosslinking agent is above 40°C, the activity of the crosslinking agent will increase, and the acrylic self-polishing antifouling resin will quickly become a gel state, which is not conducive to construction and is prone to causing coating cracking. Therefore, a mixing temperature of 15–40°C for the acrylic self-polishing antifouling resin prepolymer and crosslinking agent is suitable, preferably 18–38°C, and more preferably 20–36°C.

[0100] The reaction vessel, electric stirring device, oil bath, drying device, etc. used in this invention are all commonly used chemical equipment or devices in the field of chemical technology.

[0101] This invention also relates to the use of the aforementioned self-polishing acrylic antifouling resin, which can be peeled off in seawater, in preventing marine biofouling. This invention investigated the antifouling performance of the self-polishing acrylic antifouling resin in seawater, including its anti-protein adsorption properties, through protein adsorption experiments; its antibacterial properties, including its ability to inhibit bacterial growth and adhesion, through antifouling experiments; and its antifouling performance in actual marine environments and its peeling off in seawater, through a real-sea siding experiment. For details, please refer to the detailed embodiments section.

[0102] [Beneficial Effects]

[0103] The beneficial technical effects of this invention are as follows: The self-polishing antifouling resin of this invention, which can be peeled off in seawater in layers, allows its hydrophilic groups to combine with water molecules to form a hydration layer, preventing the adhesion of marine biofouling substances such as proteins in the first stage. The release of metal ions through side-chain hydrolysis can harm the fouling organisms and prevent the adhesion of bacteria. The layered peeling of the self-polishing resin coating surface allows for self-renewal of the coating surface, promoting the release of attached fouling substances, thereby achieving an antifouling effect. This resin has good film-forming properties, storage stability, and application performance, and exhibits excellent antifouling effects, making it suitable for large-scale production in antifouling applications. [Attached Image Description]

[0104] Appendix Figure 1 These are the experimental results of the anti-protein adsorption of the acrylic self-polishing antifouling resin that can be peeled off in seawater in Examples 1-3;

[0105] Appendix Figure 2 The diagram shows the antibacterial growth results of the acrylic self-polishing antifouling resin that can be peeled off in seawater in Examples 1-5.

[0106] Appendix Figure 3 These are actual sea-based cladding results prepared from acrylic self-polishing antifouling resins that can be peeled off in seawater in Examples 1-2 and acrylic self-polishing antifouling resins that cannot be peeled off in seawater in Example 6.

Detailed Implementation Methods

[0107] Example 1: Preparation of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to the present invention

[0108] The implementation steps of this embodiment are as follows:

[0109] A. Preparation of macromolecular acrylic acid organosilicon monomers

[0110] Hydroxypropyl acrylate and DOWSIL TM RSN-6018Resin Intermediate organosilicon monomers were mixed uniformly at a molar ratio of 1:0.5, and then 0.5% stannous octoate catalyst and 30% toluene organic solvent were added based on the mass of the organosilicon monomers. The mixture was mixed uniformly and reacted at 125°C for 5.0 hours to obtain the macromolecular acrylic organosilicon monomers.

[0111] B. Preparation of monomer mixtures

[0112] Butyl acrylate oily acrylate monomer, acrylic acid acrylic acid monomer, acrylamide acrylamide monomer, dimethylaminoethyl methacrylate watery acrylate monomer and macromolecular acrylic organosilicon monomer obtained in step A are mixed evenly in a molar ratio of 25:5:5:10:20. Then, 0.2% azobisisobutyronitrile initiator based on the total mass of monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0113] C. Preparation of acrylic acid prepolymer

[0114] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 100% xylene and n-butanol (mass ratio 3:2) mixed organic solvent and 15% initiator-containing monomer mixture were added. The mixture was stirred until homogeneous, then heated to 65°C and maintained at this temperature for 45 minutes. The remaining initiator-containing monomer mixture was then divided into three equal portions, with one portion added every 35 minutes. After the initiator-containing monomer mixture was completely added, the mixture was maintained at this temperature for 1 hour. Then, 0.05% azobisisobutyronitrile initiator (based on the total mass of the initiator-containing monomer mixture) was added, and the reaction was continued for 4 hours to obtain the acrylic acid prepolymer.

[0115] D. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0116] Under nitrogen protection, zinc oxide and copper hydroxide (molar ratio 1:1) and benzoic acid and lactic acid (molar ratio 7:3) organic acids are added to the acrylic acid prepolymer obtained in step C; wherein the total molar ratio of zinc oxide and copper hydroxide to the above acrylic acid monomer is 0.5:1.0, and the molar ratio of zinc oxide and copper hydroxide to benzoic acid and lactic acid is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the mass ratio of the mixed organic solvent to the total mass of zinc oxide and copper hydroxide and benzoic acid and lactic acid is 0:1.0, mixed evenly, and then reacted at a temperature of 85°C for 6 hours to obtain the acrylic self-polishing antifouling resin prepolymer.

[0117] E. Preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater.

[0118] The acrylic self-polishing antifouling resin prepolymer obtained in step D was mixed with aziridine CX100 crosslinking agent at a temperature of 15°C until the solvent content of the dried product was less than 1% by weight, in accordance with the crosslinking agent being 80% of the carboxyl molar amount of the acrylic self-polishing antifouling resin prepolymer.

[0119] Example 2: Preparation of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to the present invention

[0120] The implementation steps of this embodiment are as follows:

[0121] A. Preparation of macromolecular acrylic acid organosilicon monomers

[0122] Hydroxyethyl acrylate and DOWSIL TM RSN-6018ResinIntermediate organosilicon monomers were mixed uniformly at a molar ratio of 1:5.0, and then 1.5% tetrabutyl titanate catalyst and 300% toluene organic solvent (based on the mass of organosilicon monomers) were added and mixed uniformly. The mixture was then reacted at 135°C for 3.5 hours to obtain the macromolecular acrylic organosilicon monomer.

[0123] B. Preparation of monomer mixtures containing initiators

[0124] Ethyl acrylate oily acrylate monomer, itaconic acid acrylate monomer, acrylamide acrylamide monomer, dimethylaminoethyl methacrylate watery acrylate monomer, and the macromolecular acrylic organosilicon monomer obtained in step A are mixed evenly in a molar ratio of 65:25:15:40:20. Then, 1.5% azobisisobutyronitrile initiator based on the total mass of the above monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0125] C. Preparation of acrylic acid prepolymer

[0126] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 300% xylene, n-butanol, and ethanol (mass ratio 2.5:1:0.5) mixed organic solvent and 5% initiator-containing monomer mixture (based on the total mass of the initiator-containing monomer mixture obtained in step B) were added and mixed thoroughly. The mixture was then heated to 95°C and maintained at this temperature for 12 minutes. The remaining initiator-containing monomer mixture was then divided into 10 equal portions, with one portion added every 15 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for 1 hour. Then, 0.15% of the aforementioned initiator azobisisobutyronitrile (AIBN) based on the total mass of the initiator-containing monomer mixture was added, and the reaction was continued for 1 hour to obtain the acrylic acid prepolymer.

[0127] D. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0128] Under nitrogen protection, zinc oxide and copper hydroxide (molar ratio 7:3) and salicylic acid are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of zinc oxide and copper hydroxide to the above acrylic acid monomer is 1.5:1.0, and the molar ratio of zinc oxide and copper hydroxide to salicylic acid is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the mass ratio of organic solvent to zinc oxide, copper hydroxide and organic acid total mass of 10:1.0, mixed evenly, and then reacted at a temperature of 100°C for 3 hours to obtain the acrylic self-polishing antifouling resin prepolymer.

[0129] E. Preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater.

[0130] The acrylic self-polishing antifouling resin prepolymer obtained in step D, which can be peeled off in seawater, is mixed with glutaraldehyde crosslinking agent at a temperature of 40°C until the solvent content of the dried product is less than 1% by weight, in accordance with the crosslinking agent being 10% of the carboxyl or hydroxyl group of the acrylic self-polishing antifouling resin prepolymer.

[0131] Example 3: Preparation of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to the present invention

[0132] The implementation steps of this embodiment are as follows:

[0133] A. Preparation of macromolecular acrylic acid organosilicon monomers

[0134] Hydroxyethyl methacrylate hydroxy acrylate with DOWSIL TM RSN-0806Resin organosilicon monomers were mixed uniformly at a molar ratio of 1:1, and then 0.8% stannous octoate catalyst and 100% toluene solvent were added based on the mass of the organosilicon monomers. The mixture was mixed uniformly and reacted at 130°C for 4 hours to obtain the macromolecular acrylic organosilicon monomers.

[0135] B. Preparation of monomer mixtures containing initiators

[0136] A mixture of butyl acrylate and dodecyl acrylate (molar ratio 3:1), oily acrylate monomers, itaconic acid acrylate monomers, N-hydroxymethylacrylamide acrylamide monomers, hydroxyethyl acrylate, and watery acrylate monomers obtained in step A are mixed evenly in a molar ratio of 40:10:10:20:20. Then, 1% azobisisobutyronitrile initiator based on the total mass of monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0137] C. Preparation of acrylic acid prepolymer

[0138] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 200% xylene, n-butanol, and ethanol (mass ratio 2.5:2:1) mixed organic solvent and 10% of the initiator-containing monomer mixture obtained in step B were added and mixed thoroughly. The mixture was then heated to 80°C and maintained at this temperature for 20 minutes. The remaining initiator-containing monomer mixture was then divided into five equal portions, with one portion added every 20 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for another hour. Then, 0.1% azobisisobutyronitrile initiator (based on the total mass of the initiator-containing monomer mixture) was added, and the reaction was continued for 3 hours to obtain the acrylic acid prepolymer.

[0139] D. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0140] Under nitrogen protection, zinc oxide and copper hydroxide (molar ratio 1:1) and benzoic acid organic acid are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of zinc oxide and copper hydroxide to the above acrylic acid monomer is 1.2:1.0, and the molar ratio of zinc oxide and copper hydroxide to organic acid is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the total mass ratio of organic solvent to zinc oxide, copper hydroxide and benzoic acid 8.0:1.0, mixed evenly, and then reacted at a temperature of 90°C for 4 hours to obtain the acrylic self-polishing antifouling resin prepolymer.

[0141] E. Preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater.

[0142] The acrylic self-polishing antifouling resin prepolymer obtained in step D, which is delaminated in seawater, is mixed with aziridine CX300 crosslinking agent at a temperature of 25°C until the solvent content of the dried product is less than 1% by weight, in accordance with the crosslinking agent being 50% of the carboxyl molar amount of the acrylic self-polishing antifouling resin prepolymer.

[0143] Example 4: Preparation of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to the present invention

[0144] The implementation steps of this embodiment are as follows:

[0145] A. Preparation of macromolecular acrylic acid organosilicon monomers

[0146] Hydroxypropyl methacrylate hydroxy acrylate and DOWSIL TMRSN-0806Resin organosilicon monomers were mixed uniformly at a molar ratio of 1:2.0, and then 1.2% dibutyltin dilaurate catalyst and 150% toluene solvent (based on the mass of organosilicon monomers) were added and mixed uniformly. The mixture was then reacted at 128°C for 4.5 hours to obtain the macromolecular acrylic organosilicon monomers.

[0147] B. Preparation of monomer mixtures containing initiators

[0148] Butyl methacrylate and dodecyl methacrylate (molar ratio 2:1), oily acrylate monomers, acrylic acid monomers, acrylamide monomers, dimethylaminoethyl methacrylate, and watery acrylate monomers are mixed with the macromolecular acrylic organosilicon monomers obtained in step A at a molar ratio of 46:15:12:18:7. Then, 0.8% azobisisobutyronitrile initiator based on the total mass of the above monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0149] C. Preparation of acrylic acid prepolymer

[0150] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 250% xylene, cyclohexanone, and n-butanol (mass ratio 3:1:1) mixed organic solvent and 8% initiator-containing monomer mixture (based on the total mass of the initiator-containing monomer mixture obtained in step B) were added and mixed thoroughly. The mixture was then heated to 85°C and maintained at this temperature for 15 minutes. The remaining initiator-containing monomer mixture was then divided into 6 equal portions, with one portion added every 20 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for 1 hour. Then, 0.12% of the aforementioned initiator azobisisobutyronitrile (AIBN) based on the total mass of the initiator-containing monomer mixture was added, and the reaction was continued for 3.5 hours to obtain the acrylic acid prepolymer.

[0151] D. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0152] Under nitrogen protection, zinc oxide and copper hydroxide (9:1) and lactic acid organic acid are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of zinc oxide and copper hydroxide to the above acrylic acid monomer is 0.8:1.0, and the molar ratio of zinc oxide and copper hydroxide to lactic acid organic acid is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the mass ratio of mixed organic solvent to zinc oxide, copper hydroxide and organic acid total mass of 1.0:1.0, mixed evenly, and then reacted at a temperature of 95°C for 3.5 hours to obtain the acrylic self-polishing antifouling resin prepolymer;

[0153] E. Preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater.

[0154] The acrylic self-polishing antifouling resin prepolymer obtained in step D, which is delaminated in seawater, is mixed with the aziridine XR100 crosslinking agent at a temperature of 30°C until the solvent content of the dried product is less than 1% by weight, in accordance with the crosslinking agent being 60% of the hydroxyl content of the acrylic self-polishing antifouling resin prepolymer.

[0155] Example 5: Preparation of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to the present invention

[0156] The implementation steps of this embodiment are as follows:

[0157] A. Preparation of macromolecular acrylic acid organosilicon monomers

[0158] Hydroxypropyl acrylate with organosilicon monomer DOWSIL TM RSN-6018ResinIntermediate was mixed evenly at a molar ratio of 1:0.8, and then 1% catalyst and 150% solvent (based on the mass of the organosilicon monomer) were added and mixed evenly. The mixture was then reacted at 128°C for 4.2 hours to obtain the macromolecular acrylic organosilicon monomer.

[0159] B. Preparation of monomer mixtures containing initiators

[0160] Oily acrylate monomers ethyl methacrylate and butyl acrylate (molar ratio 1:2), acrylic acid monomer, acrylamide monomer acrylamide, watery acrylate monomer 4-hydroxybutyl acrylate, and the macromolecular acrylic organosilicon monomer obtained in step A are mixed evenly in a molar ratio of 30:15:12:30:13. Then, 1.2% of initiator azobisisobutyronitrile (AIBN) based on the total mass of monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0161] C. Preparation of acrylic acid prepolymer

[0162] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 180% xylene and butyl acetate mixed organic solvent (mass ratio 3:1) and 12% of the initiator-containing monomer mixture obtained in step B were added and mixed thoroughly. The mixture was then heated to 75°C and maintained at this temperature for 35 minutes. The remaining initiator-containing monomer mixture was then divided into four equal portions, with one portion added every 30 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for 1 hour. Then, 0.12% of the initiator (based on the total mass of the initiator-containing monomer mixture) was added, and the reaction was continued for 3.5 hours to obtain the acrylic acid prepolymer.

[0163] D. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0164] Under nitrogen protection, zinc oxide and copper hydroxide (molar ratio 3:1) and benzoic acid organic acid are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of zinc oxide and copper hydroxide to the above acrylic acid monomer is 0.8:1.0, and the molar ratio of zinc oxide and copper hydroxide to benzoic acid organic acid is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the mass ratio of mixed organic solvent to zinc oxide, copper hydroxide and organic acid total mass of 5.0:1.0, mixed evenly, and then reacted at a temperature of 90°C for 4 hours to obtain the acrylic self-polishing antifouling resin prepolymer;

[0165] E. Preparation of a self-polishing antifouling acrylic resin that can be peeled off in seawater.

[0166] The crosslinking agent is 30% of the carboxyl molar amount of the acrylic self-polishing antifouling resin prepolymer. The acrylic self-polishing antifouling resin prepolymer that can be delaminated in seawater obtained in step D is mixed evenly with the glycidyl ether crosslinking agent at a temperature of 35°C. Under this condition, it is dried until the solvent content of the dried product is less than 1% by weight, thus obtaining acrylic self-polishing antifouling resin A5 that can be delaminated in seawater.

[0167] Example 6: Preparation of a non-separable acrylic self-polishing antifouling resin in seawater

[0168] This embodiment is carried out according to the method described in CN113087822B, entitled "An Acrylic Metal Salt Resin and Its Preparation Method and Uses":

[0169] A. Preparation of monomer mixture containing initiator

[0170] Butyl acrylate oily acrylate monomer, acrylic acid acrylic monomer and acrylamide acrylamide monomer are mixed evenly in a mass ratio of 72:18:10. Then, 0.8% azobisisobutyronitrile initiator based on the total mass of monomers is added and mixed evenly to obtain a monomer mixture containing initiator.

[0171] B. Preparation of acrylic acid prepolymer

[0172] In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 150% xylene and n-butanol (mass ratio 3.5:2) mixed organic solvent and 10% of the initiator-containing monomer mixture obtained in step A were added and mixed thoroughly. The mixture was then heated to 80°C and maintained at this temperature for 20 minutes. The remaining initiator-containing monomer mixture was then divided into three equal portions, with one portion added every 20 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for 1 hour. Then, 0.08% of the aforementioned initiator (based on the total mass of the initiator-containing monomer mixture) was added, and the reaction was continued for 3.5 hours to obtain the acrylic acid prepolymer.

[0173] C. Preparation of acrylic self-polishing and antifouling resin prepolymer

[0174] Under nitrogen protection, zinc oxide and copper hydroxide (molar ratio 1:1) and benzoic acid and lactic acid (molar ratio 7:3) organic acids are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of zinc oxide and copper hydroxide to the above acrylic acid monomer is 0.5:1.0, and the molar ratio of zinc oxide and copper hydroxide to organic acids is 1.0:1.0; then, the same organic solvent as in step C is added according to the mass ratio of mixed organic solvent to zinc oxide, copper hydroxide and organic acids of 5:1.0, mixed evenly, and reacted at a temperature of 90°C for 4 hours to obtain the acrylic self-polishing antifouling resin prepolymer.

[0175] E. Preparation of ordinary acrylic self-polishing and antifouling resin

[0176] The acrylic self-polishing antifouling resin prepolymer obtained in step D is mixed with aziridine CX100 crosslinking agent at a temperature of 35°C until the solvent content of the dried product is less than 1% by weight, in accordance with the crosslinking agent being 30% of the carboxyl molar amount of the acrylic self-polishing antifouling resin prepolymer.

[0177] Application Example 1: Test on the anti-protein properties of the self-polishing antifouling acrylic resin of the present invention, which can be peeled off in seawater.

[0178] The implementation method of this application example is as follows:

[0179] Test samples: Acrylic self-polishing antifouling resins A1, A2 and A3 prepared in Examples 1-3 that can be peeled off in seawater; glass slides without resin coating are recorded as blanks.

[0180] Test substrate: glass slide, 20 mm in diameter;

[0181] Coating method: Conventional coating method is used.

[0182] The adsorption performance test was conducted using the fluorescence-protein colorimetric method described in the paper "Spray-Painted Hydrogel Coating for Marine Antifoulin", Vol. 6, No. 3, 2021, page 91 (2000).

[0183] The steps for testing anti-protein adsorption performance are as follows:

[0184] At room temperature, bovine serum albumin (BSA) and fluorescein isothiocyanate (FITC) were prepared into a BSA-FITC fluorescent protein solution with a concentration of 0.02 mg / ml using phosphate-buffered saline (PBS, pH 7.2).

[0185] Add 10 mL of PBS to a weighing bottle, and place the acrylic self-polishing antifouling resin coating sample (which can be peeled off in seawater according to this invention) face up in a petri dish for pre-wetting for 24 hours. Then, immerse the sample in 10 mL of BSA-FITC fluorescent protein solution at room temperature and in the dark for 6 hours. Remove the sample from the fluorescent protein solution and place it in 15 mL of PBS solution to remove proteins floating on the coating surface. Finally, observe the fluorescent area of ​​the sample surface under a fluorescence microscope.

[0186] Specifically, the test results of the anti-protein adsorption performance of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to the present invention are listed in the appendix. Figure 1 middle.

[0187] In the appendix Figure 1 In the figure, blank represents the distribution of fluorescent proteins adhering to the white glass surface of the control plate without any coating, and A1, A2 and A3 represent the distribution of fluorescent proteins adhering to the surface of the acrylic self-polishing antifouling resin prepared in seawater in Examples 1-3, respectively.

[0188] Appendix Figure 1 It is clear that a large amount of fluorescent protein adheres to the surface of the blank glass, while the coating surfaces of samples A1, A2, and A3 also have some fluorescent protein adhered to them, but the area of ​​fluorescent protein on the surface of the blank glass is significantly smaller. This demonstrates that the acrylic self-polishing antifouling resin that can be peeled off in seawater has good anti-protein adhesion properties.

[0189] Application Example 2: Experiment on the inhibition of bacterial growth by the self-polishing antifouling acrylic resin of the present invention in seawater (which can be peeled off in layers)

[0190] The implementation method of this application example is as follows:

[0191] Test samples: Acrylic self-polishing antifouling resins A1, A2, A3, A4 and A5 prepared in Examples 1-5; glass slides without resin coating are recorded as blanks.

[0192] Test substrate: Glass slide, 20 mm in diameter

[0193] Coating method: Conventional coating method is used;

[0194] The antibacterial performance testing steps are as follows:

[0195] Using a sterile inoculation loop, one Staphylococcus aureus bacterial culture disc provided by the Institute of Oceanology, Chinese Academy of Sciences, was inoculated into a liquid culture medium prepared with a product called "Nutritional Broth" sold by Beijing Luqiao Technology Co., Ltd. The culture was incubated with shaking at 37°C and 130 rpm for 24 hours. Simultaneously, a glass slide (20 mm in diameter) coated with acrylic self-polishing antifouling resin was immersed in deionized water and irradiated with UV light at 254 nm in a laminar flow hood for 24 hours to achieve complete hydration and thorough sterilization. Then, the acrylic self-polishing antifouling resin-coated slide was placed in a sterile glass tube (30 mm in diameter and 50 mm in height), and 50 μL of the bacterial suspension was inoculated onto the coating surface using a microdropper. Glass bottles without acrylic self-polishing antifouling resin samples served as a blank control group. After incubation at 37°C for 20 hours, 5 mL of sterile physiological saline (0.9% sodium chloride solution) was added to each glass tube, followed by inoculation with a product called "Nutritional Broth" sold by BRANSON. The ultrasonic cleaner sold as a tabletop ultrasonic cleaner performs ultrasonic treatment for 30 seconds at room temperature. This process helps bacteria completely detach from the coating surface and enter sterile saline (0.9% sodium chloride solution), resulting in a suspension containing the test bacteria. It is then diluted with saline (dilution ratio 10). -1 10 -2 10 -3 10 -4 10 -5 Subsequently, 100 μL of bacterial solution was evenly spread on the surface of the agar solid medium. After the bacterial solution was completely absorbed, the solid medium was covered, and then placed in an incubator at 37°C for 24 hours. Finally, the number of bacteria on the agar plate was photographed to determine the antibacterial ability of the coating.

[0196] Specifically, the test results of the antibacterial properties of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to the present invention are listed in the appendix. Figure 2 middle.

[0197] The blanks represent the number of bacteria growing on uncoated glass agar plates. A1, A2, A3, A4, and A5 represent the number of bacteria growing on the self-polishing antifouling acrylic resin agar plates prepared in Examples 1-5 that can be peeled off in seawater.

[0198] Appendix Figure 2The results clearly show that the blank control group exhibited a large number of bacteria growth on the agar plates, while the A1, A2, A3, A4, and A5 agar plates showed very few or no bacteria growth. These results demonstrate that the self-polishing antifouling acrylic resin of this invention, which can be peeled off in seawater, has excellent antibacterial growth inhibition properties.

[0199] Application Example 3: Experimental use of the self-polishing antifouling acrylic resin of the present invention in actual marine applications. The implementation method of this application example is as follows:

[0200] Test samples: Acrylic self-polishing antifouling resins A1 and A2 prepared in Examples 1-2; PVC boards without any coating on the surface are recorded as blanks; Acrylic self-polishing antifouling resin prepared in Example 6, which cannot be delaminated in seawater, is the control group and is recorded as A00.

[0201] Test substrate: PVC, dimensions 900×300×3mm 3

[0202] Coating method: Conventional coating method is used;

[0203] Antifouling performance testing was conducted according to the national standard "Test Method for Shallow Sea Immersion of Antifouling Paint Samples" (GB / T5370-2007).

[0204] Test period: October 2023;

[0205] The results of the antifouling performance test are listed in the appendix. Figure 3 middle:

[0206] From the appendix Figure 3 It can be seen that after being soaked in the ocean for one month, the surface of the blank board was covered with a thick layer of silt. The surface of the acrylic self-polishing antifouling resin A00, which cannot be peeled off in seawater, was also covered with some silt. However, the surfaces of the A1 and A2 coatings were basically free of biofilm and biological attachment.

[0207] These results demonstrate that the self-polishing antifouling resin of acrylic material prepared in this invention, which can be peeled off in seawater, has excellent antifouling capabilities in actual marine environments. After immersion in the actual ocean for 5 months, a thick layer of silt, biofilm, and some fouling organisms adhered to the surface of the blank board. The surface of the existing self-polishing antifouling resin A00 was covered with a large amount of silt without peeling off, while the surface layer of the A1 and A2 coatings with the biofilm had peeled off, with only a small amount of fouling adhering to the edges.

[0208] These results fully demonstrate that the acrylic self-polishing antifouling resin prepared in this invention, which can be delaminated in seawater, can achieve significant delamination in actual marine environments, exhibiting excellent antifouling capabilities in real-world marine environments.

Claims

1. A method for preparing a self-polishing antifouling acrylic resin that can be peeled off in seawater, characterized in that... The preparation steps of this method are as follows: A. Preparation of macromolecular acrylic acid organosilicon monomers The hydroxy acrylate and organosilicon monomer are mixed evenly at a molar ratio of 1:0.5-5.

0. Then, 0.5-1.5% catalyst and 30-300% organic solvent (based on the mass of organosilicon monomer) are added and mixed evenly. The mixture is then reacted at 125-135°C for 3.5-5.0 hours to obtain the macromolecular acrylic organosilicon monomer. B. Preparation of monomer mixtures containing initiators Oily acrylate monomers, acrylic monomers, acrylamide monomers, water-based acrylate monomers, and macromolecular acrylic silicone monomers obtained in step A are mixed evenly in a molar ratio of 25-65:5-25:5-15:10-40:3-20. Then, 0.2-1.5% of initiator based on the total mass of the above monomers is added and mixed evenly to obtain a monomer mixture containing initiator. C. Preparation of acrylic acid prepolymer In a four-necked flask equipped with a stirrer, condenser, and thermometer, under nitrogen protection, 100-300% of the total mass of the initiator-containing monomer mixture obtained in step B and 5-15% of the initiator-containing monomer mixture were added and mixed thoroughly. The mixture was then heated to 65-95°C and maintained at this temperature for 12-45 minutes. The remaining initiator-containing monomer mixture was then divided into 3-10 equal portions, with one portion added every 15-35 minutes. After all the initiator-containing monomer mixture had been added, the mixture was maintained at this temperature for 1 hour. Then, 0.05-0.15% of the initiator was added based on the total mass of the initiator-containing monomer mixture, and the reaction was continued for 1-4 hours to obtain the acrylic acid prepolymer. D. Preparation of acrylic self-polishing and antifouling resin prepolymer Under nitrogen protection, metal oxides or hydroxides and organic acids are added to the acrylic acid prepolymer obtained in step C; wherein the molar ratio of metal oxides or hydroxides to the acrylic acid monomers is 0.5-1.5:1.0, and the molar ratio of metal oxides or hydroxides to organic acids is 1.0:1.0; then, the same mixed organic solvent as in step C is added according to the total mass ratio of mixed organic solvent to metal oxides or hydroxides and organic acids of 0-10:1.0, mixed evenly, and then reacted at a temperature of 85-100°C for 3-6 hours to obtain the acrylic acid self-polishing antifouling resin prepolymer. E. Preparation of acrylic self-polishing antifouling resin that can be peeled off in seawater. The crosslinking agent is 10-80% of the molar amount of carboxyl, hydroxyl or amino groups of the acrylic self-polishing antifouling resin prepolymer. The hydrogel acrylic self-polishing antifouling resin prepolymer obtained in step D is mixed with the crosslinking agent at a temperature of 15-40°C. Under these conditions, it is dried until the solvent content of the dried product is less than 1% by weight, thus obtaining an acrylic self-polishing antifouling resin that can be peeled off in seawater.

2. The preparation method according to claim 1, characterized in that... In step A, the hydroxy acrylate is one or more hydroxy acrylates selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or hydroxybutyl 4-acrylate; the catalyst is one or more catalysts selected from tetrabutyl titanate, tetraisopropyl titanate, stannous octoate, or dibutyltin dilaurate; the organosilicon monomer is one or more catalysts selected from DOWSIL. TM RSN-6018ResinIntermediate, DOWSIL TM RSN-0249Flake Resin, DOWSIL TM RSN-0806Resin,DOWSIL TM RSN-0804Resin or DOWSIL TM RSN-0805Resin is an organosilicon monomer.

3. The preparation method according to claim 1, characterized in that... In step B, 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, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, octadecyl acrylate, or octadecyl methacrylate; the acrylic monomer is one or more acrylic monomers selected from acrylic acid, methacrylic acid, or itaconic acid; the acrylamide monomer is one or more acrylamide monomers selected from acrylamide, N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, N,N-methylenebisacrylamide, or N,N-dimethylacrylamide; the watery acrylate monomer is one or more watery acrylic monomers selected from hydroxy acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or 3-(dimethylamino)propyl acrylate.

4. The preparation method according to claim 1, characterized in that... In steps B and C, the initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, potassium persulfate, or ammonium persulfate.

5. The preparation method according to claim 1, characterized in that... In step AD, the organic solvent is one or more solvents selected from n-butanol, ethanol, toluene, xylene, butyl acetate, cyclohexanone, or methyl isobutyl ketone.

6. The preparation method according to claim 1, characterized in that... In step D, the metal oxide is zinc oxide, copper oxide, magnesium oxide, or calcium oxide; the metal hydroxide is magnesium hydroxide, calcium hydroxide, zinc hydroxide, or copper hydroxide; and the organic acid is benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, lactic acid, polylactic acid, rosin acid, amino acid, salicylic acid, or furoic acid.

7. The preparation method according to claim 1, characterized in that... In step E, the crosslinking agent is glutaraldehyde, succinaldehyde, aziridine CX100, aziridine CX300, aziridine XR100, epoxy silane crosslinking agent XR-500, or glycidyl ether.

8. An acrylic self-polishing antifouling resin that can be peeled off in seawater by the preparation method according to any one of claims 1 to 7.

9. Use of the self-polishing antifouling acrylic resin that can be peeled off in seawater according to claim 8 in preventing marine fouling adhesion.

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