Aqueous self-polishing antifouling resin, its preparation method and use thereof

Abstract

The present application relates to a kind of preparation methods of water-based self-polishing antifouling resin and its use, the preparation method of water-based self-polishing antifouling resin includes the preparation of oily acrylic monomer mixture, preparation of unsaturated organic acid aqueous solution, preparation of water-based monomer solution and water-based self-polishing antifouling resin and the like steps.Prepared with the water-based self-polishing antifouling resin of the present application as film-forming material, the water-based self-polishing antifouling coating on substrate shows good film-forming performance, adhesion, storage stability, construction performance, and shows excellent antifouling effect.

Description

[Technical Field]

[0001] This invention belongs to the field of marine biofouling control technology. More specifically, this invention relates to a water-based self-polishing antifouling resin, a method for preparing the water-based self-polishing antifouling resin, and the uses of the water-based self-polishing antifouling resin. [Background Technology]

[0002] Self-polishing antifouling coatings are currently the most important antifouling coatings due to their high efficiency, long-lasting antifouling performance, and ease of application. Self-polishing antifouling resin is the core component of these coatings. It still uses organic solvents such as xylene, toluene, butanol, and butyl acetate as dispersion systems, releasing large amounts of volatile organic compounds during use. This causes significant harm to the ecological environment and results in a huge waste of organic solvents. In response to this problem, extensive research has been conducted both domestically and internationally in recent years on the water-based formulation of self-polishing antifouling resins. However, progress has been extremely limited, and mature, commercially available water-based self-polishing antifouling coatings suitable for large-scale application are still scarce. This is because current water-based self-polishing antifouling coatings suffer from the following problems: ① Poor film-forming and water-resistant properties of the water-based self-polishing antifouling resin, leading to easy coating peeling; ② Water-based self-polishing antifouling resin emulsions are prone to demulsification under conditions such as high-speed grinding and dispersion, long-term storage, and low temperatures, posing significant difficulties in the preparation and use of water-based antifouling coatings; ③ During application, the drying time of the water-based self-polishing antifouling resin is slow, making it susceptible to the effects of temperature, rain, snow, and other weather conditions.

[0003] The aforementioned problems with currently prepared waterborne self-polishing antifouling resins are primarily due to the use of soap-based emulsion polymerization, which introduces a large amount of surfactant (approximately 6-10% of the monomer mass) into the resin. This results in a film-forming mechanism that differs significantly from that of solution-polymerized oilborne antifouling resins. In the film-forming process of soap-based emulsion polymerized resins, latex particles must first overcome the obstruction caused by the emulsifier before they can approach and fuse together. Therefore, waterborne self-polishing antifouling resins prepared using current technology struggle to form a good film, and a lower glass transition temperature is required to promote the fusion of polymers within the latex particles. Under seawater immersion, a large amount of emulsifier seeps from the coating, severely reducing its water resistance and slowing its drying speed, thus affecting the application schedule. These factors lead to poor adhesion and a significantly shortened shelf life for waterborne self-polishing antifouling coatings. Emulsifier micelles or particles can stably disperse polymer particles in an aqueous system, but they are easily demulsified by shear force, temperature, solid content, metal ions, etc., posing a huge risk of failure to water-based resin emulsions and water-based coatings.

[0004] In view of the aforementioned problems in the existing technology, this invention incorporates neutral hydrophilic monomer structural units and charged hydrophilic monomers during the preparation process, and adjusts the polymerization process to give the polymer hydrophilic segments or structural units, thereby endowing the self-polishing polymer with self-emulsifying function. This avoids the introduction of a large amount of emulsifier, which is beneficial to improving the film-forming properties of the resin. At the same time, the neutral hydrophilic monomer structural units with active groups can interact with the charged structural units, improving the water resistance and adhesion of the coating by forming hydrogen bonds or covalent bonds. Through the synergistic effect of the above-mentioned effects, a waterborne self-polishing antifouling resin and its coating with greatly extended film-forming properties, water resistance, and shelf life are obtained. The removal of emulsifiers also facilitates the drying of the paint film during the application of waterborne coatings. The self-emulsifying ability of the waterborne self-polishing antifouling resin polymer also avoids the problems of demulsification and clumping that occur in waterborne self-polishing antifouling resins under various conditions such as preparation and storage. [Summary of the Invention]

[0005] [Technical problem to be solved]

[0006] The purpose of this invention is to provide a method for preparing a water-based self-polishing and antifouling resin.

[0007] Another object of the present invention is to provide an aqueous self-polishing antifouling resin obtained by the preparation method described above.

[0008] Another object of the present invention is to provide the use of the water-based self-polishing antifouling resin obtained by the preparation method.

[0009] [Technical Solution]

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

[0011] This invention relates to a method for preparing a water-based self-polishing and antifouling resin.

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

[0013] A. Preparation of oil-based acrylic monomer mixture

[0014] The oily acrylic monomer mixture is obtained by mixing hard oily acrylic monomer, soft oily acrylic monomer and self-polishing monomer in a molar ratio of 0-30:20-70:0-30.

[0015] B. Preparation of unsaturated organic acid aqueous solution

[0016] Mix 3-20% of unsaturated organic acid (based on the molar amount of oily acrylic acid monomer) with 30-200% of water (based on the molar amount of unsaturated organic acid) until homogeneous. Then add 10-100% of sodium hydroxide (based on the molar amount of unsaturated organic acid), dissolve and mix until homogeneous to obtain the aforementioned unsaturated organic acid aqueous solution.

[0017] C. Preparation of aqueous monomer solutions

[0018] According to the molar ratio of oily acrylic monomer to aqueous monomer of 80-95:5-25, one or more aqueous monomers are added to the unsaturated organic acid aqueous solution obtained in step B, and then 0.1-1.5% initiator is added based on the total mass of oily acrylic monomer and aqueous monomer to obtain the aqueous monomer solution.

[0019] D. Preparation of water-based self-polishing antifouling resin

[0020] In a four-necked flask equipped with a stirrer, condenser and thermometer, add 100-300% of a mixed solvent composed of deionized water and alcohol based on the total mass of oily acrylic monomer and watery monomer. Then add the oily acrylic monomer solution obtained in step A and the watery monomer solution obtained in step C, each added in an amount of 5-10% of their respective volumes. Mix well to obtain a monomer mixture solution.

[0021] Then, under a nitrogen atmosphere and a stirring speed of 50–500 rpm, the above monomer mixture solution is heated to a temperature of 70–85°C. When the reaction system shows blue light, the remaining oily acrylic monomer solution and aqueous monomer solution are added dropwise or in batches at this temperature over 0.5–1.5 h. Then the temperature is lowered to 60–70°C and maintained at this temperature for 0.8–1.2 h.

[0022] Next, 0.01 to 0.02% of the above-mentioned initiator based on the total mass of all monomers is added, and the mixture is kept at 60 to 70°C for 0.4 to 0.6 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin.

[0023] According to a preferred embodiment of the present invention, in step A, the hard oily acrylic monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, or a mixture thereof; the soft oily acrylic monomer is propyl acrylate, butyl acrylate, isoamyl acrylate, dodecyl acrylate, octadecyl acrylate, or a mixture thereof; and the self-polishing monomer is acryloyloxytriisopropylsilane, methacryloxytriisopropylsilane, γ-methacryloyloxypropyltrimethoxysilane, or a mixture thereof.

[0024] According to another preferred embodiment of the present invention, in step B, the unsaturated organic acid is acrylic acid, methacrylic acid, methylene succinic acid, or a mixture thereof.

[0025] According to another preferred embodiment of the present invention, in step C, the aqueous monomer is acrylamide, hydroxyacrylamide, vinylpyrrolidone, hydroxyacrylate, or a mixture thereof.

[0026] According to another preferred embodiment of the present invention, the hydroxyacrylamide is N-hydroxymethylacrylamide, N-hydroxyethylacrylamide or N-hydroxypropylacrylamide; the hydroxyacrylate is hydroxyethyl acrylate, hydroxypropyl acrylate or 4-hydroxybutyl acrylate or a mixture thereof.

[0027] According to another preferred embodiment of the present invention, in step C, the initiator is a mixture of a water-soluble initiator and an oil-soluble initiator in a mass ratio of 70-95:0-10;

[0028] According to another preferred embodiment of the present invention, the aqueous initiator is one or more initiators selected from azobisisobutyrazoline hydrochloride, azobisisopropylimidazoline, azobisisobutyramidine hydrochloride, potassium persulfate, or ammonium persulfate; the oily initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, benzoyl tert-butyl peroxide, or methyl ethyl ketone peroxide.

[0029] According to another preferred embodiment of the present invention, in step D, the alcohol in the mixed solvent is one or more alcohols selected from methanol, ethanol, ethylene glycol or glycerol, and the amount of alcohol is 3 to 20% of the volume of the mixed solvent.

[0030] The present invention also relates to the water-based self-polishing antifouling resin prepared by the aforementioned preparation method.

[0031] This invention also relates to the use of the water-based self-polishing antifouling resin prepared by the above preparation method in the field of marine fouling biofouling control.

[0032] The invention will now be described in more detail.

[0033] This invention relates to a method for preparing a water-based self-polishing and antifouling resin.

[0034] The waterborne self-polishing antifouling resin prepared by the present invention using a soap-free emulsion polymerization method has self-emulsification ability, avoiding the use of emulsifiers, thereby improving the resin's film-forming properties, water resistance and shelf life. Moreover, the waterborne self-polishing antifouling resin is not prone to demulsification, clumping and other problems under various conditions such as preparation and storage.

[0035] The preparation steps of the preparation method of the present invention are as follows:

[0036] A. Preparation of oil-based acrylic monomer mixture

[0037] The oily acrylic monomer mixture is obtained by mixing hard oily acrylic monomer, soft oily acrylic monomer and self-polishing monomer in a molar ratio of 0-30:20-70:0-30.

[0038] In this invention, hard oil acrylic monomer should be understood as an acrylic monomer with a glass transition temperature above 0 degrees Celsius.

[0039] According to the present invention, the main role of the hard oil-based acrylic monomer in the preparation of waterborne self-polishing antifouling resin is to regulate the rigidity of the polymer chain and improve the adhesion of the waterborne self-polishing antifouling resin.

[0040] The hard oil acrylic monomers used in this invention are methyl acrylate, methyl methacrylate, ethyl acrylate, or mixtures thereof, all of which are currently commercially available products, such as methyl acrylate sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name methyl acrylate.

[0041] In this invention, soft oily acrylic monomer should be understood as an acrylic monomer with a glass transition temperature below 0 degrees Celsius.

[0042] According to the present invention, the main role of soft oily acrylic monomers in the preparation of waterborne self-polishing antifouling resins is to improve the adhesion of waterborne self-polishing antifouling resins to substrates.

[0043] The soft, oily acrylic monomers used in this invention are propyl acrylate, butyl acrylate, isoamyl acrylate, dodecyl acrylate, octadecyl acrylate, or mixtures thereof, all of which are currently commercially available products, such as butyl acrylate sold by Tianjin Tianjiao Chemical Co., Ltd. under the trade name butyl acrylate.

[0044] In this invention, the self-polishing monomer should be understood as a functional monomer having chemical properties that allow it to be chemically hydrolyzed or biodegraded in seawater.

[0045] According to the present invention, the main role of the self-polishing monomer in the preparation of waterborne self-polishing antifouling resin is to enhance the antifouling ability of the waterborne self-polishing antifouling resin by continuously dissolving and detaching the self-polishing monomer.

[0046] The self-polishing monomers used in this invention are acryloyloxytriisopropylsilane, methacryloxytriisopropylsilane, γ-methacryloyloxypropyltrimethoxysilane, or mixtures thereof, all of which are currently commercially available products, such as methacryloxytriisopropylsilane sold by Wuhan Yuancheng Technology Development Co., Ltd. under the trade name methacryloxytriisopropylsilane.

[0047] When preparing the oily acrylic monomer solution, if the amounts of soft oily acrylic monomer and self-polishing monomer are within the specified range, and the rigidity of the water-based self-polishing antifouling resin coating meets the mechanical property requirements for crack resistance, the amount of hard oily acrylic monomer can be zero. If the amount of hard oily acrylic monomer exceeds 30%, it will result in excessive polymer rigidity, leading to a decrease in the mechanical properties of the resulting water-based self-polishing antifouling resin, which is detrimental to its adhesion to the substrate. Therefore, an amount of hard oily acrylic monomer of 0–30% is reasonable, and preferably 5–25%.

[0048] When the amounts of hard oil-based acrylic monomer and self-polishing monomer are within the specified range, if the amount of soft oil-based acrylic monomer is less than 20%, the resulting waterborne self-polishing antifouling resin has lower hardness, which is detrimental to the fusion of resin latex particles, film formation, and adhesion to the substrate. If the amount of soft oil-based acrylic monomer is greater than 70%, the resulting waterborne self-polishing antifouling resin has a lower glass transition temperature during film formation, resulting in lower hardness and reduced mechanical properties. Therefore, an amount of soft oil-based acrylic monomer of 20–70% is reasonable, and preferably 30–65%.

[0049] When the amounts of hard and soft acrylic monomers are within the specified range, and the self-polishing abrasion rate of the waterborne self-polishing antifouling resin coating is relatively stable, the amount of self-polishing monomer can be zero. If the amount of self-polishing monomer is higher than 30%, the self-polishing rate of the waterborne self-polishing antifouling resin coating is too fast, which is not conducive to its long-term antifouling effect. Therefore, an amount of 0-30% of the self-polishing monomer is suitable, preferably 6-25%.

[0050] Preferably, the molar ratio of hard oily acrylic monomer, soft oily acrylic monomer and self-polishing monomer is 5-25:30-65:6-25.

[0051] B. Preparation of unsaturated organic acid aqueous solution

[0052] Mix 3-20% of unsaturated organic acid (based on the molar amount of oily acrylic acid monomer) with 30-200% of water (based on the molar amount of unsaturated organic acid) until homogeneous. Then add 10-100% of sodium hydroxide (based on the molar amount of unsaturated organic acid), dissolve and mix until homogeneous to obtain the aforementioned unsaturated organic acid aqueous solution.

[0053] According to the present invention, the main role of unsaturated organic acids in the preparation of waterborne self-polishing antifouling resins is that they can form hydrogen bonds with other monomers having hydroxyl, amine or carboxyl groups, thereby affecting the mechanical properties of waterborne self-polishing antifouling resins.

[0054] The unsaturated organic acids used in this invention are acrylic acid, methacrylic acid, methylene succinic acid, or mixtures thereof, all of which are currently commercially available products, such as acrylic acid sold by Tianjin Damao Chemical Reagent Co., Ltd. under the trade name acrylic acid.

[0055] In this step, the main purpose of adding sodium hydroxide after the unsaturated organic acid and water are mixed evenly is to avoid the acid-base neutralization releasing a large amount of heat, which would cause the reaction temperature to be too high.

[0056] In this invention, when the amount of water is within the aforementioned range, if the amount of unsaturated organic acid is less than 3%, the mechanical properties of the water-based self-polishing antifouling resin coating will be reduced; if the amount of unsaturated organic acid is greater than 20%, the water-based self-polishing antifouling resin coating will easily become brittle, crack, and peel off. Therefore, an amount of unsaturated organic acid of 3-20% is preferable, preferably 3-18%. When the amount of unsaturated organic acid is within the aforementioned range, if the amount of water in the acid-base neutralization reaction is less than 30%, the cooling will be slow, and the large amount of heat released by the neutralization reaction will disrupt the equilibrium of the reaction system. If the amount of water is greater than 200%, the unsaturated organic acid will be over-diluted, and the acid-base neutralization reaction will be incomplete. Therefore, an amount of water of 30-200% is appropriate, preferably 55-175%.

[0057] In this step, when the amounts of unsaturated organic acid and water are within the specified range, if the amount of sodium hydroxide is less than 10%, fewer acrylic monomers containing carboxylate ions will be generated, the polymerization reaction will be unstable, and the reaction rate will decrease. If the amount of sodium hydroxide is greater than 100%, more acrylic monomers containing carboxylate ions will be generated, affecting the performance of the water-based self-polishing antifouling resin coating. Therefore, an amount of sodium hydroxide of 10-100% is reasonable, preferably 25-90%.

[0058] C. Preparation of aqueous monomer solutions

[0059] According to the molar ratio of oily acrylic monomer to aqueous monomer of 80-95:5-25, one or more aqueous monomers are added to the unsaturated organic acid aqueous solution obtained in step B, and then 0.1-1.5% initiator is added based on the total mass of oily acrylic monomer and aqueous monomer to obtain the aqueous monomer solution.

[0060] In this invention, the aqueous monomer should be understood as a monomer that has good solubility in water.

[0061] According to the present invention, the main role of waterborne monomers in the preparation of waterborne self-polishing antifouling resins is to promote the normal progress of the reaction and improve the antifouling performance of the waterborne self-polishing antifouling resins.

[0062] The aqueous monomers used in this invention are acrylamide, hydroxyacrylamide, vinylpyrrolidone, hydroxyacrylate, or mixtures thereof, wherein the hydroxyacrylamide is N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, or N-hydroxypropylacrylamide; and the hydroxyacrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, or 4-hydroxybutyl acrylate, or mixtures thereof. These are all products currently sold on the market, such as acrylamide sold by Jiangxi Changjiu Agricultural Science and Chemical Co., Ltd. under the trade name acrylamide, N-hydroxypropylacrylamide sold by Qingdao Datang Chemical Co., Ltd. under the trade name N-hydroxypropylacrylamide, and hydroxyethyl acrylate sold by Sinopharm Chemical Reagent Co., Ltd. under the trade name hydroxyethyl acrylate.

[0063] In this invention, when the amount of water-based monomer is within the specified range, if the amount of oil-based acrylic monomer is less than 80%, the adhesion performance of the water-based self-polishing antifouling resin on the substrate is poor; if the amount of oil-based acrylic monomer is greater than 95%, it will lead to emulsion instability; therefore, the amount of oil-based acrylic monomer is appropriate at 80-95%. When the amount of oil-based acrylic monomer is within the specified range, if the amount of water-based monomer is less than 5%, it will lead to emulsion demulsification and reduced stability; if the amount of water-based monomer is greater than 25%, it will lead to reduced water resistance and peeling of the coating; therefore, the amount of water-based monomer is reasonable at 5-25%.

[0064] According to the present invention, the main role of the initiator in the preparation of waterborne self-polishing antifouling resin is that the initiator decomposes into active free radicals, thereby initiating the polymerization reaction of the monomer to generate waterborne self-polishing antifouling resin.

[0065] According to the present invention, the initiator is a mixture of a water-soluble initiator and an oil-soluble initiator in a mass ratio of 70–95:0–10; wherein the water-soluble initiator is understood to be an initiator with a solubility of at least 1 g / 100 g deionized water at 20°C and 1 atmosphere, and its main function is to promote the participation of aqueous monomers in the copolymerization reaction. The oil-soluble initiator is understood to be an initiator with a solubility of less than 1 g / 100 g deionized water at 20°C and 1 atmosphere, and its main function is to promote the participation of oil-based monomers in the copolymerization reaction.

[0066] In this invention, when the amount of oil-soluble initiator is within the specified range, if the amount of water-soluble initiator is less than 70%, the aqueous monomer reaction will be incomplete; if the amount of water-soluble initiator is greater than 95%, the prepared emulsion is prone to phase separation, and the oily monomers in the emulsion will not polymerize completely. Therefore, an amount of 70-95% of water-soluble initiator is appropriate. When the amount of water-soluble initiator is within the specified range, if the oily monomers fully participate in polymerization, the amount of oil-soluble initiator can be 0; if the amount of oil-soluble initiator is greater than 10%, the emulsion viscosity will be high, and large latex particles will be present in the emulsion. Therefore, an amount of 0-10% of oil-soluble initiator is preferable.

[0067] The aqueous initiator used in this invention is one or more initiators selected from azobisisobutyrazoline hydrochloride, azobisisopropylimidazoline, azobisisobutyramidine hydrochloride, potassium persulfate or ammonium persulfate. These are all products currently sold on the market, such as azobisisobutyramidine hydrochloride sold by Tianjin Damao Chemical Reagent Co., Ltd. under the trade name azobisisobutyramidine hydrochloride.

[0068] The oily initiator used in this invention is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, benzoyl tert-butyl peroxide, or methyl ethyl ketone peroxide. These are all products currently sold on the market, such as azobisisobutyronitrile sold by Tianjin Damao Chemical Reagent Co., Ltd. under the trade name azobisisobutyronitrile.

[0069] In this step, the amount of initiator used is 0.1-1.5% based on the total mass of the oil-based acrylic monomer and the water-based monomer. If the amount of initiator is less than 0.1%, the polymerization reaction will be unstable or fail to initiate; if the amount of initiator is greater than 1.5%, the molecular weight of the water-based self-polishing antifouling resin will decrease, which is detrimental to improving its mechanical properties. Therefore, an initiator amount of 0.1-1.5% is reasonable, and preferably 0.3-1.2%.

[0070] D. Preparation of water-based self-polishing antifouling resin

[0071] In a four-necked flask equipped with a stirrer, condenser and thermometer, add 100-300% of a mixed solvent composed of deionized water and alcohol based on the total mass of oily acrylic monomer and watery monomer. Then add the oily acrylic monomer solution obtained in step A and the watery monomer solution obtained in step C, each added in an amount of 5-10% of their respective volumes. Mix well to obtain a monomer mixture solution.

[0072] The main purpose of using a mixed solvent of deionized water and alcohol when preparing monomer mixture solutions is to enhance the solubility of oily monomers in the solvent medium, which helps to form latex particles with smaller particle size and accelerates the rate of soap-free emulsion polymerization.

[0073] According to the present invention, in the mixed solvent, the alcohol is one or more alcohols selected from methanol, ethanol, ethylene glycol, or glycerol, and the amount of alcohol used is 3-20% of the volume of the mixed solvent. Using more than the stated range of alcohol is undesirable because excessive alcohol will increase the emission of volatile organic compounds, which will have adverse effects on economic and environmental aspects.

[0074] In this step, the main purpose of adding 5-10% of the oily acrylic monomer solution obtained in step A and 5-10% of the aqueous monomer solution obtained in step C is to allow the initiator to slowly decompose and initiate the polymerization reaction during the heating process of the system, thereby enabling the polymerization reaction to be initiated and carried out more stably.

[0075] Then, under a nitrogen atmosphere and a stirring speed of 50–500 rpm, the above monomer mixture solution is heated to a temperature of 70–85°C; when the reaction system shows blue light, the remaining oily acrylic monomer solution and aqueous monomer solution are added dropwise or in batches over 0.5–1.5 h, and then the temperature is lowered to 60–70°C and maintained at this temperature for 0.8–1.2 h.

[0076] In this step, nitrogen gas is introduced to remove oxygen from the reaction system, thereby ensuring that the initiator can function fully.

[0077] Next, 0.01 to 0.02% of the above-mentioned initiator based on the total mass of all monomers is added, and the mixture is kept at 60 to 70°C for 0.4 to 0.6 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin.

[0078] 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.

[0079] The obtained milky white emulsion-like waterborne self-polishing antifouling resin was subjected to routine infrared spectroscopy analysis, and the analytical results are listed in the appendix. Figure 1 middle.

[0080] From the appendix Figure 1 As can be seen from this, the water-based self-polishing antifouling resins prepared in Examples 1-5 (denoted as resins MA0, MA10, MA20, MA30, and MA40, respectively) showed a high viscosity at 2957 cm⁻¹. -1 Up to 2869cm -1 The -CH stretching vibrations, belonging to saturated alkanes on the main chain and side chains of polymers, appear at 1726 cm⁻¹. -1 A stretching vibration peak belonging to the -C=O group of saturated esters (-C=O(-COO-)) appears at 1726 cm⁻¹. -1 and 932cm -1At 3500 cm⁻¹, stretching vibration peaks of -C=O and bending vibration peaks of -OH, belonging to carboxylic acids (-COOH), respectively, appear. -1 Up to 3000cm -1 The broad and diffuse absorption peak at 1500 cm⁻¹ is due to the stretching vibration of the -OH group in carboxylic acid (-COOH). -1 Up to 1450cm -1 A symmetric stretching vibration peak belonging to the carboxylate group appears at 3364 cm⁻¹. -1 1688cm -1 1567cm -1 and 1246cm -1 The infrared spectra of MA0, MA10, MA20, MA30, and MA40 resins, belonging to the amide group (-CONH2), show stretching vibration peaks of -NH, -C=O, -NH, and -CN, respectively. These infrared spectral results indicate that the characteristic absorption peaks of the comonomers (butyl acrylate, methyl acrylate, acrylic acid, and acrylamide) all appear in the infrared absorption spectra of the resins MA0, MA10, MA20, MA30, and MA40, thus confirming the obtained waterborne self-polishing antifouling resin.

[0081] From the appendix Figure 1 b. It can be seen that the water-based self-polishing antifouling resins prepared in Examples 6-10 (denoted as resins TSi5, TSi10, TSi15, TSi20, and TSi25, respectively) at 2956 cm⁻¹ -1 Up to 2864cm -1 The -CH stretching vibrations, belonging to saturated alkanes on the main chain and side chains of polymers, appear at 1726 cm⁻¹. -1 A stretching vibration peak belonging to the C=O group of a saturated ester (-C=O(–COO-)) appears at 1726 cm⁻¹. -1 A stretching vibration peak belonging to the -C=O group of carboxylic acids (-COOH) appears at 3500 cm⁻¹. -1 Up to 3000cm -1 The broad and diffuse absorption peak at 1500 cm⁻¹ is due to the stretching vibration of the OH group in carboxylic acid (-COOH). -1 Up to 1450cm -1 A symmetric stretching vibration peak belonging to the carboxylate group appears at 3379 cm⁻¹. -1 and 1726cm -1 At 1087 cm⁻¹, stretching vibration peaks of -NH and -C=O, belonging to amide (-CONH₂), respectively, appeared. -1 A stretching vibration peak belonging to the -Si-O bond appears at 837 cm⁻¹. -1Stretching vibration peaks belonging to -Si-C appear on both sides. These infrared spectral results indicate that the characteristic absorption peaks of the comonomers (butyl acrylate, methyl acrylate, acrylic acid, acrylamide, and methacryloxytriisopropylsilane) all appear in the infrared absorption spectra of resins TSi5, TSi10, TSi15, TSi20, and TSi25, thus confirming the expected waterborne self-polishing antifouling resin.

[0082] The present invention also relates to an aqueous self-polishing antifouling resin prepared by the aforementioned preparation method.

[0083] This invention also relates to the use of the aforementioned waterborne self-polishing antifouling resin in the field of marine fouling control. The invention investigated the emulsion properties by observing the emulsion state, examined the adhesion properties of the waterborne self-polishing antifouling resin coating using the static bubble plate method, examined its self-polishing performance by calculating the self-polishing abrasion rate, and examined its antifouling performance by inhibiting microalgae adhesion, etc. For details, please refer to the Embodiments section.

[0084] [Beneficial Effects]

[0085] The beneficial technical effects of this invention are as follows: This invention prepares a water-based self-polishing antifouling resin through a soap-free emulsion polymerization method. This water-based self-polishing antifouling resin has self-emulsifying ability, which is beneficial to improving the resin's film-forming properties, water resistance, and shelf life, overcoming the technical defects of the prior art. The water-based self-polishing emulsion of this invention has good stability and will not experience phase separation or clumping problems even after long-term storage. Furthermore, this water-based self-polishing antifouling resin is not prone to demulsification or clumping under various conditions during preparation and storage. Water-based self-polishing antifouling coatings prepared using the water-based self-polishing antifouling resin prepared by this invention exhibit good film-forming properties, adhesion properties, storage stability, and application performance on substrates, and demonstrate excellent antifouling effects. [Attached Image Description]

[0086] Figure 1 This is the infrared spectrum of the water-based self-polishing and antifouling resin of the present invention;

[0087] In the figure: a - Examples 1-5, b - Examples 6-10;

[0088] Figure 2 This is a graph showing the test results of the adhesion performance of the water-based self-polishing antifouling resin of the present invention;

[0089] In the figure: a - Examples 1-5, b - Examples 6-10;

[0090] Figure 3 This is a graph showing the test results of the self-polishing performance of the water-based self-polishing and antifouling resin of the present invention;

[0091] In the figure: a - Examples 1-5, b - Examples 6-10;

[0092] Figure 4 This is a graph showing the test results of the algae-inhibiting performance of the water-based self-polishing antifouling resin of this invention;

[0093] In the figure: a - Examples 1-5, b - Examples 6-10;

[0094] Figure 5 The following is a diagram showing the test results of the antifouling coating using the water-based self-polishing antifouling resin of this invention as the film-forming material on a marine siding:

[0095] In the figure: a - Example 3, b - Example 6.

Detailed Implementation Methods

[0096] The invention will be better understood through the following examples.

[0097] Example 1: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0098] The implementation method of this embodiment is as follows:

[0099] A. Preparation of oil-based acrylic monomer mixture

[0100] The oily acrylic monomer mixture is obtained by mixing methyl acrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 10:70:0.

[0101] B. Preparation of unsaturated organic acid aqueous solution

[0102] Mix 3.6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 140% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0103] C. Preparation of aqueous monomer solutions

[0104] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1.1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 80:8 to obtain the aqueous monomer solution.

[0105] D. Preparation of water-based self-polishing antifouling resin

[0106] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and methanol is added at 130% of the total mass of oily acrylic monomer and aqueous monomer. The amount of methanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0107] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0108] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as MA0.

[0109] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 a.

[0110] Example 2: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0111] The implementation method of this embodiment is as follows:

[0112] A. Preparation of oil-based acrylic monomer mixture

[0113] The oily acrylic monomer mixture is obtained by mixing methyl acrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 15:70:0.

[0114] B. Preparation of unsaturated organic acid aqueous solution

[0115] Mix 3.6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 140% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0116] C. Preparation of aqueous monomer solutions

[0117] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1.1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 80:8 to obtain the aqueous monomer solution.

[0118] D. Preparation of water-based self-polishing antifouling resin

[0119] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and methanol is added at 130% of the total mass of oily acrylic monomer and aqueous monomer. The amount of methanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0120] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0121] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as MA10.

[0122] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 a.

[0123] Example 3: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0124] The implementation method of this embodiment is as follows:

[0125] A. Preparation of oil-based acrylic monomer mixture

[0126] The oily acrylic monomer mixture is obtained by mixing methyl acrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 20:65:0.

[0127] B. Preparation of unsaturated organic acid aqueous solution

[0128] Mix 3.6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 140% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0129] C. Preparation of aqueous monomer solutions

[0130] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1.1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 80:8 to obtain the aqueous monomer solution.

[0131] D. Preparation of water-based self-polishing antifouling resin

[0132] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and methanol is added at 130% of the total mass of oily acrylic monomer and aqueous monomer. The amount of methanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0133] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0134] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as MA20.

[0135] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 a.

[0136] Example 4: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0137] The implementation method of this embodiment is as follows:

[0138] A. Preparation of oil-based acrylic monomer mixture

[0139] The oily acrylic monomer mixture is obtained by mixing methyl acrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 25:60:0.

[0140] B. Preparation of unsaturated organic acid aqueous solution

[0141] Mix 3.6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 140% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0142] C. Preparation of aqueous monomer solutions

[0143] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1.1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 80:8 to obtain the aqueous monomer solution.

[0144] D. Preparation of water-based self-polishing antifouling resin

[0145] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and methanol is added at 130% of the total mass of oily acrylic monomer and aqueous monomer. The amount of methanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0146] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0147] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as MA30.

[0148] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 a.

[0149] Example 5: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0150] The implementation method of this embodiment is as follows:

[0151] A. Preparation of oil-based acrylic monomer mixture

[0152] The oily acrylic monomer mixture is obtained by mixing methyl acrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 30:55:0.

[0153] B. Preparation of unsaturated organic acid aqueous solution

[0154] Mix 3.6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 140% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0155] C. Preparation of aqueous monomer solutions

[0156] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1.1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 80:8 to obtain the aqueous monomer solution.

[0157] D. Preparation of water-based self-polishing antifouling resin

[0158] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and methanol is added at 130% of the total mass of oily acrylic monomer and aqueous monomer. The amount of methanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0159] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0160] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as MA40.

[0161] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 a.

[0162] Example 6: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0163] The implementation method of this embodiment is as follows:

[0164] A. Preparation of oil-based acrylic monomer mixture

[0165] The oily acrylic monomer mixture is obtained by mixing methyl methacrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 20:60:5.

[0166] B. Preparation of unsaturated organic acid aqueous solution

[0167] Mix 6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 150% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0168] C. Preparation of aqueous monomer solutions

[0169] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 90:9 to obtain the aqueous monomer solution.

[0170] D. Preparation of water-based self-polishing antifouling resin

[0171] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and ethanol, weighing 140% of the total mass of oily acrylic monomer and aqueous monomer, is added. The amount of ethanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0172] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0173] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as TSi5.

[0174] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 b.

[0175] Example 7: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0176] The implementation method of this embodiment is as follows:

[0177] A. Preparation of oil-based acrylic monomer mixture

[0178] The oily acrylic monomer mixture is obtained by mixing methyl methacrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 20:55:10.

[0179] B. Preparation of unsaturated organic acid aqueous solution

[0180] Mix 6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 150% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0181] C. Preparation of aqueous monomer solutions

[0182] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 90:9 to obtain the aqueous monomer solution.

[0183] D. Preparation of water-based self-polishing antifouling resin

[0184] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and ethanol, weighing 140% of the total mass of oily acrylic monomer and aqueous monomer, is added. The amount of ethanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0185] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0186] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as TSi10.

[0187] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 b.

[0188] Example 8: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0189] The implementation method of this embodiment is as follows:

[0190] A. Preparation of oil-based acrylic monomer mixture

[0191] The oily acrylic monomer mixture is obtained by mixing methyl methacrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 20:50:15.

[0192] B. Preparation of unsaturated organic acid aqueous solution

[0193] Mix 6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 150% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0194] C. Preparation of aqueous monomer solutions

[0195] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 90:9 to obtain the aqueous monomer solution.

[0196] D. Preparation of water-based self-polishing antifouling resin

[0197] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and ethanol, weighing 140% of the total mass of oily acrylic monomer and aqueous monomer, is added. The amount of ethanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0198] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0199] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as TSi15.

[0200] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 b.

[0201] Example 9: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0202] The implementation method of this embodiment is as follows:

[0203] A. Preparation of oil-based acrylic monomer mixture

[0204] The oily acrylic monomer mixture is obtained by mixing methyl methacrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 20:45:20.

[0205] B. Preparation of unsaturated organic acid aqueous solution

[0206] Mix 6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 150% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0207] C. Preparation of aqueous monomer solutions

[0208] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 90:9 to obtain the aqueous monomer solution.

[0209] D. Preparation of water-based self-polishing antifouling resin

[0210] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and ethanol, weighing 140% of the total mass of oily acrylic monomer and aqueous monomer, is added. The amount of ethanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0211] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0212] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as TSi20.

[0213] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 b.

[0214] Example 10: Preparation of the water-based self-polishing and antifouling resin of the present invention

[0215] The implementation method of this embodiment is as follows:

[0216] A. Preparation of oil-based acrylic monomer mixture

[0217] The oily acrylic monomer mixture is obtained by mixing methyl methacrylate hard oily acrylic monomer, butyl acrylate soft oily acrylic monomer and methacryloxytriisopropylsilane self-polishing monomer in a molar ratio of 20:40:25.

[0218] B. Preparation of unsaturated organic acid aqueous solution

[0219] Mix 6% of unsaturated organic acid based on the molar amount of oily acrylic acid monomer with 150% of water based on the molar amount of unsaturated organic acid, then add 89% of sodium hydroxide based on the molar amount of unsaturated organic acid, dissolve and mix evenly to obtain the aforementioned unsaturated organic acid aqueous solution.

[0220] C. Preparation of aqueous monomer solutions

[0221] According to the molar ratio of oily acrylic monomer to aqueous monomer of 85:15, add acrylamide aqueous monomer to the unsaturated organic acid aqueous solution obtained in step B, and then add an initiator of 1% based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture composed of azobisisobutyronitrile hydrochloride water-soluble initiator and azobisisobutyronitrile oil-soluble initiator in a mass ratio of 90:9 to obtain the aqueous monomer solution.

[0222] D. Preparation of water-based self-polishing antifouling resin

[0223] In a four-necked flask equipped with a stirrer, condenser and thermometer, a mixed solvent consisting of deionized water and ethanol, weighing 140% of the total mass of oily acrylic monomer and aqueous monomer, is added. The amount of ethanol is 14% of the volume of the mixed solvent. Then, the oily acrylic monomer solution obtained in step A and the aqueous monomer solution obtained in step C are added, each at 10% of their respective volumes. The mixture is stirred until homogeneous to obtain a monomer mixture solution.

[0224] Then, under a nitrogen atmosphere and a stirring speed of 300 rpm, the above monomer mixture solution was heated to 70°C; when the reaction system showed blue light, the remaining oily acrylic monomer solution and aqueous monomer solution were added dropwise at this temperature within 1 hour, and then the temperature was lowered to 70°C and maintained at this temperature for 1 hour.

[0225] Next, 0.01% of the above-mentioned initiator based on the total mass of all monomers was added, and the mixture was kept at 70°C for 0.5 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin, denoted as TSi25.

[0226] The infrared spectrum of the milky white, emulsion-like, water-based self-polishing and antifouling resin was detected according to the method described in this application specification. The results are shown in the appendix. Figure 1 b.

[0227] Application Example 1: Performance Test of the Waterborne Self-Polishing Antifouling Resin Emulsion of the Present Invention

[0228] The implementation method of this application example is as follows:

[0229] The emulsion-like waterborne self-polishing antifouling resins prepared in Examples 1-10 were immediately observed and their appearance, including color, transparency, uniformity, and blue light, was recorded visually. Then, they were placed in sample vials, sealed, and stored at room temperature for 6 months. The phenomena of emulsion layering, coagulation, and solid precipitation were observed in the same manner to analyze their stability.

[0230] Observations revealed that the water-based self-polishing antifouling resins prepared in Examples 1-5 were uniform and stable milky-white emulsions. After being stored at room temperature for 6 months, these emulsions did not exhibit stratification or agglomeration. While slight latex particle sedimentation was observed at the bottom of the emulsion, it could be shaken evenly. The water-based self-polishing antifouling resins prepared in Examples 6-10 were uniform and stable milky-white with a bluish tint. The emulsions prepared in Examples 6 and 7 did not exhibit stratification or agglomeration after being stored at room temperature for 6 months, while the water-based self-polishing antifouling resin emulsions prepared in the other examples showed latex particle sedimentation at the bottom, but were generally uniform and stable.

[0231] Application Example 2: Adhesion Performance Test of the Water-Based Self-Polishing Antifouling Resin of the Present Invention

[0232] The implementation method of this application example is as follows:

[0233] Test sample: Waterborne self-polishing antifouling resin prepared in Examples 1-10;

[0234] Test substrate: Acrylonitrile / butadiene / styrene copolymer (ABS) sheet, ABS sheet size 50×50×1mm 3 ;

[0235] Pretreatment of test substrate: The ABS board used in the test was polished evenly with 80-grit sandpaper, then cleaned with ethanol and water respectively, and dried at room temperature to constant weight.

[0236] Coating method: The water-based self-polishing antifouling resin of the present invention is uniformly coated on the ABS board using a conventional coating method, with a coating amount of 300μg.

[0237] The adhesion performance test was conducted according to the following standard: "Determination of Salt Water Resistance of Marine Coatings—Immersion Method with Salt Water and Hot Salt Water" (GB / T10834-2008).

[0238] Specifically, the adhesion properties of the water-based self-polishing antifouling resin of this invention were first tested using the static seawater bubble plate method, and the test results are listed in the appendix. Figure 2 middle.

[0239] From the appendix Figure 2 As can be seen, the water-based self-polishing antifouling resins prepared in Examples 1-5 did not detach during the 300-day static bubble board test, demonstrating good adhesion. With the increase in the content of hard oil-based acrylic monomers, the water-based self-polishing antifouling resin exhibited poor water resistance and was more easily eroded by water, resulting in more surface peeling of the coating. However, the underlying layer still showed good adhesion to the substrate.

[0240] From the appendix Figure 2 As can be seen from b, the water-based self-polishing antifouling resins prepared in Examples 6-10 did not detach during the 300-day static bubble plate test, exhibiting good adhesion and no surface peeling. This demonstrates that the introduction of methacryloxytriisopropylsilane improved the resin's water resistance.

[0241] Application Example 3: Study on the self-polishing performance of the water-based self-polishing and antifouling resin of the present invention

[0242] The implementation method of this application example is as follows:

[0243] Test sample: Waterborne self-polishing antifouling resin prepared in Examples 1-10;

[0244] Test substrate: ABS sheet, ABS sheet size 350×100×3mm 3 ;

[0245] Coating method: Conventional coating method, coating amount is 400μg;

[0246] At room temperature, ABS sheets coated with a water-based self-polishing coating were dried and weighed (M1). The samples were then fixed in a dynamic water-spraying acceleration simulation device and immersed in seawater for a 10-day immersion cycle. After one immersion cycle, the samples were removed and rinsed with deionized water. The samples were then dried in a 40°C oven for two days, and the dry weight (M1) was recorded. t The sample was then placed back into the seawater for further immersion. The seawater temperature was room temperature, the drum rotation speed was 80 rpm, and the device radius was 60 cm.

[0247] The formula for calculating the self-polishing abrasion rate (N) is:

[0248]

[0249] Where: M i The quality of the water-based self-polishing coating dried in the previous cycle, of which M in the first cycle i The initial mass M1, M is the mass of the water-based self-polishing coating after drying. t S represents the mass of the water-based self-polishing coating dried in this cycle, and S represents the area occupied by the water-based self-polishing coating.

[0250] Test results: From the attached Figure 3 As can be seen, the self-polishing erosion rate of the waterborne self-polishing resins prepared in Examples 1-5 showed a basically consistent trend. In the initial soaking period (10 days), the self-polishing erosion rate of the resin was the highest and the mass loss was the fastest due to the rapid dissolution of residual solvent and unreacted monomers in seawater. As the soaking time increased (20-50 days), the self-polishing erosion rate of the resin gradually decreased and gradually stabilized at 5 × 10⁻⁶. -4 ~3×10 -3 g · cm -2 between.

[0251] From the appendix Figure 3 As can be seen from b, the waterborne self-polishing resins prepared in Examples 6-10 exhibited the highest self-polishing abrasion rate during the initial immersion period (10 days). With increasing immersion time, the self-polishing abrasion rate gradually decreased and stabilized at 1×10⁻⁶. -3 ~2×10 -3 g · cm -2 The results show that the self-polishing rate of the waterborne self-polishing and antifouling resins prepared in Examples 6-10 is more stable than that in Examples 1-5, and stable uniform polishing can be achieved after a certain period of time. The waterborne self-polishing resins prepared in Examples 6-10 have a more stable self-polishing abrasion rate and good self-polishing performance. The introduction of methacryloxytriisopropylsilane improves the self-polishing rate of the resin.

[0252] Application Example 4: Study on the Algae-inhibiting Performance of the Water-based Self-polishing Antifouling Resin of the Present Invention

[0253] The implementation method of this application example is as follows:

[0254] Test sample: Waterborne self-polishing antifouling resin prepared in Examples 1-10;

[0255] Test substrate: ABS sheet, ABS sheet size 50×50×1mm 3 ;

[0256] Coating method: Conventional coating method, coating amount is 300μg;

[0257] Experimental basis: The evaluation method described in the literature "Comparison of algal cell counting methods in algal growth inhibition experiments" was used.

[0258] The method for inhibiting algal adsorption is as follows: Filtered, sterilized, and cooled seawater was mixed with vitamins, sodium nitrate, sodium phosphate, sodium silicate, and trace elements in a certain proportion to prepare a nutrient solution. This solution was then mixed with *Nyctaginea crescentis* cultured to its exponential growth cycle to prepare an algal solution with an absorbance of 0.09 at a UV absorption wavelength of 680 nm. The water-based self-polishing antifouling resin prepared in Examples 1-10 was coated onto an ABS plate and placed face up at the bottom of a 10 cm diameter culture dish. 40 mL of algal solution was then added. The culture dish was placed in an intelligent artificial climate chamber and cultured under conditions of 4000 lux light intensity, a light-to-dark ratio of 14:10, and a temperature of 21°C. The algal solution was shaken at the same time every day. On the 5th day, the sample was removed, and the coating surface was rinsed clean with the nutrient solution. The absorbance of the rinsing solution was measured at a wavelength of 680 nm using a UV spectrophotometer. The algal concentration was then calculated based on a standard curve.

[0259] Test results: From the attached Figure 4 As can be seen, with the increase of methyl acrylate content in the resin, the concentration of algae (small crescent algae and small chlorella) adsorbed on the surface of the water-based self-polishing antifouling resin coating prepared in Examples 1-5 gradually decreases, and the resin has a stronger ability to inhibit algae adsorption.

[0260] From the appendix Figure 4 b. It can be seen that the algae concentration adsorbed on the surface of the water-based self-polishing antifouling resin coating prepared in Examples 6-10 is generally low, indicating that the introduction of methacryloyloxytriisopropylsilane increases the antifouling performance of the resin.

[0261] Application Example 5: Research on antifouling coatings using water-based self-polishing antifouling resin as film-forming material for marine cladding

[0262] The implementation method of this application example is as follows:

[0263] Test samples: waterborne self-polishing antifouling resin MA20 prepared in Example 3 and waterborne self-polishing antifouling resin TSi5 prepared in Example 6;

[0264] The implementation method of this application example is as follows:

[0265] At room temperature, 35g of the waterborne self-polishing antifouling resin MA20 obtained in Example 3, 1.5g of film-forming aid polyethylene glycol 3000, 25g of inorganic antifouling agent Cu2O, 10g of antifouling agent TMTD, 4.5g of ZnO, 3.0g of TiO2, 3.0g of Fe2O3, 3.0g of talc, and 0.7g of activated carbon were placed in a grinding cup and dispersed at 3000rpm for 30min using a rapid dispersion tester to obtain waterborne self-polishing antifouling coating M1. The fineness of the sample was measured, and it met the requirements when the fineness was less than 50μm. The sample was then dispensed for later use. The dosages of Cu2O, TMTD, and chlorothalonil can also be adjusted as shown in the table below using the above method.

[0266]

[0267] Test substrate: PVC board, dimensions 900×300×3mm 3 A blank board was used as a control.

[0268] Pretreatment of test substrate: The PVC board used in the test was evenly sanded with 80-grit sandpaper, then cleaned with ethanol and water respectively, and dried at room temperature to constant weight.

[0269] Coating method: Conventional coating method, coating amount is 8000μg;

[0270] Antifouling performance testing is based on: "Test Method for Templates of Shallow Sea Impregnated Coatings" (GB / T5370-2007);

[0271] The implementation method is as follows: At room temperature, the antifouling coatings obtained by the above method were applied to treated PVC boards, air-dried indoors for 2 days, and then dried in an oven at 40℃ for 2 days, yielding antifouling coatings with water-based self-polishing antifouling resins MA20 and TSi5 as film-forming agents, respectively, for later use. In December 2022, a test was conducted in the waters near Qingdao Port, China, with the samples submerged to a depth of 1.5 meters below sea level. At regular intervals, the samples were removed from the sea and their surfaces were gently rinsed with seawater to remove dirt. After inspecting and photographing the samples, they were returned to their original positions as soon as possible to avoid affecting the growth of fouling organisms on the sample surface. The antifouling performance of the water-based self-polishing antifouling coatings was evaluated by observing the amount of fouling on the sample surface and the types of fouling organisms.

[0272] Test results: From the attached Figure 5 It can be seen that after 90 days, all water-based self-polishing antifouling coatings remained intact on the offshore panels, and there were no visible fouling organisms attached to the surface. Since the offshore panels were installed in December, biological growth and development are slow, so the blank sample also showed only a small amount of fouling organisms.

Claims

1. A method for preparing a water-based self-polishing and antifouling resin, characterized in that... The preparation steps of the preparation method are as follows: A. Preparation of oil-based acrylic monomer mixture The oily acrylic monomer mixture is obtained by mixing hard oily acrylic monomer, soft oily acrylic monomer and self-polishing monomer in a molar ratio of 5-30:20-70:0-30, and the amount of self-polishing monomer is not zero; the self-polishing monomer is acryloyloxytriisopropylsilane, methacryloxytriisopropylsilane, γ-methacryloyloxypropyltrimethoxysilane or a mixture thereof. B. Preparation of unsaturated organic acid aqueous solution Mix 3-20% of unsaturated organic acid (based on the molar amount of oily acrylic acid monomer) with 30-200% of water (based on the molar amount of unsaturated organic acid) until homogeneous. Then add 10-100% of sodium hydroxide (based on the molar amount of unsaturated organic acid), dissolve and mix until homogeneous to obtain the aforementioned unsaturated organic acid aqueous solution. C. Preparation of aqueous monomer solutions One or more aqueous monomers are added to the unsaturated organic acid aqueous solution obtained in step B according to a molar ratio of oily acrylic monomer to aqueous monomer of 80-95:5-25, followed by the addition of 0.1-1.5% initiator based on the total mass of oily acrylic monomer and aqueous monomer. The initiator is a mixture of a water-soluble initiator and an oil-soluble initiator in a mass ratio of 70-95:0-10, to obtain the aqueous monomer solution. The aqueous monomer is acrylamide, hydroxyacrylamide, vinylpyrrolidone, hydroxyacrylate, or a mixture thereof. D. Preparation of water-based self-polishing antifouling resin In a four-necked flask equipped with a stirrer, condenser and thermometer, add 100-300% of a mixed solvent composed of deionized water and alcohol based on the total mass of oily acrylic monomer and watery monomer. Then add the oily acrylic monomer solution obtained in step A and the watery monomer solution obtained in step C, each added in an amount of 5-10% of their respective volumes. Mix well to obtain a monomer mixture solution. Then, under a nitrogen atmosphere and a stirring speed of 50–500 rpm, the above monomer mixture solution is heated to a temperature of 70–85°C. When the reaction system shows blue light, the remaining oily acrylic monomer solution and aqueous monomer solution are added dropwise or in batches at this temperature over 0.5–1.5 h. Then the temperature is lowered to 60–70°C and maintained at this temperature for 0.8–1.2 h. Next, 0.01 to 0.02% of the above-mentioned initiator based on the total mass of all monomers is added, and the mixture is kept at 60 to 70°C for 0.4 to 0.6 hours and then cooled to room temperature to obtain a milky white emulsion-like waterborne self-polishing antifouling resin.

2. The preparation method according to claim 1, characterized in that... In step A, the hard oily acrylic monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, or a mixture thereof; the soft oily acrylic monomer is propyl acrylate, butyl acrylate, isoamyl acrylate, dodecyl acrylate, octadecyl acrylate, or a mixture thereof.

3. The preparation method according to claim 1, characterized in that... In step B, the unsaturated organic acid is acrylic acid, methacrylic acid, methylene succinic acid, or a mixture thereof.

4. The preparation method according to claim 1, characterized in that... The hydroxyacrylamide is N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, or N-hydroxypropylacrylamide; the hydroxyacrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, or 4-hydroxybutyl acrylate, or a mixture thereof.

5. The preparation method according to claim 1, characterized in that... The water-soluble initiator is one or more initiators selected from azobisisobutyrazoline hydrochloride, azobisisopropylimidazoline, azobisisobutyramidine hydrochloride, potassium persulfate, or ammonium persulfate; the oil-soluble initiator is one or more initiators selected from azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, benzoyl tert-butyl peroxide, or methyl ethyl ketone peroxide.

6. The preparation method according to claim 1, characterized in that... In step D, the alcohol in the mixed solvent is one or more alcohols selected from methanol, ethanol, ethylene glycol or glycerol, and the amount of alcohol used is 3 to 20% of the volume of the mixed solvent.

7. The water-based self-polishing antifouling resin prepared by the preparation method according to any one of claims 1-6.

8. The use of the water-based self-polishing antifouling resin according to claim 7 in the field of marine fouling control.

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