Slow-release polishing acrylic acid metal salt composite coating as well as preparation method and application thereof

Abstract

The invention relates to the technical field of coating preparation, in particular to a slow-release polishing acrylic acid metal salt composite coating as well as a preparation method and application thereof. The preparation method comprises the following steps: carrying out hydrothermal crystallization at 150-200 DEG C for 12-36 hours by taking a TS-1 molecular sieve as a seed crystal in a system in which ammonium sulfate and ammonium carbonate coexist, and calcining at 600-800 DEG C for 4-8 hours. The special porous titanosilicate carrier with proper aperture and surface chemical properties is synthesized by adjusting each process parameter in a targeted manner, so that the special porous titanosilicate carrier can efficiently and saturatively adsorb silicone oil to form an independent silicone oil slow-release unit. Subsequently, this unit is physically blended with an acrylic metal salt resin matrix. In the composite coating, the silicone oil is stably released for a long time according to the structural design of a carrier pore channel, and excellent static antifouling capacity is continuously provided; and meanwhile, the resin matrix keeps the dynamic self-polishing function. The two components cooperate with each other, so that the comprehensive antifouling efficiency and the service life of the coating in dynamic and static complex marine environments are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of coating preparation technology, and in particular to a slow-release polishing acrylic metal salt composite coating, its preparation method, and its application. Background Technology

[0002] Marine biofouling is a major challenge restricting the long-term reliable operation of ships, offshore platforms, and other facilities. Antifouling coatings are currently the most economical and effective solution. However, there is a significant performance gap between current mainstream technologies: self-polishing coatings, represented by zinc acrylate and copper acrylate resins, achieve dynamic antifouling through surface ion exchange and dissolution. But under still water or low flow conditions, their surface renewal is slow, and they are easily covered by biofilms and become ineffective.

[0003] To impart static antifouling capabilities to coatings, the introduction of lubricating components such as silicone oil has become a common improvement direction. However, existing methods still have two main problems: First, simply physically mixing silicone oil and resin leads to rapid migration and loss of the lubricant, resulting in a very short effective protection period. Second, chemical grafting is used to bond the silicone oil structure to the resin backbone (e.g., Chinese patent CN202011354017.9). Although this method extends the retention time, the release of silicone oil is constrained by the hydrolysis and polishing process of the resin backbone. This strong coupling makes it impossible to independently and stably control the release rate, with the risk of insufficient release in the early stage and sudden detachment of fragments in the later stage coexisting, making it difficult to achieve long-term and controllable slow release, and resulting in insufficient durability and reliability of the antifouling effect.

[0004] Therefore, it is of great significance to develop a special carrier with independent structure and stable oil storage to achieve long-term and controllable sustained release of silicone oil, thereby forming a stable and lasting synergy with the self-polishing function of acrylic metal salt resin. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem in the prior art that the strong coupling between silicone oil release and resin self-polishing process in methods such as chemical grafting leads to uncontrollable silicone oil release and short-lasting static anti-fouling effect. This invention provides a slow-release polishing acrylic metal salt composite coating, its preparation method, and its application.

[0006] The first aspect of this invention provides a method for preparing a slow-release polishing acrylic metal salt composite coating, comprising the following steps: S1. Preparation of porous titanate supports: Tetraethyl orthosilicate and tetrapropylammonium hydroxide template agent are dissolved in water and reacted at 60-90℃ for 4-8 hours to obtain a silicon source solution; titanium trichloride solution, triethanolamine complexing agent and hydrogen peroxide solution are mixed to obtain a titanium source solution; The titanium source solution and the silicon source solution were mixed, and ammonium sulfate, ammonium carbonate, TiO2 powder and TS-1 molecular sieve were added as seed crystals. The mixture was then transferred to a high-pressure reactor and hydrothermally crystallized at 150-200℃ for 12-36 hours. The crystallized product was centrifuged and dried sequentially, and then calcined at 600-800℃ for 4-8 hours to remove the template agent and obtain a porous titanosilicon support. S2. Preparation of the silicone oil slow-release unit: The porous titanate support obtained in step S1 is immersed in silicone oil with a dynamic viscosity of 20-200 mPa·s for 6-24 hours until saturation adsorption is achieved. Then, the free silicone oil on the surface is removed to obtain a slow-release unit loaded with silicone oil inside. S3. Forming of composite coating: The silicone oil slow-release unit obtained in step S2 is uniformly mixed with the acrylic metal salt resin matrix, and then coated onto the substrate surface to form a coating with a wet film thickness of 150-300 micrometers. After curing, a composite coating is obtained.

[0007] This invention provides a method for preparing a slow-release polishing acrylic metal salt composite coating. First, using TS-1 molecular sieve as seed crystals, hydrothermal crystallization is performed at 150-200℃ for 12-36 hours in a system containing ammonium sulfate and ammonium carbonate, followed by calcination at 600-800℃ for 4-8 hours. By specifically adjusting various process parameters, a porous titanosilicon carrier with suitable pore size and surface chemical properties is synthesized, enabling it to efficiently and saturately adsorb silicone oil, forming an independent silicone oil slow-release unit. Subsequently, this unit is physically blended with an acrylic metal salt resin matrix. In this composite coating, silicone oil is released long-term and stably according to the carrier's pore structure design, continuously providing excellent static antifouling capabilities; simultaneously, the resin matrix maintains its dynamic self-polishing function. The synergistic effect of these two aspects significantly improves the overall antifouling performance and service life of the coating in complex dynamic and static marine environments, achieving remarkable progress.

[0008] Furthermore, in step S1, the amount of TiO2 powder added is 1%-10% of the mass of tetraethyl orthosilicate; the amount of TS-1 molecular sieve seed crystals added is 0.1%-1% of the mass of tetraethyl orthosilicate. The added TiO2 powder is used to supplement the titanium source and adjust the grain size and pore structure of the final support.

[0009] Furthermore, in step S1, the particle size of the TiO2 powder is 20-50 nm.

[0010] Furthermore, in step S1, the total amount of ammonium sulfate and ammonium carbonate added, relative to the molar number of tetraethyl orthosilicate, is 0.5-2.0 mol / mol. Furthermore, the molar ratio of ammonium sulfate to ammonium carbonate is 1:0.8-1:1.2.

[0011] Furthermore, in the silicone oil sustained-release unit obtained in step S2, the loading of silicone oil is 50%-70% of the dry basis mass of the porous titanate support.

[0012] Furthermore, in step S2, the silicone oil is at least one of dimethyl silicone oil and benzyl silicone oil.

[0013] Furthermore, in S2, the temperature of the impregnation process is 20-30℃. During the impregnation period, the container is gently shaken for 1-2 minutes every 2-3 hours to ensure that the carrier particles are in full contact with the silicone oil. The criterion for saturated adsorption is: the carrier mass no longer increases for 2 consecutive hours (accuracy 0.01g).

[0014] Furthermore, in step S3, the acrylate metal salt resin matrix is ​​at least one of zinc acrylate resin and copper acrylate resin.

[0015] Further, in step S3, the amount of silicone oil slow-release unit added is 5%-20% of the solid mass of the acrylate metal salt resin matrix. Preferably, in step S3, the amount of silicone oil slow-release unit added is 10%-15% of the solid mass of the acrylate metal salt resin matrix.

[0016] Further, in step S3, the synthesis method of the acrylic metal salt resin matrix includes: using a mixed solvent of xylene and n-butanol (volume ratio 3-4:1) as the reaction medium, using acrylate monomers (ethyl acrylate, butyl acrylate, etc.) and methacrylic acid as comonomers (methacrylic acid accounts for 15%-25% of the total mass of monomers), and copolymerizing at 85-95℃ for 4-6 hours under the action of an initiator (benzoyl peroxide, amounted to 0.8%-1.2% of the total mass of monomers) to obtain an acrylic prepolymer; subsequently adding a metal oxide (zinc oxide or copper oxide, molar ratio to methacrylic acid 1:1.0-1.2) and naphthenic acid (acid value 180-220 mg KOH / g, amounted to 3-3.5 times the mass of the metal oxide), and reacting at 110-125℃ for 4-6 hours to dehydrate, to obtain an acrylic metal salt resin matrix with a solid content of 45%-55% and an acid value of 35-55 mg KOH / g.

[0017] A second aspect of the present invention provides a slow-release polishing acrylic metal salt composite coating prepared by the above preparation method.

[0018] A third aspect of the invention provides the application of the slow-release polishing acrylic metal salt composite coating as described above as an antifouling coating on the surface of ships, offshore platforms or aquaculture cage facilities.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides a method for preparing a slow-release polishing acrylic metal salt composite coating. First, using TS-1 molecular sieve as seed crystals, hydrothermal crystallization is performed at 150-200℃ for 12-36 hours in a system containing ammonium sulfate and ammonium carbonate, followed by calcination at 600-800℃ for 4-8 hours. By specifically adjusting various process parameters, a porous titanosilicon carrier with suitable pore size and surface chemical properties is synthesized, enabling it to efficiently and saturately adsorb silicone oil, forming an independent silicone oil slow-release unit. Subsequently, this unit is physically blended with an acrylic metal salt resin matrix. In this composite coating, silicone oil is released long-term and stably according to the carrier's pore structure design, continuously providing excellent static antifouling capabilities; simultaneously, the resin matrix maintains its dynamic self-polishing function. The synergistic effect of these two aspects significantly improves the overall antifouling performance and service life of the coating in complex dynamic and static marine environments, achieving remarkable progress. Attached Figure Description

[0020] Figure 1 To assess the antibacterial properties of the polished acrylic metal salt composite coating: (a) blank; (b) zinc acrylate naphthenic acid resin; (c) composite coating of Example 1; (d) composite coating of Example 2.

[0021] Figure 2 This is a morphology diagram of the TS-1 molecular sieve. Detailed Implementation

[0022] The present invention will now be described in further detail with reference to specific embodiments. However, this should not be construed as limiting the scope of the present invention to the following embodiments; all technologies implemented based on the content of the present invention fall within the scope of the present invention.

[0023] The following examples and comparative examples are used to further illustrate the present invention, and are not intended to limit the scope of protection of the present invention. Unless otherwise specified, all raw materials are commercially available industrial grade or chemically pure, and all ratios are mass ratios or mass percentages.

[0024] Example 1 1.1 Preparation of porous titanosilicon supports 1040 g of tetraethyl orthosilicate (TEOS) and 1080 g of a 25% (w / w) tetrapropylammonium hydroxide (TPAOH) aqueous solution were weighed and dissolved in 2000 mL of deionized water. The mixture was reacted at 80 °C and 120 rpm for 6 hours with mechanical stirring to obtain a clear silicon source solution. 142 g of a 20% (w / w) titanium trichloride (TiCl3) aqueous solution and 134 g of triethanolamine (TEOA) were mixed, and 52 g of a 30% (w / w) hydrogen peroxide aqueous solution was slowly added dropwise under an ice-water bath with stirring to form a stable, deep red, transparent titanium source solution. Under continuous stirring, the titanium source solution was slowly added to the silicon source solution, followed by 198 g of ammonium sulfate, 144 g of ammonium carbonate, 52 g of titanium dioxide (TiO2, P25 type) powder, and 5.2 g of TS-1 molecular sieve seed crystals. The mixture was stirred for 2 hours to form a homogeneous gel. The gel was transferred to a 5 L high-pressure reactor and statically hydrothermally crystallized at 180 °C for 24 hours. After the reaction was completed, the product was allowed to cool naturally, centrifuged, washed with deionized water until neutral, and dried in an oven at 110°C for 12 hours. The dried precursor powder was placed in a muffle furnace and heated to 750°C at a programmed rate of 2°C / min, and calcined at this temperature for 6 hours to completely remove the organic template agent, yielding a white powdery porous titanosilicon support, denoted as support-TS.

[0025] 1.2 Preparation of silicone oil sustained-release unit 100.0 g of the above-mentioned carrier-TS was weighed and placed in 500 mL of dimethyl silicone oil (Dow Corning PMX-200) with a dynamic viscosity of 50 mPa·s. The mixture was allowed to stand at 25°C for 18 hours, with gentle shaking every 2 hours during this period. After impregnation, the mixture was transferred to a 200-mesh stainless steel sieve and drained for 4 hours to remove free silicone oil adhering to the particles and surfaces, resulting in a semi-transparent silicone oil slow-release unit, denoted as slow-release unit-TS. By accurately weighing the carrier before and after impregnation, its silicone oil adsorption capacity was calculated to be 62.3% of the dry weight of the carrier itself (i.e., oil loading rate).

[0026] 1.3 Synthesis of Zinc Acrylate Resin Matrix In a 2000 mL four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen inlet, 400 g of xylene and 100 g of n-butanol were added as a mixed solvent. Nitrogen gas was introduced for protection, and the temperature was raised to 90 °C. 10% (approximately 47 g) of the pre-mixed monomer mixture (176 g ethyl acrylate, 208 g butyl acrylate, and 86 g methacrylic acid) was added to the reaction flask along with 4.7 g benzoyl peroxide (BPO) as an initiator. After reacting at 90 °C for 30 minutes, the remaining 90% of the monomer mixture was added dropwise over 3 hours using a constant-pressure dropping funnel. After the addition was complete, the reaction was continued at 90 °C for 2 hours to obtain a pale yellow, viscous acrylic acid prepolymer solution. The system was cooled to 60 °C, and 40.0 g of zinc oxide powder and 140 g of naphthenic acid (acid value 200 mg KOH / g) were added sequentially. The temperature was then slowly increased to 120°C, and the reaction and dehydration were carried out at this temperature for 5 hours. The water generated during the reaction was discharged through a water separator until no water was distilled from the system. After the reaction was completed, the temperature was lowered to below 80°C and the product was discharged, yielding a brownish-yellow transparent zinc acrylate resin solution with a solid content of 50.5%. Its acid value was determined by titration to be 45 mgKOH / g.

[0027] 1.4 Preparation of Composite Coating Weigh 150 g of the above zinc acrylate resin solution (75.8 g of solid resin) and place it in a mixing tank. While stirring at low speed, slowly add 11.37 g (15.0% of the resin solids mass) of the slow-release unit-TS. Then, use a high-speed disperser (IKA T25) to disperse the mixture at 1000 rpm for 30 minutes until a uniform grayish-white slurry is formed, with no visible particle agglomeration. Use a 100-micron wire rod coater to evenly coat the slurry onto the surface of a tinplate sheet (150 mm × 70 mm × 0.3 mm) that has been sanded with 400# sandpaper and cleaned with acetone. The wet film thickness is controlled at approximately 250 microns. Place the coated sample horizontally in a ventilated environment at 23±2℃ and 50±5% relative humidity for 7 days to cure, obtaining a composite coating sample, denoted as Coating-TS.

[0028] Example 2 The carrier synthesis steps were the same as in Example 1.1, except for the following parameters: the hydrothermal crystallization temperature was adjusted to 160℃ and the time to 30 hours; the calcination temperature was adjusted to 680℃ and the time to 7 hours. The resulting carrier was designated as Carrier-TS-2, with a BET specific surface area of ​​365 m² / g. Following the same method as in Example 1.2, a sustained-release unit was prepared by impregnation with dimethyl silicone oil with a dynamic viscosity of 100 mPa·s, exhibiting a silicone oil adsorption capacity of 57.8%. Following the method in Example 1.4, a coating was composited with zinc acrylate resin at an addition amount of 10.0%, and the resulting coating was designated as Coating-TS-2.

[0029] Comparative Example 1 Base resin coating without sustained-release unit The zinc acrylate resin solution synthesized in Example 1.3 was used to coat the film without adding any slow-release unit or silicone oil, and this film is referred to as coating-Zn.

[0030] Comparative Example 2 Silicone oil direct blend coating Weigh 7.08 g of the same 50 mPa·s dimethyl silicone oil and mix it directly with 150 g of zinc acrylate resin solution (75.8 g solids) using high-speed mechanical mixing to prepare a coating, denoted as coating-blend.

[0031] Comparative Example 3 Using an amorphous porous silica carrier Commercially available hydrophilic fumed silica (Evonik Aerosil 200, BET specific surface area 200 ± 25 m² / g, amorphous structure, hydrophilic surface) was used to replace the carrier-TS. 100 g of Aerosil 200 was weighed and impregnated using the same method as in Example 1.2. Its silicone oil adsorption capacity was 48.2%. A coating was prepared at an addition amount of 15.0%, denoted as Coating-A200.

[0032] Comparative Example 4 Hydrothermal Synthesis without TS-1 Seeds The support was prepared according to the method in Example 1.1, but without the addition of TS-1 molecular sieve seeds. The coating was prepared according to the methods in Examples 1.2 and 1.4, and is designated as Coating-NoSeed.

[0033] Comparative Example 5 Hydrothermal synthesis without ammonium sulfate / ammonium carbonate additives The support was prepared according to the method of Example 1.1, but without the addition of ammonium sulfate and ammonium carbonate. The resulting product was designated as support-NoSalt, and its total pore volume was 0.25 cm³ / g as shown by nitrogen adsorption testing. The coating was prepared according to the methods of Examples 1.2 and 1.4, and was designated as coating-NoSalt.

[0034] Comparative Example 6 Hydrothermal Synthesis without Added TiO2 Powder The support was prepared according to the method of Example 1.1, but without the addition of external TiO2 powder (P25). The resulting product is denoted as support-NoTiO2. The coating was prepared according to the methods of Examples 1.2 and 1.4, and is denoted as coating-NoTiO2.

[0035] Comparative Example 7 Low-temperature hydrothermal synthesis The support was prepared according to the method in Example 1.1, but the hydrothermal crystallization temperature was adjusted to 120°C (below 150°C), and the time was extended to 48 hours. The resulting product is denoted as support-LowT. The prepared coating is denoted as coating-LowT.

[0036] Comparative Example 8 Low-temperature calcination treatment The dried precursor obtained in Example 1.1 was calcined in a muffle furnace at 500°C (below 600°C) for 6 hours. The resulting product is denoted as carrier-LowC. The prepared coating is denoted as coating-LowC.

[0037] Performance testing and data analysis Test 1: Long-lasting sustained-release performance test of silicone oil Procedure: Each coated sample (5cm × 5cm) was immersed in artificial seawater (ASTM D1141) and placed in a 30°C constant-temperature shaker (60 rpm). Samples were taken on days 1, 7, 14, 30, 60, and 90. Each sample was gently rinsed three times with 50 mL of n-hexane, and the rinse solution (component A: free and easily desorbed silicone oil on the surface) was collected. The sample was then placed in a Soxhlet extractor and extracted with 150 mL of toluene for 6 hours (component B: silicone oil migrating from the coating interior to the near-surface region). The solvents of components A and B were combined, rotary evaporated, dried at 105°C, and weighed. The cumulative release rate was calculated. Each sample was tested in triplicate.

[0038] Table 1 The above data shows that, although the absence of any key process elements of the present invention may result in a certain degree of antifouling effect in the short term, it is impossible to achieve long-term, stable, and slow-release of silicone oil. Its antifouling life and reliability will be significantly lower than the composite coating provided by the present invention.

[0039] Test 2: Static antifouling performance test Antibacterial activity: Referencing GB / T 21866-2008, *Escherichia coli* was selected. The bacterial suspension concentration was 1×10⁻⁶. 6 CFU / mL. Take 0.1 mL and drop it onto the surface of a coated sample plate (2cm × 2cm), cover with a sterile film, incubate at 30℃ for 24 hours, then wash, spread on the plate, and count. Calculate the antibacterial rate (R) using an uncoated ABS plate as a blank control. Figure 1 As shown.

[0040] Anti-algae adhesion: Navicula was selected and cultured under light in f / 2 medium. The sample was immersed in the algal solution and cultured under static low light. Samples were taken on day 7 and day 30, and the percentage of diatom coverage area on the surface was observed and calculated using a fluorescence microscope.

[0041] The data and conclusions are shown in Table 2: Table 2 In some embodiments, in step S1, the amount of TiO2 powder added is 1%-10% of the mass of tetraethyl orthosilicate; the amount of TS-1 molecular sieve seed crystals added is 0.1%-1% of the mass of tetraethyl orthosilicate. The added TiO2 powder is used to supplement the titanium source and adjust the grain size and pore structure of the final support.

[0042] In some embodiments, in step S1, the total amount of ammonium sulfate and ammonium carbonate added is 0.5-2.0 mol / mol relative to the moles of tetraethyl orthosilicate.

[0043] In some embodiments, in the silicone oil sustained-release unit obtained in step S2, the loading of silicone oil is 50%-70% of the dry basis mass of the porous titanate support.

[0044] In some embodiments, in step S2, the silicone oil is at least one of dimethyl silicone oil and benzyl silicone oil.

[0045] In some embodiments, in S2, the temperature of the impregnation process is 20-30°C, and the container is gently shaken for 1-2 minutes every 2-3 hours during the impregnation period to ensure that the carrier particles are in full contact with the silicone oil; the criterion for saturated adsorption is: the carrier mass no longer increases for 2 consecutive hours (accuracy 0.01g).

[0046] In some embodiments, in step S3, the acrylate metal salt resin matrix is ​​at least one of zinc acrylate resin and copper acrylate resin.

[0047] In some embodiments, in step S3, the amount of silicone oil slow-release unit added is 5%-20% of the solid mass of the acrylate metal salt resin matrix. Preferably, in step S3, the amount of silicone oil slow-release unit added is 10%-15% of the solid mass of the acrylate metal salt resin matrix.

[0048] In some embodiments, in step S3, the method for synthesizing the acrylic metal salt resin matrix includes: using a mixed solvent of xylene and n-butanol (volume ratio 3-4:1) as the reaction medium, using acrylate monomers (ethyl acrylate, butyl acrylate, etc.) and methacrylic acid as comonomers (methacrylic acid accounts for 15%-25% of the total mass of monomers), copolymerizing at 85-95℃ for 4-6 hours under the action of an initiator (benzoyl peroxide, amounted to 0.8%-1.2% of the total mass of monomers) to obtain an acrylic prepolymer; subsequently adding a metal oxide (zinc oxide or copper oxide, molar ratio to methacrylic acid 1:1.0-1.2) and naphthenic acid (acid value 180-220 mg KOH / g, amounted to 3-3.5 times the mass of the metal oxide), reacting at 110-125℃ for 4-6 hours to dehydrate, to obtain an acrylic metal salt resin matrix with a solid content of 45%-55% and an acid value of 35-55 mg KOH / g.

[0049] This embodiment also provides an application of the slow-release polishing acrylic metal salt composite coating as described above as an antifouling coating on the surface of ships, offshore platforms, or aquaculture cage facilities.

[0050] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a slow-release polishing acrylic metal salt composite coating, characterized in that, Includes the following steps: S1. Preparation of porous titanate supports: Tetraethyl orthosilicate and tetrapropylammonium hydroxide template agent are dissolved in water and reacted at 60-90℃ for 4-8 hours to obtain a silicon source solution; titanium trichloride solution, triethanolamine complexing agent and hydrogen peroxide solution are mixed to obtain a titanium source solution; The titanium source solution and the silicon source solution are mixed, and ammonium sulfate, ammonium carbonate, TiO2 powder and TS-1 molecular sieve are added as seed crystals. The mixture is then transferred to a high-pressure reactor and hydrothermally crystallized at 150-200℃ for 12-36 hours. The crystallized product was centrifuged and dried sequentially, and then calcined at 600-800℃ for 4-8 hours to remove the template agent and obtain a porous titanosilicon support. S2. Preparation of the silicone oil slow-release unit: The porous titanate support obtained in step S1 is immersed in silicone oil with a dynamic viscosity of 20-200 mPa·s for 6-24 hours until saturation adsorption is achieved. Then, the free silicone oil on the surface is removed to obtain a slow-release unit loaded with silicone oil inside. S3. Forming of composite coating: The silicone oil slow-release unit obtained in step S2 is uniformly mixed with the acrylic metal salt resin matrix, and then coated on the surface of the substrate to form a coating with a wet film thickness of 150-300 micrometers. After curing, a composite coating is obtained.

2. The preparation method according to claim 1, characterized in that, In step S1, the amount of TiO2 powder added is 1%-10% of the mass of tetraethyl orthosilicate; the amount of TS-1 molecular sieve seed crystals added is 0.1%-1% of the mass of tetraethyl orthosilicate.

3. The preparation method according to claim 1, characterized in that, In step S1, the total amount of ammonium sulfate and ammonium carbonate added is 0.5-2.0 mol / mol relative to the molar number of tetraethyl orthosilicate.

4. The preparation method according to any one of claims 1-3, characterized in that, In step S2, the silicone oil is at least one of dimethyl silicone oil and benzyl silicone oil.

5. The preparation method according to any one of claims 1-3, characterized in that, In step S3, the acrylate metal salt resin matrix is ​​at least one of zinc acrylate resin and copper acrylate resin.

6. The preparation method according to claim 1, characterized in that, In step S3, the amount of silicone oil slow-release unit added is 5%-20% of the solid mass of the acrylate metal salt resin matrix.

7. A slow-release polishing acrylic metal salt composite coating prepared by the preparation method according to any one of claims 1-6.

8. The application of the slow-release polishing acrylic metal salt composite coating of claim 7 as an antifouling coating on the surface of ships, offshore platforms or aquaculture cage facilities.

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