A piezoelectric allyl indole antifouling coating material, a preparation method and application thereof

Abstract

The present application relates to a kind of piezoelectric allyl indole antifouling paint and its preparation method and application, by mass parts, its raw materials include: 15~25 parts piezoelectric material, 20~30 parts zinc acrylate resin containing antifouling agent, 50~60 parts acrylic polyurethane paint, 0.1~0.9 parts defoaming agent, 0.1~0.9 parts anti-settling agent, 130~135 parts organic solvent and 14~18 parts curing agent;Antifouling agent is allyl indole antifouling agent.The present application utilizes the synergistic antifouling ability of zinc acrylate resin containing antifouling agent and piezoelectric material to improve the antifouling effect;By matching acrylic polyurethane paint, defoaming agent and anti-settling agent, the overall adhesion of the paint is strong, the hardness is high, the seawater scouring resistance is good, the piezoelectric material is prevented from falling off, and the continuous synergistic antifouling effect is achieved;The present application is applied to marine antifouling paint system, and the antifouling property and mechanical property can achieve excellent effect, and the biocompatibility is good.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of marine antifouling agents, in particular to a piezoelectric allyl indole antifouling coating and a preparation method and application thereof. BACKGROUND

[0002] Marine biofouling is caused by the undesirable accumulation of marine microorganisms, plants and animals on the underwater surface of ships, which can reduce the speed of the ship, cause pipe blockage and instrument failure, and cause huge economic losses and serious problems to the shipping industry. At present, the most effective and convenient method to prevent marine biofouling is to control the release rate of toxic molecules by the coating to inhibit the growth of adhering organisms. However, the high durability and toxicity of traditional antifouling coatings are not conducive to marine organisms and the marine environment. Therefore, it is urgent to develop environmentally friendly, non-toxic or low-toxic antifouling coatings. Natural products isolated from marine microorganisms, seaweed and aquatic plants, marine invertebrates, and terrestrial and other sources have the potential to become antifouling bactericides, which have the advantages of compatibility with biological systems and are more specific than heavy metals.

[0003] Piezoelectric materials can convert mechanical force into electric field through piezoelectric effect, and the effective interfacial charge transfer caused by piezoelectric effect is one of the reasons why piezoelectric materials have good redox catalytic activity. Under the trigger of mechanical energy, piezoelectric catalysts release electrons and holes to catalyze the redox reaction of the substrate. Under mechanical stimulation, piezoelectric catalysts can catalyze the redox reaction of water molecules and oxygen to generate reactive oxygen species (ROS), which will participate in the electron transfer chain of bacterial metabolism, thereby destroying the bacterial cell wall and denaturing bacterial proteins. Therefore, piezoelectric catalysts may play an important role in sterilization.

[0004] Compounds extracted from marine organisms not only have high antifouling performance, but also are harmless to the marine environment. Fatty acid esters extracted from soft corals have good inhibitory effect on the growth and adhesion of biofouling bacteria. However, the extraction is difficult and the yield is low. Piezoelectric materials can convert mechanical energy into electrical energy using the pressure of seawater, catalyze the redox reaction of water molecules and oxygen to generate ROS, thereby destroying the bacterial cell wall and achieving broad-spectrum antibacterial effect while having little impact on the marine environment. However, there is no related technology for using piezoelectric materials for marine antifouling, and how to combine them with coatings to achieve antibacterial effect while not affecting the performance of the coatings is a factor to be considered. SUMMARY

[0005] The present application aims to overcome the above technical deficiencies, and provides a piezoelectric allyl indole antifouling coating and a preparation method and application thereof, which solves the technical problems of poor biocompatibility of marine antifouling agents or difficult extraction of raw materials for antifouling coatings and poor antifouling performance in the prior art.

[0006] To achieve the above technical purposes, the technical scheme provided by the present application is:

[0007] In a first aspect, the present application provides a piezoelectric allyl indole antifouling paint, the raw materials of which include, by mass fraction: 15-25 parts of piezoelectric material, 20-30 parts of zinc acrylate resin containing antifouling agent, 50-60 parts of acrylic polyurethane paint, 0.1-0.9 parts of defoaming agent, 0.1-0.9 parts of anti-settling agent, 130-135 parts of organic solvent, and 14-18 parts of curing agent; in the zinc acrylate resin containing antifouling agent, the antifouling agent is an allyl indole antifouling agent.

[0008] In a second aspect, the present application provides a preparation method of piezoelectric allyl indole antifouling paint, including the following steps:

[0009] The piezoelectric material, zinc acrylate resin containing antifouling agent, acrylic polyurethane paint, defoaming agent, anti-settling agent, and organic solvent are mixed, heated to 70-85℃, and then completely stirred and dispersed, after which the curing agent is added and uniformly mixed to obtain a piezoelectric allyl indole antifouling paint.

[0010] In a third aspect, the present application provides an application of piezoelectric allyl indole antifouling paint in marine antifouling paint.

[0011] Compared with the prior art, the present application has the following beneficial effects:

[0012] The antifouling agent in the antifouling paint of the present application is an allyl indole antifouling agent, and the main hydrolysis product, indole derivative, can be naturally degraded, reducing the harm of the paint to the marine environment; the piezoelectric material cannot be hydrolyzed in seawater, does not pollute the marine environment, and is very stable; the piezoelectric material converts the mechanical energy of seawater into electrical energy, catalyzes the oxidation-reduction reaction of water molecules and oxygen to generate ROS, has good and wide antifouling effect, the present application utilizes the synergistic antifouling ability of the environmentally friendly zinc acrylate resin containing antifouling agent and the piezoelectric material to improve the antifouling effect; by matching the acrylic polyurethane paint, defoaming agent, and anti-settling agent, the overall adhesion of the paint is strong, the hardness is high, the paint is resistant to seawater erosion, effectively avoids the peeling of the piezoelectric material, and plays a continuous synergistic antifouling role; the antifouling paint of the present application is applied to the marine antifouling paint system, and both the antifouling property and the mechanical property can achieve excellent effects, and has good biocompatibility. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 is the piezoelectric performance data of the piezoelectric allyl indole antifouling paint of the present application;

[0014] Figure 2 is the antibacterial experiment graph of the piezoelectric allyl indole antifouling paint of the present application;

[0015] Figure 3 is the shallow sea hanging plate experiment photo of the piezoelectric allyl indole antifouling paint of the present application. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application is further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0017] In the treatment of marine biofouling, the extract of natural products is usually used as an antifouling bactericide, which is difficult to extract and has a low yield. In theory, piezoelectric catalysts may play an important role in sterilization. The piezoelectric material does not hydrolyze in seawater and does not pollute the marine environment. In addition, the piezoelectric material is very stable.

[0018] In theory, the piezoelectric material does not fall off from the coating, and can always impart piezoelectric properties to the coating. However, there is no related technology for using piezoelectric materials for marine antifouling. How to combine it with the coating to achieve antibacterial while not affecting the performance of the coating, especially the adhesion, is a key factor to be considered.

[0019] In the first aspect, the present application provides a piezoelectric allyl indole antifouling coating, the raw materials of which include, by mass fraction:

[0020] 15-25 parts of piezoelectric material, 20-30 parts of zinc acrylate resin containing antifouling agent, 50-60 parts of acrylic polyurethane paint, 0.1-0.9 parts of defoaming agent, 0.1-0.9 parts of anti-settling agent, 130-135 parts of organic solvent, and 14-18 parts of curing agent; in the zinc acrylate resin containing antifouling agent, the antifouling agent is an allyl indole antifouling agent.

[0021] The allyl indole antifouling agent used in the present application has a simple preparation method, a wide source and a low cost. The main hydrolysis product, indole derivative, can be naturally degraded, even if it is absorbed by plants and animals, it can also be degraded in the body, and will not accumulate in the body, which can reduce the harm of the coating to the marine environment. The piezoelectric material does not hydrolyze in seawater and does not pollute the marine environment and is very stable. The piezoelectric material converts the mechanical energy of seawater into electrical energy, catalyzes the oxidation-reduction reaction of water molecules and oxygen to generate ROS, has good and wide antifouling effect. By matching the acrylic polyurethane paint, the defoaming agent and the anti-settling agent, the overall adhesion of the coating is strong, the hardness is high, the seawater washing resistance is good, the piezoelectric material is effectively prevented from falling off, and a continuous and synergistic antifouling effect is achieved. The present application reduces the use amount of the allyl indole antifouling agent, which further reduces the pollution to the ocean. The use of the allyl indole antifouling agent and the piezoelectric material together also increases the broad-spectrum antifouling effect of the antifouling coating.

[0022] The acrylic polyurethane paint is used as the main part of the coating, and too much amount of the acrylic polyurethane paint will result in less relative content of the antifouling agent, which is not conducive to antifouling, and too less amount of the acrylic polyurethane paint will result in poor film forming effect and poor durability of the coating.

[0023] Preferably, the piezoelectric material comprises barium titanate, zinc oxide, quartz or tourmaline.

[0024] Preferably, the zinc acrylate resin containing the antifouling agent has the following structural formula:

[0025]

[0026] wherein R1 is halogen or nitro.

[0027] Preferably, the preparation steps of the zinc acrylate resin containing the antifouling agent comprise: adding 20-30 parts of n-butanol and 120-130 parts of dimethylbenzene into a reaction kettle according to mass fraction, controlling the temperature to 80-90 DEG C and stirring, then adding a mixed solution containing 10-20 parts of allyl ester indole antifouling agent, 65-75 parts of acrylic ester monomer with carbon-carbon double bond and 0.4-0.5 parts of initiator drop by drop, adding 10-20 parts of zinc hydroxide after 4-8 hours of reaction, and continuing to react for 3-6 hours, so as to obtain the zinc acrylate resin containing the antifouling agent.

[0028] Further preferably, the allyl ester indole antifouling agent has the following structural formula:

[0029]

[0030] wherein R1 is halogen or nitro.

[0031] Preferably, the defoaming agent comprises BYK-358N or BYK-354.

[0032] Preferably, the anti-settling agent comprises organic bentonite, modified hydrogenated castor oil or phthalate ester coupling agent.

[0033] Preferably, the organic solvent is a mixture of dimethylbenzene and n-butanol in a mass ratio of (110-130):(20-35). The mixture of dimethylbenzene and n-butanol is the most suitable solvent for the acrylic polyurethane paint.

[0034] Preferably, the curing agent comprises vinyltriamine, tetraethylenepentamine, m-xylylenediamine or diamino diphenyl sulfone.

[0035] In the second aspect, the application provides a preparation method of the piezoelectric allyl ester indole antifouling coating, comprising the following steps:

[0036] The piezoelectric material, the zinc acrylate resin containing the antifouling agent, the acrylic polyurethane paint, the defoaming agent, the anti-settling agent and the organic solvent are mixed, heated to 70-85 DEG C, completely dispersed under stirring, then the 14-18 parts of curing agent are added and uniformly mixed, so that a piezoelectric allyl indole antifouling paint is obtained.

[0037] In a third aspect, the application provides a piezoelectric allyl indole antifouling paint for use in marine antifouling paint.

[0038] To avoid redundancy, the main raw materials used in the examples and comparative examples of the application are described as follows:

[0039] The main raw materials are as follows: the acrylic polyurethane paint, the defoaming agent, the anti-settling agent and the curing agent are provided by Wuhan Guojia Co., Ltd.; the barium titanate, the zinc oxide, the quartz and the tourmaline are from Aladdin Biochem Technology Co., Ltd.; and the other reagents are purchased from Shanghai Macklin Biochemical Technology Co., Ltd.

[0040] The zinc acrylate resin containing the antifouling agent is prepared as follows: 25 parts of n-butanol and 125 parts of dimethylbenzene are added to a reaction kettle, the temperature is controlled to 80 DEG C and stirred, then a mixed solution containing 15 parts of allyl indole antifouling agent, 70 parts of acrylic ester monomer with carbon-carbon double bond and 0.5 part of initiator (azobisisobutyronitrile) is added dropwise, 15 parts of zinc hydroxide is added after 5 hours of reaction, and the reaction is continued for 4 hours, so that a zinc acrylate resin containing the antifouling agent is obtained.

[0041] The allyl indole antifouling agent has the following structural formula:

[0042]

[0043] R1 is chlorine.

[0044] The other raw materials not described separately are conventional products which can be purchased in the market.

[0045] The application is further described in detail through specific examples.

[0046] Example 1

[0047] A piezoelectric allyl indole antifouling paint preparation method comprises the following steps:

[0048] According to mass fraction, 20 parts of barium titanate powder, 25 parts of zinc acrylate resin containing the antifouling agent, 55 parts of acrylic polyurethane paint, 0.5 part of defoaming agent, 0.8 part of anti-settling agent, 125 parts of dimethylbenzene and 25 parts of n-butanol are added to a reaction kettle, heated to 80 DEG C, stirred for 1 hour, then 16 parts of curing agent are added and uniformly stirred after dispersion is completed, so that a piezoelectric allyl indole antifouling paint is obtained.

[0049] The piezoelectric material is barium titanate, the defoamer is BYK-354, the anti-settling agent is organic bentonite, and the curing agent is vinyltriamine.

[0050] Example 2

[0051] The only difference from Example 1 is that barium titanate is replaced with zinc oxide, while the other steps and conditions are the same as in Example 1.

[0052] Example 3:

[0053] The only difference from Example 1 is that barium titanate is replaced with quartz, while the other steps and conditions are the same as in Example 1.

[0054] Example 4:

[0055] The only difference from Example 1 is that barium titanate is replaced with tourmaline; all other steps and conditions are the same as in Example 1.

[0056] Comparative Example 1

[0057] The only difference from Example 1 is that no piezoelectric material is added; the other steps and conditions are the same as in Example 1.

[0058] Comparative Example 2

[0059] The only difference from Example 1 is that zinc acrylate resin containing antifouling agent is not added; the other steps and conditions are the same as in Example 1.

[0060] Comparative Example 3

[0061] The only difference from Example 1 is that the defoamer BYK-354 is replaced with BYK-3560, while the other steps and conditions are the same as in Example 1.

[0062] Application examples

[0063] The piezoelectric allyl ester indole antifouling coatings obtained in the above embodiments and comparative examples were sprayed. The sample used for marine sidings had a spray thickness of 200 μm, while the others were sprayed with 50 μm. After curing at room temperature for 7 days, the piezoelectric allyl ester indole antifouling coating film was obtained.

[0064] Performance testing

[0065] (1) Mechanical properties test of paint film: The hardness, impact resistance and adhesion of the coating film were tested according to the national standards GB / T 6739-2022 Pencil method for determination of hardness of paint film, GB / T 1732-2020 Impact resistance test of paint film, and GB / T 1720-2020 Cross-cut test of paint film. The results are shown in Table 1 below.

[0066] Table 1. Test results of mechanical properties of the coating film

[0067] Group Hardness Impact resistance Adhesion Example 1 6H 50 cm Grade 1 Example 2 5H 50 cm Grade 1 Example 3 6H 50 cm Grade 2 Example 4 5H 45 cm Grade 2 Comparative Example 1 3H 40 cm Grade 1 Comparative Example 2 5H 45 cm Grade 1 Comparative Example 3 4H 40 cm Grade 3

[0068] The results show that the samples in Examples 1-4 have high hardness, good impact resistance, and excellent adhesion. Comparative Example 1 shows that without the addition of piezoelectric materials, the hardness and impact resistance of the coating both decrease significantly. Comparative Example 2 shows that the absence of zinc acrylate resin containing antifouling agents also affects the overall mechanical properties of the coating, especially the hardness and impact resistance. Comparative Example 3 shows that replacing the defoamer with another less suitable defoamer results in a significant decrease in the hardness, impact resistance, and adhesion of the resulting coating.

[0069] (2) Piezoelectric performance test: The piezoelectric performance of the sample was tested using an electrochemical workstation.

[0070] Take 5g of the prepared coating and spray it 50μm thick onto a conductive copper sheet using a spray gun. Connect the wire to the copper sheet using conductive tape and secure the wire and copper sheet together with the tape. Measure the piezoelectric properties of the sample using an electrochemical workstation. Connect the wire to the working electrode and reference electrode of the electrochemical workstation, open the software, measure the open-circuit voltage, and adjust the relevant parameters. Apply a force of 20N to the piezoelectric element every 2 seconds and collect data using the electrochemical workstation.

[0071] piezoelectric test results as follows Figure 1 As shown, where:

[0072] (a) is a blank control, showing the piezoelectric performance data of a conductive copper sheet coated only with epoxy resin;

[0073] (b) is the piezoelectric performance data of the conductive copper sheet coated with the coating of Example 1 in Experiment 1;

[0074] (c) is the piezoelectric performance data of experimental group 2, which is the conductive copper sheet coated with the coating of Example 2;

[0075] (d) is the piezoelectric performance data of experimental group 3, which is the conductive copper sheet coated with the coating of Example 3;

[0076] (e) is the piezoelectric performance data of experimental group 4, which is the conductive copper sheet coated with the coating of Example 4;

[0077] (f) is the piezoelectric performance data of experimental group 5, which is a conductive copper sheet coated with the paint of Comparative Example 1.

[0078] (g) is the piezoelectric performance data of experimental group 6, which is a conductive copper sheet coated with the coating of comparative example 2.

[0079] in, Figure 1 (a) shows that it has virtually no piezoelectric properties;Figure 1 The data from experimental groups 1-4 shown in (b) to (e) indicate that the product of the present invention has good piezoelectric properties, and the conductive copper sheet coated with the coating of Example 1 has the best piezoelectric properties (the larger the amplitude of the curve vibration, the better the piezoelectricity), followed by the conductive copper sheet coated with the coating of Example 2, then the conductive copper sheet coated with the coating of Example 3, and the conductive copper sheet coated with the coating of Example 4 has the worst piezoelectric properties.

[0080] Figure 1 In (f), the conductive copper sheet coated with the paint of Comparative Example 1 did not exhibit piezoelectric properties because it did not contain piezoelectric materials. Figure 1 In (g), the conductive copper sheet coated with Comparative Example 2 and the conductive copper sheet coated with the coating of Example 1 have comparable piezoelectric properties, but their stability is poor.

[0081] (3) Antibacterial performance test: Escherichia coli and Staphylococcus aureus were used to test the antibacterial properties of the prepared piezoelectric allyl ester indole antifouling coating.

[0082] Staphylococcus aureus and Escherichia coli were activated at 37°C for 2 hours, and then cultured in nutrient broth for 20 hours. Bacteria in the exponential growth phase were diluted to appropriate concentrations for antibacterial testing. A layer of piezoelectric allyl ester indole antifouling coating with a thickness of 0.05 mm was brushed onto a 24-well bacterial culture plate (this plate is used for bacterial culture and is generally made of polystyrene; hereinafter, it will be referred to as a well plate). After curing at room temperature, it was sterilized with UV light for 2 hours, and then diluted to 10... 6 CFU / ml bacterial suspension (1 mL), each experimental group contained three replicates, and the materials were co-cultured with bacteria for 24 h. Then the above bacterial suspension (50) L) was evenly spread on a solid culture medium. After complete absorption, it was incubated at 37°C for 18 hours. The above antibacterial experiment was carried out under sterile conditions. The inhibition rate was determined by formula (1).

[0083] Equation (1)

[0084] In the formula, S is the inhibition rate, So is the average colony count of the control group, and Si is the average colony count of the experimental group.

[0085] Antibacterial results such as Figure 2 As shown, where:

[0086] (a) is a blank sample, which is an antibacterial test of E. coli in a well plate that does not contain any polymer;

[0087] (b) is a blank sample, which is an antibacterial test of Staphylococcus aureus performed on a well plate without any polymer;

[0088] (c) is the experimental group, which is used to conduct antibacterial experiments on Escherichia coli by coating the well plate of Example 1;

[0089] (d) is the experimental group, which is used to conduct antibacterial experiments on Staphylococcus aureus for coating the well plate of Example 1;

[0090] (e) is the experimental group, which was used to conduct an antibacterial experiment on Escherichia coli to coat the well plate of Comparative Example 1;

[0091] (f) is the experimental group, which was used to conduct an antibacterial experiment against Staphylococcus aureus on the well plate of Comparative Example 1.

[0092] (g) is the experimental group, used to conduct antibacterial experiments on Escherichia coli by coating the well plate of Comparative Example 2;

[0093] (h) is the experimental group, which is used to conduct an antibacterial experiment against Staphylococcus aureus on the well plate of Comparative Example 2.

[0094] Combined with blank samples ( Figure 2 (a) and (b)), based on the results of Comparative Example 1, it can be seen that the sample with only zinc acrylate resin containing antifouling agent added has a higher kill rate of Escherichia coli. Figure 2 (e)), but the kill rate against Staphylococcus aureus is relatively low ( Figure 2 (f)). Based on the results of Comparative Example 2, it can be seen that the sample with only piezoelectric material added has a high kill rate against Staphylococcus aureus (f) Figure 2 (h) actually exceeded the kill rate of E. coli ( Figure 2 (g)). And according to the results of Example 1 ( Figure 2 (c) and (d) show that the sample with both piezoelectric material and zinc acrylate resin containing antifouling agent has a 100% kill rate against Escherichia coli and Staphylococcus aureus, which indicates that the product of the present invention has excellent antibacterial effect.

[0095] (4) Shallow sea hanging plate experiment: The field test was conducted from October 2023 to January 2024 near the Asian Science and Technology City in Sanya, China (109°51'E, 18°25'N).

[0096] The piezoelectric allyl ester-based indole antifouling coating prepared by the method shown in the examples was applied to an epoxy resin board (300 × 150 × 3 mm) with a film thickness of 200 μm and cured at room temperature for 7 days as the test group. The epoxy resin board was immersed in seawater at a depth of 0.2-2.0 m. After immersion in seawater for 90 days, the coated board was removed from the seawater and photographed to record the adhesion of dirt and organisms.

[0097] The results are as follows Figure 3 As shown, where:

[0098] (a) is a blank sample, which is an epoxy resin panel without any polymers;

[0099] (b) is a control sample, which is an epoxy resin panel coated with zinc acrylate resin containing antifouling agent (i.e., without other components in the piezoelectric allyl ester indole antifouling coating of the present invention, except for zinc acrylate resin containing antifouling agent).

[0100] (c) is test group 1, which is an epoxy resin panel coated with the coating of Example 1;

[0101] (d) is test group 2, which is an epoxy resin panel coated with the coating of Example 2;

[0102] (e) is test group 3, which is an epoxy resin panel coated with the coating of Example 3;

[0103] (f) is test group 4, which is an epoxy resin panel coated with the coating of Example 4.

[0104] Depend on Figure 3 It can be seen that the antifouling coating of the present invention has good antifouling performance, and its antifouling effect is significantly better than that of the blank sample and the control sample within 90 days.

[0105] In summary, the antifouling coating prepared by this invention can achieve uniform hydrolysis of ester groups in a seawater environment, releasing antifouling components and achieving the purpose of controlling the release rate of allyl ester-based indole antifouling agents. Moreover, the main hydrolysis product, indole derivatives, is biodegradable, effectively preventing the growth of fouling organisms while reducing the harm of the coating to the marine environment, and exhibiting good biocompatibility. The piezoelectric material converts mechanical energy into electrical energy, catalyzing the redox reaction of water molecules and oxygen to generate ROS, thereby destroying bacterial cell walls and achieving excellent antibacterial effects. This invention combines zinc acrylate resin containing antifouling agents with piezoelectric materials to produce a synergistic effect, achieving a 100% kill rate against both Escherichia coli and Staphylococcus aureus. At the same time, the coating prepared by this invention has good mechanical properties.

[0106] Compared with existing technologies, this invention provides a piezoelectric allyl ester-based indole antifouling coating, its preparation method, and its application. The method includes the following steps: an allyl ester-based indole antifouling agent is copolymerized with an acrylate monomer containing carbon-carbon double bonds in an initiator and solvent environment; zinc hydroxide is then added for further copolymerization to obtain a zinc acrylate resin containing the antifouling agent; the zinc acrylate resin containing the antifouling agent, acrylic polyurethane paint, piezoelectric materials, and solvents are thoroughly mixed and a curing agent is added for subsequent curing to obtain the piezoelectric allyl ester-based indole antifouling coating of this invention. This invention's piezoelectric allyl ester-based indole antifouling coating utilizes the synergistic antifouling capabilities of environmentally friendly novel synthetic compounds and piezoelectric materials in marine antifouling coating systems. It is an effective and environmentally friendly method. The piezoelectric allyl ester-based indole antifouling coating of this invention achieves excellent antifouling and mechanical properties and exhibits good biocompatibility.

[0107] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A piezoelectric allyl ester-based indole antifouling coating, characterized in that, By weight, its raw materials include: 15-25 parts piezoelectric material, 20-30 parts zinc acrylate resin containing antifouling agent, 50-60 parts acrylic polyurethane paint, 0.1-0.9 parts defoamer, 0.1-0.9 parts antisettling agent, 130-135 parts organic solvent, and 14-18 parts curing agent. In the zinc acrylate resin containing the antifouling agent, the antifouling agent is an allyl ester indole antifouling agent; The preparation steps of the zinc acrylate resin containing the antifouling agent include: adding 20-30 parts of n-butanol and 120-130 parts of xylene to a reaction vessel according to the mass ratio, controlling the temperature to 80-90℃ and stirring, then adding dropwise a mixed solution containing 10-20 parts of allyl ester indole antifouling agent, 65-75 parts of acrylate monomer with carbon-carbon double bonds and 0.4-0.5 parts of initiator, reacting for 4-8 hours, then adding 10-20 parts of zinc hydroxide, and continuing the reaction for 3-6 hours to obtain the zinc acrylate resin containing the antifouling agent; The structural formula of the allyl ester indole antifouling agent is as follows: Wherein, R1 is a halogen or nitro group; The defoamer includes BYK-358N or BYK-354.

2. The piezoelectric allyl ester indole antifouling coating according to claim 1, characterized in that, The piezoelectric material includes barium titanate, zinc oxide, quartz, or tourmaline.

3. The piezoelectric allyl ester indole antifouling coating according to claim 1, characterized in that, The anti-settling agent includes organobentonite, modified hydrogenated castor oil, or titanate coupling agent.

4. The piezoelectric allyl ester indole antifouling coating according to claim 1, characterized in that, The organic solvent is a mixture of xylene and n-butanol in a mass ratio of (110-130):(20-35).

5. The piezoelectric allyl ester indole antifouling coating according to claim 1, characterized in that, The curing agent includes tetraethylenepentamine, m-phenylenediamine, or diaminodiphenyl sulfone.

6. The method for preparing the piezoelectric allyl ester indole antifouling coating according to any one of claims 1-5, characterized in that, Includes the following steps: A piezoelectric material, zinc acrylate resin containing antifouling agent, acrylic polyurethane paint, defoamer, antisettling agent and organic solvent are mixed, heated to 70-85℃, and after complete stirring and dispersion, a curing agent is added and mixed evenly to obtain a piezoelectric allyl ester indole antifouling coating.

7. The application of the piezoelectric allyl ester indole antifouling coating as described in any one of claims 1-5 in marine antifouling coatings.

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