Acrylic acid silane ester self-updating antifouling resin based on cation-pi interaction as well as preparation method and application of acrylic acid silane ester self-updating antifouling resin

Abstract

The invention discloses an acrylic acid silane ester self-renewal antifouling resin based on cation-pi interaction as well as a preparation method and application of the acrylic acid silane ester self-renewal antifouling resin. Methyl methacrylate, ethyl acrylate, triisopropylsilyl methacrylate, acrylic acid-2-methyl ethyl ester, paeonol methacrylate and acryloyloxyethyl trimethyl ammonium chloride are synthesized through a random free radical polymerization reaction with azodiisobutyronitrile and benzoyl peroxide as initiators. Wherein the methacrylic acid paeonol ester monomer is prepared by carrying out substitution reaction on paeonol and methacryloyl chloride. The anti-fouling agent is anchored on the surface of the coating again through cation-pi interaction, so that the anti-fouling effect is enhanced, and the coating still has good anti-fouling capacity even in a static environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of marine antifouling coatings, and particularly relates to a silane ester self-renewal antifouling resin based on cation-π interaction and a preparation method and application thereof. BACKGROUND

[0002] Marine biofouling causes harm to marine engineering equipment, such as accelerating equipment corrosion, increasing ship sailing resistance, thus increasing fuel consumption and greenhouse gas emissions, so effective antifouling means are needed. However, although traditional organotin self-renewal coatings have good antifouling effect, they have relatively large toxicity, causing great harm to the marine ecological environment. With the enhancement of environmental awareness and the emphasis on marine ecological protection, the International Convention on the Control of Harmful Antifouling Systems on Ships prohibits the use of antifouling paint containing organotin, limiting the use of traditional antifouling paint, which promotes the development of antifouling coatings in the direction of low toxicity, environmental protection and high efficiency. Tin-free self-renewal antifouling coating is one of the mainstream marine antifouling coatings at present, and silane ester self-renewal antifouling coating is a relatively advanced technology among them. It can realize self-renewal of the coating surface through hydrolysis of the silane ester side chain, and can reduce sailing friction during ship sailing and fuel consumption.

[0003] However, the silane ester self-renewal antifouling coating also has some deficiencies. First, the traditional silane ester self-renewal antifouling coating has poor static antifouling performance, which makes the antifouling effect not ideal when the ship is at rest or low speed. Second, the traditional silane ester self-renewal antifouling coating usually needs to add a large amount of cuprous oxide as an antifouling agent, and the accumulation of copper ions in the ocean will seriously threaten the marine ecological environment. The research of natural products in the field of antifouling brings a new direction for technological breakthrough. As an extract of peony, paeonol has a significant inhibitory effect on marine fouling organisms, is green and environmentally friendly, and has good biocompatibility. Cation-π interaction is a special non-covalent interaction that can regulate intermolecular forces and material surface properties.

[0004] Therefore, paeonol and cation-π interaction are introduced into the silane ester self-renewal antifouling coating system, the antifouling performance of the coating is improved through the natural antifouling activity of paeonol, the coating surface structure is optimized by using cation-π interaction, and the hydrolysis rate is regulated, so as to prepare a new antifouling coating with high performance and environmental friendliness.

[0005] Chinese patent CN117659259A discloses a preparation method of a vanillin ester-based acrylate self-renewal antifouling resin. The phenolic ester side chain of vanillin methyl acrylate in the vanillin ester-based acrylate self-renewal antifouling resin can be hydrolyzed to realize self-renewal in seawater, and at the same time, a biologically active substance vanillin is released from the material surface, which is an environmentally friendly self-renewal antifouling resin that has resistance to multi-scale fouling organisms.

[0006] Chinese patent CN112322161B discloses a method for preparing a superhydrophilic coating based on cation-π interaction. This coating is prepared by mixing polyphenolic tannins with a series of cations, and exhibits excellent self-cleaning and antifouling properties.

[0007] Starting from different inventive concepts, this invention is the first to combine the natural extract paeonol with cationic-π interactions and introduce them into a self-renewing silane acrylate resin. Although the selection of some monomers is similar, the addition of the natural extract paeonol and cationic-π interactions optimizes the surface structure of traditional silane acrylate, enhances the static antifouling ability of the coating, and extends the antifouling period of the coating. This is something that has not been studied in previous technologies. The inventor still needs to put in creative effort to optimize and improve many aspects such as the synthesis process, the ratio of monomers, and the selection of solvents in order to prepare an environmentally friendly self-renewing antifouling resin that is different from existing technologies.

[0008] It should be noted that, except for explicitly cited public documents, the information disclosed in this background art is only intended to enhance the understanding of the overall background of the present invention, to understand the context in which the inventors developed the inventive concept, and should not be regarded as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0009] In view of this, in order to solve the above-mentioned technical problems, the purpose of this invention is to propose a self-renewing antifouling resin of silane acrylate based on cation-π interaction, its preparation method and application. This self-renewing antifouling resin of silane acrylate based on cation-π interaction can enhance the surface antifouling performance, and can carry out rapid surface self-renewal in seawater. It also has a good antifouling effect in static environment and is an environmentally friendly self-renewing antifouling resin that resists multi-scale marine fouling organisms.

[0010] The technical solution adopted is as follows:

[0011] The present invention discloses a self-renewing antifouling resin of silane acrylate based on cation-π interaction, the structural formula of which is as follows:

[0012]

[0013] Where a, b, c, d, e, and f represent the number of repeating units in the random copolymerization, with methyl methacrylate being the repeating monomer in a; butyl acrylate being the repeating monomer in b; triisopropylsilyl methacrylate being the repeating monomer in c; acryloyloxyethyltrimethylammonium chloride being the repeating monomer in d; 2-methylethyl acrylate being the repeating monomer in e; and paeonol methacrylate being the repeating monomer in f; and co represents random copolymerization of monomers.

[0014] The present invention provides a method for preparing a self-renewing antifouling resin of silane acrylate based on cation-π interaction, comprising the following steps, by weight:

[0015] (1) Mix and dissolve 40-60 parts of methyl methacrylate, 20-40 parts of butyl acrylate, 0.5-25 parts of paeonol methacrylate, 5-15 parts of triisopropylsilyl methacrylate, 2-10 parts of 2-methyl ethyl acrylate, 1-10 parts of acryloyloxyethyltrimethylammonium chloride and 0.5-2 parts of azobisisobutyronitrile in a mixed solution of 40-60 parts of N,N-dimethylformamide and propylene glycol methyl ether to obtain mixture A;

[0016] (2) Add another 40-60 parts of the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether to a four-necked flask and heat to 80-95°C. Slowly add the above mixed solution A in a protective atmosphere and continue adding. After the addition is complete, slowly add the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether containing 0.1-1 parts of benzoyl peroxide for secondary initiation and continue adding. Then maintain the same temperature and continue stirring to ensure that the reaction is complete. Finally, obtain the self-renewing antifouling resin of silane acrylate based on cation-π interaction.

[0017] Further, in step (1), the paeonol methacrylate is obtained by the following preparation method, which, by weight, includes the following steps:

[0018] Dissolve 1-10 parts of paeonol and 1-10 parts of triethylamine, an acid-binding agent, in 15-35 parts of tetrahydrofuran; slowly add 1-8 parts of methacryloyl chloride dropwise to the above solution at a low temperature of 0-5℃, while continuously stirring throughout the process; after the addition is complete, stir at room temperature to allow the reaction to proceed fully; filter the mixture obtained from the reaction to remove the ammonium salt precipitate, take the filtrate, and vacuum dry it to remove tetrahydrofuran and triethylamine, to obtain paeonol methacrylate monomer.

[0019] Furthermore, in the preparation method of paeonol methacrylate, after the addition is completed, the mixture is stirred at room temperature for 12-36 hours to allow it to react fully.

[0020] Furthermore, in step (1), the mass ratio of N,N-dimethylformamide to propylene glycol methyl ether is 2:1.

[0021] Furthermore, in step (2), the protective atmosphere is one or more of nitrogen, argon, and helium.

[0022] Further, in step (2), the above mixture A is slowly added dropwise in a protective atmosphere, and the addition is continuous. During the addition process, the mixture is stirred continuously at a speed of 100-200 rpm, and the addition is completed in 2-3 hours.

[0023] Further, in step (2), a mixed solution of N,N-dimethylformamide containing 0.1-1 part of benzoyl peroxide and propylene glycol methyl ether is continuously added dropwise for 20-40 minutes, and then the same temperature is maintained and stirred for 2-3 hours to ensure a complete reaction.

[0024] The present invention relates to the application of a self-renewing antifouling resin of silane acrylate based on cation-π interaction in the preparation of marine antifouling coatings.

[0025] Furthermore, the ester bonds in the triisopropylsilyl methacrylate and paeonol methacrylate in the cation-π interaction-based self-renewing antifouling resin can both be hydrolyzed in the ocean, enabling rapid renewal of the coating surface; some of the hydrolyzed paeonol will be re-adsorbed onto the coating surface through cation-π interactions; the hydrolysis reaction formula and cation-π interaction process of the cation-π interaction-based self-renewing antifouling resin are as follows:

[0026] .

[0027] In the above technical solutions,

[0028] (1) Paeonol methacrylate, as a functional monomer with broad-spectrum antifouling ability, hydrolyzes its ester bonds after contact with weakly alkaline seawater, allowing paeonol to be released from the coating surface, which can kill fouling organisms and thus achieve the purpose of antifouling.

[0029] (2) Acryloyloxyethyltrimethylammonium chloride monomer provides cations that can re-anchor hydrolyzed paeonol, enhance the antifouling activity of the coating, and extend the antifouling period of the coating.

[0030] (3) Triisopropylsilyl methacrylate monomer can not only ensure the hydrophobicity of the resin, but also give it dynamic self-renewal properties.

[0031] (4) The glass transition temperature, hardness and flexibility of the resin are adjusted by methyl methacrylate and butyl acrylate.

[0032] (5) 2-methyl ethyl acrylate monomer can improve the adhesion of coatings to different substrates.

[0033] (6) Using a mixed solution of N,N-dimethylformamide and propylene glycol methyl ether as a solvent has good compatibility with the resin and makes the coating easy to cure. Controlling the resin solid content to about 40% can ensure that the resin viscosity is moderate, allowing for long-term storage and convenient coating application.

[0034] To inhibit the adhesion of marine biofouling to the surfaces of marine engineering equipment and ships, this invention creatively combines the natural extract paeonol with cationic-π interactions and introduces it into a silane acrylate self-renewal system. A self-renewing antifouling resin based on cationic-π interactions was successfully prepared by random radical copolymerization with other acrylate monomers. The ester groups of the side chains can hydrolyze in seawater, releasing the biofouling agent paeonol, which is then re-anchored to the coating surface through cationic-π interactions, resisting the adhesion of small fouling organisms such as bacteria and algae. Furthermore, the hydrolysis of the silane ester side chains and phenolic ester groups increases the carboxyl groups on the coating surface, leading to enhanced hydrophilicity and ultimately causing the main chain to detach, thus renewing the surface. This resists the adhesion of large fouling organisms, ultimately constructing an environmentally friendly self-renewing antifouling resin resistant to fouling organisms at multiple scales.

[0035] In summary, compared with the prior art, the beneficial effects of the present invention are:

[0036] 1. This invention is the first to combine the environmentally friendly antifouling monomer of paeonol methacrylate with cationic-π interaction and introduce it into the field of self-renewing antifouling coatings of silane acrylates, which has certain application prospects;

[0037] 2. By utilizing the hydrolysis of the ester bond of paeonol methacrylate under a weakly alkaline environment, paeonol is released and re-anchored to the coating surface through cation-π interaction, thereby inhibiting the adhesion of bacteria and algae;

[0038] 3. By introducing a variety of hydrolyzable monomers, the resin can be hydrolyzed quickly in seawater, and it also has a good surface self-renewal effect in a static environment;

[0039] 4. The self-renewal rate and service life of the resin can be controlled by adjusting the ratio of acryloyloxyethyltrimethylammonium chloride cationic monomer and paeonol methacrylate aromatic monomer.

[0040] 5. Marine antifouling coatings achieve surface self-renewal through the hydrolysis of the side chain ester bonds of paeonol methacrylate in seawater. At the same time, paeonol is released from the material surface and re-anchored to the coating surface through cation-π interactions, giving the coating a triple antifouling capability of "defense-release-attack".

[0041] 6. The self-renewing antifouling resin of silane acrylate of this invention is mainly synthesized in a protective atmosphere by random radical polymerization of methyl methacrylate, ethyl acrylate, triisopropylsilyl methacrylate, 2-methylethyl acrylate, paeonol methacrylate, and acryloyloxyethyltrimethylammonium chloride with azobisisobutyronitrile and benzoyl peroxide as initiators. The paeonol methacrylate monomer is obtained by a substitution reaction between paeonol and methacryloyl chloride.

[0042] This invention relates to a self-renewing antifouling resin based on cation-π interactions. This resin achieves self-renewal of the coating surface through side-chain hydrolysis, while simultaneously utilizing cation-π interactions to re-adsorb the released aromatic antifouling agent onto the coating surface, extending the antifouling period. In a seawater environment, the ester bonds on the resin side chains break through hydrolysis, releasing the antifouling active substance paeonol. Some paeonol undergoes cation-π interactions with the quaternary ammonium cations in the resin and is re-adsorbed onto the coating surface to inhibit the adhesion of fouling organisms. As seawater washes over the surface, the main chain gradually becomes brittle due to the increase in hydrophilic carboxyl groups, thus exposing a new antifouling surface. Compared to traditional zinc / copper acrylate and silane acrylate antifouling coatings, this invention introduces bio-based paeonol into the self-renewing antifouling resin, as paeonol possesses excellent antibacterial and anti-algae properties. Simultaneously, the introduction of an acryloyloxyethyltrimethylammonium chloride cationic monomer enhances the antifouling effect by re-anchoring the antifouling agent to the coating surface through cation-π interactions, ensuring good antifouling performance even in static environments. Attached Figure Description

[0043] Figure 1 The figure shows the contact angle results of the silane acrylate self-renewing antifouling coating based on cation-π interaction before and after 20 days of hydrolysis in artificial seawater.

[0044] Figure 2 The hydrolysis weight loss curve of the acrylate silane ester self-renewing antifouling coating in artificial seawater after 30 days is shown.

[0045] Figure 3 The XPS full spectrum and high-resolution C1s spectrum of the silane acrylate self-renewing antifouling coating based on cation-π interaction were obtained before and after 7 days of hydrolysis.

[0046] Figure 4 The experimental results of the self-renewing antifouling coating of silane acrylate based on cation-π interaction are shown in the fluorescence confocal microscope image.

[0047] Figure 5 The figure shows the experimental results of antifouling of the silane acrylate self-renewing antifouling coating based on cation-π interaction;

[0048] Figure 6 The figure shows the experimental results of antifouling of *Rhizoctonia solani* with a silane acrylate self-renewing antifouling coating based on cation-π interaction.

[0049] Figure 7 These are digital photographs and experimental results of the anti-E. coli effect of the silane acrylate self-renewing antifouling coating based on cation-π interaction;

[0050] Figure 8 These are digital photographs and experimental results of an antifouling coating of silane acrylate based on cation-π interactions against *Pseudomonas aeruginosa*. Detailed Implementation

[0051] The present invention will be described in detail below through specific embodiments. However, the uses and purposes of these exemplary embodiments are only for illustrating the present invention and do not constitute any limitation on the actual protection scope of the present invention, nor are they intended to limit the protection scope of the present invention to these embodiments.

[0052] Unless otherwise specified, all quantities in the following examples are by weight.

[0053] Example 1

[0054] This embodiment describes a self-renewing antifouling resin based on cation-π interactions of silane acrylate, prepared through the following steps:

[0055] 1. Synthesis of Paeonol Methacrylate

[0056] Dissolve 1 part paeonol and 0.9 parts triethylamine, an acid-binding agent, in 20 parts tetrahydrofuran; slowly add 0.6 parts methacryloyl chloride, dissolved in 10 parts tetrahydrofuran, to the above solution at 0°C with continuous stirring. After the addition is complete, stir the reaction at room temperature for 12-15 hours; filter the mixture obtained from the reaction to remove the ammonium salt precipitate, take the filtrate, and vacuum dry it to remove tetrahydrofuran and triethylamine to obtain paeonol methacrylate.

[0057] 2. Synthesis of self-renewing antifouling resin based on cation-π interaction of silane acrylate

[0058] (1) Dissolve 52.1 parts of methyl methacrylate, 28.9 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methyl ethyl acrylate, 4 parts of acryloyloxyethyltrimethylammonium chloride, 1 part of paeonol methacrylate and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture A1.

[0059] (2) Another 50 parts of the N,N-dimethylformamide and propylene glycol methyl ether mixed solution were added to a 500 mL four-necked flask and heated to 85°C. The above mixed solution A1 was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding 10 parts of a N,N-dimethylformamide and propylene glycol methyl ether mixed solution containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The reaction was then maintained at 85°C and stirred for another 2-3 hours to ensure a complete reaction. Finally, a self-renewing antifouling resin based on cation-π interaction of silane acrylate was obtained, which can be directly used to formulate marine antifouling coatings. This resin was named MBECTP-1.

[0060] 3. Coating performance characterization

[0061] (1) Laboratory contact angle test: The static contact angle of the thiazolinone methacrylate silane ester self-renewing antifouling coating before and after hydrolysis in artificial seawater and deionized water was measured using OCA-20. Figure 1 The image shows a comparison of the contact angles of the coating prepared from the sample of Example 1 before and after hydrolysis in artificial seawater for 10 and 20 days. It can be seen that as the hydrolysis time increases, the contact angle of the coating gradually decreases, from 87.7° to 80.0° and 66.6° after 10 and 20 days, respectively.

[0062] (2) Laboratory static self-renewal test: Weigh a glass slide with dimensions of 2.5 cm × 7.5 cm, apply the sample from Example 1 evenly to the glass slide, weigh it after complete curing, immerse it in artificial seawater for 30 days, remove it every 5-7 days to dry and weigh it, calculate the coating weight loss rate using the following formula (a):

[0063] (a)

[0064] Where M is the coating weight loss rate, M0 is the mass of the blank glass slide, M1 is the total mass of the coating and glass slide after the sample is fully cured, and M2 is the total mass of the coating and glass slide after the sample is soaked for a certain time and then fully dried.

[0065] See Figure 2 As shown, Figure 2 This is the hydrolysis weight loss curve of a silane acrylate self-renewing antifouling coating based on cation-π interaction in artificial seawater over 30 days.

[0066] In this embodiment, the calculated weight loss rate is 2.7%.

[0067] (3) Laboratory static inhibition experiment of diatoms: The sample of Example 1 was evenly coated on a glass slide with a size of 2.5 cm × 3.5 cm. A blank glass slide was used as a blank control. The sample slide and the blank glass slide were immersed in two model algae species (Diamondsia spp. and Rhomboidia spp.) for 7 days. After the sample was taken out, the unattached algae were washed off. The algae attachment on the coating was photographed under a fluorescence confocal microscope. Figure 4 Five areas were randomly selected from each coating and photographed. The average number of diatoms on the blank slide and the sample of Example 1 was calculated using the following formula (b):

[0068] (b)

[0069] Where K represents the inhibition rate of diatom adhesion, and N... B is the average number of diatoms on the surface of the blank slide, and N is the average number of diatoms on the surface of the sample.

[0070] Calculate the inhibition rate of *Dystropharia* attachment after 7 days ( Figure 5 ) and inhibiting the attachment rate of *Nyctaginosa* (small crescent algae) Figure 6 The figures were 80.4% and 59.4%, respectively.

[0071] (4) Laboratory static antibacterial experiment: The sample coating size was prepared as 2.5 cm × 3.5 cm. Glass slides were selected as blank controls. The samples and blanks were co-cultured with bacterial strains at 37°C (Escherichia coli, Staphylococcus aureus) and at 28°C for 12 h and 24 h respectively. After dilution to the same concentration, the bacterial solution was spread on solid culture medium by plate coating method (each sample was coated 3 times in parallel). The plates were incubated at 37°C and 28°C for 12 h and 24 h respectively. The plates were removed and the number of bacteria adhering to the coating surface was determined by plate counting. Figures 7-8 The images show digital images and corresponding antibacterial rates of the acrylate self-renewing antifouling coating based on cation-π interactions. It can be seen that the number of colonies on the coating surface is significantly reduced compared to the blank. Colony counts were used to calculate the colony counts on both the sample and the blank. The antibacterial rates against *Escherichia coli*, *Aureobasidium*, and *Pseudomonas aeruginosa* based on the acrylate self-renewing antifouling coating based on cation-π interactions were calculated in Example 1 to be 34.4%, 39.0%, and 44.9%, respectively.

[0072] The static contact angle of the methacrylate silane ester self-renewing antifouling coating based on cation-π interaction decreased from 87.7° to 80.0° and 66.6° after immersion in artificial seawater for 10 and 20 days, respectively; the hydrolysis weight loss rate was 2.7%; the inhibition rate of *Dendrolimus fasciatus* was 80.4%, the inhibition rate of *Nyctaginus simonii* was 59.4%; the inhibition rate of *Escherichia coli* was 34.4%, the inhibition rate of *Aureobasidium aureum* was 39.0%, and the inhibition rate of *Pseudomonas aeruginosa* was 44.9%.

[0073] Example 2

[0074] This embodiment describes a self-renewing antifouling resin based on cation-π interactions of silane acrylate, prepared through the following steps:

[0075] 1. Synthesis of Paeonol Methacrylate

[0076] Dissolve 2.5 parts of paeonol and 2.3 parts of triethylamine, an acid-binding agent, in 20 parts of tetrahydrofuran. Slowly add 1.58 parts of methacryloyl chloride, dissolved in 10 parts of tetrahydrofuran, to the above solution at 0°C with continuous stirring. After the addition is complete, stir the reaction at room temperature for 12-15 hours. Filter the mixture obtained from the reaction to remove the ammonium salt precipitate. Take the filtrate and dry it under vacuum to remove tetrahydrofuran and triethylamine to obtain paeonol methacrylate.

[0077] 2. Synthesis of self-renewing antifouling resin based on cation-π interaction of silane acrylate

[0078] (1) Dissolve 51.1 parts of methyl methacrylate, 28.4 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methyl ethyl acrylate, 4 parts of acryloyloxyethyltrimethylammonium chloride, 2.5 parts of paeonol methacrylate and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture A2.

[0079] (2) Another 50 parts of the N,N-dimethylformamide and propylene glycol methyl ether mixed solution were added to a 500 mL four-necked flask and heated to 85°C. The above mixed solution A2 was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding 10 parts of a N,N-dimethylformamide and propylene glycol methyl ether mixed solution containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The reaction was then maintained at 85°C and stirred for another 2-3 hours to ensure a complete reaction. Finally, a self-renewing antifouling resin based on cation-π interactions of silane acrylate was obtained, which can be directly used to formulate marine antifouling coatings. This resin was named MBECTP-2.5.

[0080] The tests were conducted according to the test method in Example 1. The results were as follows: the static contact angle of the acrylate silane ester self-renewing antifouling coating based on cation-π interaction decreased from 88.1° to 81.7° and 66.8° after immersion in artificial seawater for 10 and 20 days, respectively; the hydrolysis weight loss rate was 3.0%; after 7 days, the inhibition rate of *Dendrocalamus fasciatus* was 83.0%, the inhibition rate of *Nyctaginus simonii* was 73.5%, the inhibition rate of *Escherichia coli* was 54.9%, the inhibition rate of *Aureobasidium aureum* was 49.2%, and the inhibition rate of *Pseudomonas aeruginosa* was 51.4%.

[0081] Example 3

[0082] This embodiment describes a self-renewing antifouling resin based on cation-π interactions of silane acrylate, prepared through the following steps:

[0083] 1. Synthesis of Paeonol Methacrylate

[0084] Dissolve 5 parts of paeonol and 4.6 parts of triethylamine, an acid-binding agent, in 20 parts of tetrahydrofuran; slowly add 3.2 parts of methacryloyl chloride, dissolved in 10 parts of tetrahydrofuran, to the above solution at 0°C with continuous stirring. After the addition is complete, stir the reaction at room temperature for 12-15 hours; filter the mixture obtained from the reaction to remove the ammonium salt precipitate, take the filtrate, and vacuum dry it to remove tetrahydrofuran and triethylamine to obtain paeonol methacrylate.

[0085] 2. Synthesis of self-renewing antifouling resin based on cation-π interaction of silane acrylate

[0086] (1) Dissolve 49.5 parts of methyl methacrylate, 27.5 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methyl ethyl acrylate, 4 parts of acryloyloxyethyltrimethylammonium chloride, 5 parts of paeonol methacrylate and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture A3.

[0087] (2) Another 50 parts of the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether were added to a 500 mL four-necked flask and heated to 85°C. The above mixture A3 was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding a mixed solution (10 parts) of N,N-dimethylformamide and propylene glycol methyl ether containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The mixture was then stirred at 85°C for another 2-3 hours to ensure a complete reaction. The final product was a self-renewing antifouling resin of silane acrylate based on cation-π interactions, which can be directly used to formulate marine antifouling coatings. This resin was named MBECTP-5.

[0088] The tests were conducted according to the method described in Example 1. The results showed that the static contact angle of the acrylate silane ester self-renewing antifouling coating based on cation-π interaction decreased from 91.6° to 80.7° and 61.8°, respectively, after immersion in artificial seawater for 10 and 20 days; the hydrolysis weight loss rate was 3.4%; after 7 days, the inhibition rate of *Dendrocalamus fasciatus* was 85.0%, the inhibition rate of *Nyctaginus simonii* was 81.8%, the inhibition rate of *Escherichia coli* was 70.8%, the inhibition rate of *Aureobasidium aureum* was 55.5%, and the inhibition rate of *Pseudomonas aeruginosa* was 64.4%.

[0089] Example 4

[0090] This embodiment describes a self-renewing antifouling resin based on cation-π interactions of silane acrylate, prepared through the following steps:

[0091] 1. Synthesis of Paeonol Methacrylate

[0092] Dissolve 7.5 parts of paeonol and 6.9 parts of triethylamine, an acid-binding agent, in 20 parts of tetrahydrofuran. Slowly add 4.8 parts of methacryloyl chloride, dissolved in 10 parts of tetrahydrofuran, to the above solution at 0°C with continuous stirring. After the addition is complete, stir the reaction at room temperature for 12-15 hours. Filter the mixture obtained from the reaction to remove the ammonium salt precipitate. Take the filtrate and dry it under vacuum to remove tetrahydrofuran and triethylamine to obtain paeonol methacrylate.

[0093] 2. Synthesis of self-renewing antifouling resin based on cation-π interaction of silane acrylate

[0094] (1) Dissolve 47.9 parts of methyl methacrylate, 26.6 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methyl ethyl acrylate, 4 parts of acryloyloxyethyltrimethylammonium chloride, 7.5 parts of paeonol methacrylate and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture A4.

[0095] (2) Another 50 parts of the N,N-dimethylformamide and propylene glycol methyl ether mixed solution were added to a 500 mL four-necked flask and heated to 85°C. The above mixture A4 was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding 10 parts of a N,N-dimethylformamide and propylene glycol methyl ether mixed solution containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The mixture was then stirred at 85°C for another 2-3 hours to ensure a complete reaction. The final product was a self-renewing antifouling resin based on cation-π interactions, which can be directly used to formulate marine antifouling coatings. This resin was named MBECTP-7.5.

[0096] The tests were conducted according to the test method in Example 1. The results were as follows: the static contact angle of the acrylate silane ester self-renewing antifouling coating based on cation-π interaction decreased from 92.6° to 80.8° and 60.3° after immersion in artificial seawater for 10 and 20 days, respectively; the hydrolysis weight loss rate was 3.5%; after 7 days, the inhibition rate of *Dendrocalamus fasciatus* was 89.9%, the inhibition rate of *Nyctaginus simonii* was 84.7%, the inhibition rate of *Escherichia coli* was 67.8%, the inhibition rate of *Aureobasidium aureum* was 56.0%, and the inhibition rate of *Pseudomonas aeruginosa* was 77.0%.

[0097] Example 5

[0098] This embodiment describes a self-renewing antifouling resin based on cation-π interactions of silane acrylate, prepared through the following steps:

[0099] 1. Synthesis of Paeonol Methacrylate

[0100] Dissolve 10 parts of paeonol and 9.1 parts of triethylamine, an acid-binding agent, in 20 parts of tetrahydrofuran; slowly add 6.3 parts of methacryloyl chloride, dissolved in 10 parts of tetrahydrofuran, to the above solution at 0°C with continuous stirring. After the addition is complete, stir the reaction at room temperature for 12-15 hours; filter the mixture obtained from the reaction to remove the ammonium salt precipitate, take the filtrate, and vacuum dry it to remove tetrahydrofuran and triethylamine to obtain paeonol methacrylate.

[0101] 2. Synthesis of self-renewing antifouling resin based on cation-π interaction of silane acrylate

[0102] (1) Dissolve 46.3 parts of methyl methacrylate, 25.7 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methyl ethyl acrylate, 4 parts of acryloyloxyethyltrimethylammonium chloride, 10 parts of paeonol methacrylate and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture A5.

[0103] (2) Another 50 parts of the N,N-dimethylformamide and propylene glycol methyl ether mixed solution were added to a 500 mL four-necked flask and heated to 85°C. The above mixture A5 was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding 10 parts of a N,N-dimethylformamide and propylene glycol methyl ether mixed solution containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The mixture was then stirred at 85°C for another 2-3 hours to ensure a complete reaction. The final product was a self-renewing antifouling resin based on cation-π interactions, which can be directly used to formulate marine antifouling coatings. This resin was named MBECTP-10.

[0104] The tests were conducted according to the method described in Example 1. The results showed that the static contact angle of the acrylate silane ester self-renewing antifouling coating, based on cation-π interactions, decreased from 99.6° to 82.3° and 57.6°, respectively, after immersion in artificial seawater for 10 and 20 days; the hydrolysis weight loss rate was 3.8%. X-ray photoelectron spectroscopy (XPS) tests were performed on the sample from Example 5 and the MBETP-10 sample without cations, demonstrating that paeonol could be re-adsorbed onto the coating surface via cation-π interactions after hydrolysis. (See [link to relevant documentation]). Figure 3 As shown, Figure 3 The XPS full spectrum and high-resolution C1s spectra of the acrylate silane ester self-renewing antifouling coating based on cation-π interaction are shown. After 7 days, the inhibition rate of *Dendrobium nobile* was 93.9%, the inhibition rate of *Nyctaginus simonii* was 91.5%, the inhibition rate of *Escherichia coli* was 90.0%, the inhibition rate of *Aureobasidium aureum* was 67.3%, and the inhibition rate of *Pseudomonas aeruginosa* was 77.9%.

[0105] Comparative Example 1

[0106] This embodiment describes a self-renewing antifouling resin based on cation-π interactions of silane acrylate, prepared through the following steps:

[0107] 1. Synthesis of self-renewing antifouling resin made of silane acrylate

[0108] (1) Dissolve 55.3 parts of methyl methacrylate, 30.7 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methylethyl acrylate and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture B.

[0109] (2) Another 50 parts of the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether were added to a 500 mL four-necked flask and heated to 85°C. The above mixture B was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding a mixed solution (10 parts) of N,N-dimethylformamide and propylene glycol methyl ether containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The mixture was then stirred at 85°C for another 2-3 hours to ensure a complete reaction. The final product was a self-renewing antifouling resin of silane acrylate, which can be directly used to formulate marine antifouling coatings. This resin was named MBETP-0.

[0110] The tests were conducted according to the test method in Example 1. The results showed that the static contact angle of the acrylate silane ester self-renewing antifouling coating decreased from 92.0° to 79.1° and 75.9° after immersion in artificial seawater for 10 and 20 days, respectively; the hydrolysis weight loss rate was 1.7%; the inhibition rate against Escherichia coli was 19.4%, against Aureococcus faecium was 10.3%, and against Pseudomonas aeruginosa was 16.6%.

[0111] Comparative Example 2

[0112] The self-renewing antifouling resin of silane acrylate based on cation-π interaction in this comparative example was prepared by the following steps:

[0113] 1. Synthesis of self-renewing antifouling resin made of silane acrylate

[0114] (1) Dissolve 52.7 parts of methyl methacrylate, 29.3 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methyl ethyl acrylate, 4 parts of acryloyloxyethyltrimethylammonium chloride and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture C.

[0115] (2) Another 50 parts of the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether were added to a 500 mL four-necked flask and heated to 85°C. The above mixed solution C was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding a mixed solution (10 parts) of N,N-dimethylformamide and propylene glycol methyl ether containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The mixture was then stirred at 85°C for another 2-3 hours to ensure a complete reaction. The final product was a self-renewing antifouling resin of silane acrylate, which can be directly used to formulate marine antifouling coatings. This resin was named MBECTP-0.

[0116] The tests were conducted according to the test method in Example 1. The results were as follows: the static contact angle of the acrylate silane ester self-renewing antifouling coating decreased from 83.7° to 67.3° and 68.4° after immersion in artificial seawater for 10 and 20 days, respectively; the hydrolysis weight loss rate was 1.2%; after 7 days, the inhibition rate of *Dendrobium nobile* was 81.0%, the inhibition rate of *Nyctaginus simonii* was 58.8%, the inhibition rate of *Escherichia coli* was 27.9%, the inhibition rate of *Aureobasidium aureum* was 36.2%, and the inhibition rate of *Pseudomonas aeruginosa* was 37.5%.

[0117] Comparative Example 3

[0118] The self-renewing antifouling resin of silane acrylate based on cation-π interaction in this comparative example was prepared by the following steps:

[0119] 1. Synthesis of self-renewing antifouling resin made of silane acrylate

[0120] (1) Dissolve 48.9 parts of methyl methacrylate, 27.1 parts of butyl acrylate, 10 parts of triisopropylsilyl methacrylate, 4 parts of 2-methylethyl acrylate, 10 parts of paeonol methacrylate and 1.2 parts of azobisisobutyronitrile in a mixed solution of 40 parts of N,N-dimethylformamide and propylene glycol methyl ether (the mass ratio of N,N-dimethylformamide and propylene glycol methyl ether is 2:1) to obtain mixture D.

[0121] (2) Another 50 parts of the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether were added to a 500 mL four-necked flask and heated to 85°C. The above mixture D was added dropwise under a nitrogen atmosphere, with continuous stirring at 150 rpm, over 2-3 hours. After 1-2 hours of reaction, a secondary initiation was initiated by adding 10 parts of a mixed solution of N,N-dimethylformamide and propylene glycol methyl ether containing 0.32 parts of benzoyl peroxide dropwise over 30 minutes. The mixture was then stirred at 85°C for another 2-3 hours to ensure a complete reaction. The final product was a self-renewing antifouling resin of silane acrylate, which can be directly used to formulate marine antifouling coatings. This resin was named MBETP-10.

[0122] The test was conducted according to the test method in Example 1, and the results were as follows: the hydrolysis weight loss rate of the acrylate silane ester self-renewing antifouling coating was 5.5%; the inhibition rate of Escherichia coli was 54.5%, the inhibition rate of Aureococcus aureus was 48.0%, and the inhibition rate of Pseudomonas aeruginosa was 66.6%.

[0123] The detailed descriptions listed above are merely specific illustrations of feasible embodiments of the present invention and are not intended to limit the scope of protection of the present invention. All equivalent embodiments or modifications made without departing from the spirit of the present invention should be included within the scope of protection of the present invention.

Claims

1. A self-renewing antifouling resin of silane acrylate based on cation-π interaction, characterized in that, Its structural formula is as follows: Where a, b, c, d, e, and f represent the number of repeating units in the random copolymerization, with methyl methacrylate being the repeating monomer in a; butyl acrylate being the repeating monomer in b; triisopropylsilyl methacrylate being the repeating monomer in c; acryloyloxyethyltrimethylammonium chloride being the repeating monomer in d; 2-methylethyl acrylate being the repeating monomer in e; and paeonol methacrylate being the repeating monomer in f; and co represents random copolymerization of monomers.

2. A method for preparing the silane acrylate self-renewing antifouling resin based on cation-π interaction as described in claim 1, characterized in that, By weight, the steps include: (1) Mix and dissolve 40-60 parts of methyl methacrylate, 20-40 parts of butyl acrylate, 0.5-25 parts of paeonol methacrylate, 5-15 parts of triisopropylsilyl methacrylate, 2-10 parts of 2-methyl ethyl acrylate, 1-10 parts of acryloyloxyethyltrimethylammonium chloride and 0.5-2 parts of azobisisobutyronitrile in a mixed solution of 40-60 parts of N,N-dimethylformamide and propylene glycol methyl ether to obtain mixture A; (2) Add another 40-60 parts of the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether to a four-necked flask and heat to 80-95°C. Slowly add the above mixed solution A in a protective atmosphere and continue adding. After the addition is complete, slowly add the mixed solution of N,N-dimethylformamide and propylene glycol methyl ether containing 0.1-1 parts of benzoyl peroxide for secondary initiation and continue adding. Then maintain the same temperature and continue stirring to ensure that the reaction is complete. Finally, obtain the self-renewing antifouling resin of silane acrylate based on cation-π interaction.

3. The method for preparing the silane acrylate self-renewing antifouling resin based on cation-π interaction according to claim 2, characterized in that, In step (1), the paeonol methacrylate is obtained by the following preparation method, which, by weight, includes the following steps: Dissolve 1-10 parts of paeonol and 1-10 parts of triethylamine, an acid-binding agent, in 15-35 parts of tetrahydrofuran; slowly add 1-8 parts of methacryloyl chloride dropwise to the above solution at a low temperature of 0-5℃, while continuously stirring throughout the process; after the addition is complete, stir at room temperature to allow the reaction to proceed fully; filter the mixture obtained from the reaction to remove the ammonium salt precipitate, take the filtrate, and vacuum dry it to remove tetrahydrofuran and triethylamine, to obtain paeonol methacrylate monomer.

4. The method for preparing the silane acrylate self-renewing antifouling resin based on cation-π interaction according to claim 3, characterized in that, In the preparation method of paeonol methacrylate, after the addition is completed, the mixture is stirred at room temperature for 12-36 hours to allow it to react fully.

5. The method for preparing the silane acrylate self-renewing antifouling resin based on cation-π interaction according to claim 2, characterized in that, In step (1), the mass ratio of N,N-dimethylformamide to propylene glycol methyl ether is 2:

1.

6. The method for preparing the silane acrylate self-renewing antifouling resin based on cation-π interaction according to claim 2, characterized in that, In step (2), the protective atmosphere is one or more of nitrogen, argon, and helium.

7. The method for preparing the silane acrylate self-renewing antifouling resin based on cation-π interaction according to claim 2, characterized in that, In step (2), the above mixture A is slowly added dropwise under a protective atmosphere. The addition is continuous and the mixture is stirred continuously at a speed of 100-200 rpm. The addition is completed in 2-3 hours.

8. The method for preparing the silane acrylate self-renewing antifouling resin based on cation-π interaction according to claim 2, characterized in that, In step (2), a mixed solution of N,N-dimethylformamide containing 0.1-1 part of benzoyl peroxide and propylene glycol methyl ether is continuously added dropwise for 20-40 minutes, and then the same temperature is maintained and stirred for 2-3 hours to ensure a complete reaction.

9. The application of the methacrylate silane ester self-renewing antifouling resin based on cation-π interaction as described in claim 1 in the preparation of marine antifouling coatings.

10. The application according to claim 9, characterized in that, The ester bonds in the triisopropylsilyl methacrylate and paeonol methacrylate in the cation-π interaction-based self-renewing antifouling resin can be hydrolyzed in the ocean, enabling rapid renewal of the coating surface. Partially hydrolyzed paeonol will be re-adsorbed onto the coating surface through cation-π interactions. The hydrolysis reaction formula and cation-π interaction process of the cation-π interaction-based self-renewing antifouling resin are as follows: 。

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