Antifouling nanofillers and methods of making the same

Abstract

The present disclosure provides an antifouling nano filler and a preparation method thereof. The antifouling nano filler comprises a nano carrier material and an antifouling bactericide. The nano carrier material comprises a nano carrier material grafted with a natural organic compound, and the natural organic compound comprises at least one of a natural antibacterial alcohol or phenolic compound and a derivative thereof. The preparation method of the antifouling nano filler comprises the following steps: purifying the nano carrier material; modifying the purified nano carrier material; grafting the modified purified nano carrier material with a natural organic compound; and loading the obtained product with an antifouling bactericide to obtain the antifouling nano filler. The natural organic compound comprises at least one of a natural antibacterial alcohol or phenolic compound and a derivative thereof. The antifouling nano filler prepared by the method has good intelligent response effect and improves the antifouling effect of the loaded antifouling agent.

Description

Technical Field

[0001] This disclosure relates to the field of nanomaterials and coating materials, specifically to antifouling nanofillers and their preparation methods. Background Technology

[0002] With the development of the marine industry, the problem of marine fouling of facilities such as buildings, ship hulls, pipelines, oil platforms, and marine sensors has become increasingly prominent. Marine fouling is mainly caused by the large-scale accumulation of marine organisms such as bacteria, algae, and barnacles on the surface of underwater facilities. This biological pollution leads to the continuous accumulation of dirt on building surfaces, causing pipeline blockages, increasing the drag and fuel consumption of ships, and accelerating corrosion, all of which can cause huge economic losses and serious problems for the marine industry.

[0003] The most effective and convenient way to prevent marine fouling is through coatings that release toxic bactericidal molecules at a controlled rate. Traditional antifouling coatings mainly rely on compounds containing heavy metals (such as copper and tin), which inhibit biofouling by slowly releasing toxic substances. However, these toxic substances can cause serious pollution to marine ecosystems and have toxic effects on non-target organisms. Therefore, developing long-lasting, environmentally friendly antifouling agents is extremely important.

[0004] Currently, because antifouling agents are usually physically incorporated into coatings, their release rate is difficult to control, resulting in a short coating lifespan. Nanomaterials can be used to encapsulate antifouling agents that hydrolyze or break down under external stimuli, thereby controlling their release. However, directly encapsulating bactericides into nanomaterials cannot guarantee the effective load of the antifouling and bactericide, nor can it guarantee long-lasting bactericidal performance. Summary of the Invention

[0005] To address the problems existing in the background art, this disclosure provides an antifouling nanofiller and its preparation method.

[0006] The antifouling nanofiller disclosed herein comprises nanocarrier materials and antifouling bactericides as raw materials; characterized in that the nanocarrier materials comprise nanocarrier materials grafted with natural organic compounds, wherein the natural organic compounds comprise at least one of natural antibacterial alcohols or phenolic compounds and their derivatives.

[0007] In some embodiments, the natural organic compound includes at least one of 7-hydroxy-4-methylcoumarin, catechin, resveratrol, and lavenderol.

[0008] The method for preparing antifouling nanofillers disclosed herein includes steps 1 to 4: Step 1: Purifying nanocarrier materials; Step 2: Modifying the purified nanocarrier materials; Step 3: Grafting natural organic compounds onto the modified purified nanocarrier materials; Step 4: Loading an antifouling and bactericidal agent onto the product obtained in Step 3 to obtain antifouling nanofillers; wherein, the natural organic compounds include at least one of natural antibacterial alcohols or phenolic compounds and their derivatives.

[0009] In some embodiments, the natural organic compound includes at least one of 7-hydroxy-4-methylcoumarin, catechin, resveratrol, and lavenderol.

[0010] In some embodiments, in step 1, the purified nanocarrier material is obtained by reacting substances including halloysite nanotubes, deionized water, and sodium hexametaphosphate.

[0011] In some embodiments, step 1 is as follows: dispersing the nanocarrier material in deionized water to form dispersion 1, adding sodium hexametaphosphate to dispersion 1, adjusting the pH of dispersion 1 to 8-11, stirring and reacting for 12-24 hours; then letting it stand for 4-8 hours; then centrifuging to take the supernatant; then further centrifuging to take the supernatant solution until the solution is neutral, and freeze-drying to obtain a solid precipitate, which is the purified nanocarrier material.

[0012] In some embodiments, in step 2, the modification process is achieved by reacting materials including purified halloysite nanotubes, 3-aminopropyltriethoxysilane, dimethyl sulfoxide, and succinic anhydride in an organic solvent.

[0013] In some embodiments, step 2 is as follows: the purified nanocarrier material is dispersed in anhydrous toluene to form mixture 1, and mixture 1 is degassed with argon for 40-60 min; a silane coupling agent is added to mixture 1 to form mixture 2, and mixture 2 is stirred and refluxed at 100-120°C for 12-24 h in an argon atmosphere to obtain mixture 3; mixture 3 is centrifuged and dried to obtain a precipitate; the precipitate is dispersed in dimethyl sulfoxide, and then succinic anhydride and triethylamine are added, and the mixture is stirred at 40-80°C for 48-60 h, and centrifuged to obtain the modified product.

[0014] In some embodiments, step 3 is as follows: adding butyl acetate, the modified nanocarrier material grafted onto a three-necked flask, and a natural organic compound; filling the three-necked flask with nitrogen to maintain the reaction under nitrogen atmosphere; refluxing and stirring the reaction at 60–100°C for 12–24 h; and then precipitating the grafted product in cold ethanol to obtain the grafted product.

[0015] In some embodiments, step 4 is as follows: the grafting product obtained in step 3, the antifouling and bactericidal agent, ethanol, anhydrous toluene, oleic acid, and oleylamine are added to a container to form a mixture, and ascorbic acid is added. The mixture is stirred continuously at 50-80°C for 30-60 minutes to obtain a dark-colored solution. The solution is then centrifuged, washed, and dried to obtain the antifouling nanofiller.

[0016] This disclosure includes at least the following beneficial effects: First, the raw materials are inexpensive and environmentally friendly; second, the antifouling nanofiller prepared by the method described in this disclosure has a good intelligent response effect and improves the antifouling effect of the loaded antifouling agent; third, when applied to coatings, it can enhance the bactericidal and antibacterial properties of the coating and extend the antifouling cycle, highlighting its antifouling advantages. Attached Figure Description

[0017] Figure 1 The images show the infrared spectra of different products prepared in Example 1.

[0018] Figure 2 The images show the UV-Vis absorption spectra of different products prepared in Example 1.

[0019] Figure 3 The particle size distribution of different products during the preparation process of Example 1 is shown in the diagram.

[0020] Figure 4 The image shows the zeta potential diagrams of different products during the preparation process of Example 1.

[0021] Figure 5 The diagram shows the antibacterial effects of different products during the preparation process of Example 1.

[0022] Figure 6 The image shows a SEM image of the HTHA product prepared in Example 1.

[0023] Figure 7 The image shows a SEM image of the antifouling nanofiller product prepared in existing literature.

[0024] Figure 8 The images show the long-lasting UV-Vis absorption spectra of different products during the preparation process of Example 1; where d0, d3, d13, d21, and d28 represent the curves for day 0, day 3, day 12, day 21, and day 28, respectively. Detailed Implementation

[0025] It should be understood that the disclosed embodiments are merely examples, and this disclosure can be implemented in various forms. Therefore, the specific details of this disclosure should not be construed as limiting, but rather serve as the basis for the claims, intended to teach those skilled in the art how to implement this disclosure in various ways. In the description of this disclosure, terms and technical terms not explicitly stated are common knowledge to those skilled in the art, and methods not explicitly stated are conventional methods known to those skilled in the art. In the description of this disclosure, the term "grafting" refers to the combination of substances in chemistry, including but not limited to complexation, bonding, growth, and all other forms of objective combination.

[0026] The endpoints and any values ​​of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and such ranges or values ​​should be understood to include values ​​close to such ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed herein.

[0027] The following describes the antifouling nanofiller and its preparation method.

[0028] The main concept of this disclosure is to prepare antifouling nanofillers by reacting natural organic compounds as modifiers with carboxylated nanocarrier materials. The antifouling nanofillers not only have the advantages of broad bactericidal activity, low toxicity, and diverse antibacterial mechanisms, but also have the function of intelligent response. They use the aquatic environment as a stimulating factor to promote the slow and intelligent release of bactericides, thereby achieving long-term effective bactericidal effect.

[0029] [Anti-fouling nanofiller]

[0030] The antifouling nanofiller disclosed herein comprises nanocarrier materials and antifouling bactericides as raw materials; characterized in that the nanocarrier materials comprise nanocarrier materials grafted with natural organic compounds, wherein the natural organic compounds comprise at least one of natural antibacterial alcohols or phenolic compounds and their derivatives.

[0031] In some embodiments, the natural organic compound includes at least one of 7-hydroxy-4-methylcoumarin, catechin, resveratrol, and lavenderol.

[0032] In some embodiments, the antifouling and bactericidal agent includes at least one selected from metal nitrates, metal chlorides, and metal oxides. In some embodiments, the antifouling and bactericidal agent includes at least one selected from silver nitrate, copper chloride, copper sulfate, and zinc sulfate.

[0033] In some embodiments, the nanocarrier material includes at least one of tubular nanocarrier materials, sheet-like nanocarrier materials, and spherical nanocarrier materials. In some embodiments, the nanocarrier material includes natural nanomaterials. In some embodiments, the natural nanomaterial includes at least one of nano-silica, halloysite nanotubes, and nano-titanium dioxide, preferably halloysite nanotubes. Halloysite nanotubes are tubular aluminosilicate clays with good biocompatibility and environmental friendliness, and will not cause serious pollution to the environment, making them a sustainable choice for antifouling carriers. Simultaneously, their unique hollow structure and high specific surface area enable them to effectively adsorb and load antifouling agents, improving the stability and release efficiency of the antifouling agents. Using them as carriers for antifouling agents allows for slow release of the antifouling agents, extending the service life of the antifouling filler. Furthermore, due to the chemical composition of their inner and outer surfaces, after modification and alteration, flexible design and application schemes can be provided, enhancing the antifouling loading effect.

[0034] In some embodiments, for the tubular nanocarrier material, an organic compound is grafted onto the inner and / or outer walls of the tubular nanocarrier material. In some embodiments, for the sheet-like nanocarrier material, an organic compound is grafted onto at least one side of the sheet-like nanocarrier material. In some embodiments, for the spherical nanocarrier material, an organic compound is grafted onto the inner and / or outer sides of the spherical nanocarrier material.

[0035] [Preparation method of antifouling nanofillers]

[0036] The method for preparing the antifouling nanofiller described in this disclosure includes steps 1 to 4:

[0037] Step 1: Purify the nanocarrier material; Step 2: Modify the purified nanocarrier material; Step 3: Graft the modified purified nanocarrier material with natural organic compounds; Step 4: Load the product obtained in Step 3 with an antifouling and bactericidal agent to obtain an antifouling nanofiller; wherein, the natural organic compound includes at least one of natural antibacterial alcohols or phenolic compounds and their derivatives.

[0038] In some embodiments, in step 1, the nanocarrier material includes at least one of nano-silica, halloysite nanotubes, and nano-titanium dioxide, preferably halloysite nanotubes.

[0039] In some embodiments, in step 1, the purified nanocarrier material is obtained by reacting substances including halloysite nanotubes, deionized water, and sodium hexametaphosphate.

[0040] In some embodiments, step 1 is as follows: dispersing the nanocarrier material in deionized water to form dispersion 1, adding sodium hexametaphosphate to dispersion 1, adjusting the pH of dispersion 1 to 8-11, stirring and reacting for 12-24 hours; then letting it stand for 4-8 hours; then centrifuging to take the supernatant; then further centrifuging to take the supernatant solution until the solution is neutral, and freeze-drying to obtain a solid precipitate, which is the purified nanocarrier material.

[0041] In some embodiments, in step 2, the modification process is achieved by reacting materials including purified halloysite nanotubes, 3-aminopropyltriethoxysilane, dimethyl sulfoxide, and succinic anhydride in an organic solvent.

[0042] In some embodiments, step 2 comprises: dispersing the purified nanocarrier material in anhydrous toluene to form mixture 1; degassing mixture 1 with argon for 40–60 min; adding a silane coupling agent to mixture 1 to form mixture 2; stirring and refluxing mixture 2 at 100–120 °C for 12–24 h in an argon atmosphere to obtain mixture 3; centrifuging and drying mixture 3 to obtain a precipitate; dispersing the precipitate in dimethyl sulfoxide, then adding succinic anhydride and triethylamine, stirring at 40–80 °C for 48–60 h, and centrifuging to obtain the modified product. In some embodiments, the silane coupling agent is selected from at least one of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane.

[0043] In some embodiments, in step 3, the natural organic compound includes at least one of 7-hydroxy-4-methylcoumarin, catechin, resveratrol, and lavenderol.

[0044] In some embodiments, step 3 is as follows: adding butyl acetate, the modified nanocarrier material grafted onto a three-necked flask, and a natural organic compound; filling the three-necked flask with nitrogen to maintain the reaction under nitrogen atmosphere; refluxing and stirring the reaction at 60–100°C for 12–24 h; and then precipitating the grafted product in cold ethanol to obtain the grafted product.

[0045] In some embodiments, in step 4, the antifouling and bactericidal agent includes at least one selected from metal nitrates, metal chlorides, and metal oxides. In some embodiments, in step 4, the antifouling and bactericidal agent includes at least one selected from silver nitrate, copper chloride, copper sulfate, and zinc sulfate.

[0046] In some embodiments, step 4 is as follows: the grafting product obtained in step 3, the antifouling and bactericidal agent, ethanol, anhydrous toluene, oleic acid, and oleylamine are added to a container to form a mixture, and ascorbic acid is added. The mixture is stirred continuously at 50-80°C for 30-60 minutes to obtain a dark-colored solution. The solution is then centrifuged, washed, and dried to obtain the antifouling nanofiller.

[0047] [Example]

[0048] The present disclosure is further illustrated below with reference to the embodiments. Unless otherwise specified, the reagents, materials and instruments used in the following embodiments and comparative examples are commercially available or prepared by methods known in the art.

[0049] Example 1

[0050] Step 1: Weigh 100g of halloysite nanotubes into a 500mL beaker, add 300mL of deionized water, and stir mechanically for 1h. Add 10g of sodium hexametaphosphate, adjust the pH of the solution in the beaker to 8 with 10wt% sodium hydroxide solution, and continue stirring for 12h. After standing for 4h, centrifuge the supernatant (4000rpm, 15min); centrifuge the supernatant (10000rpm, 25min) to obtain a solid precipitate, and wash it 5 times with deionized water (10000rpm, 25min). Take the solid precipitate and place it in a vacuum freeze dryer for vacuum drying to obtain purified halloysite nanotubes (denoted as HNTs).

[0051] Step 2: Disperse 1.5 g of pulverized HNTs in 15 mL of anhydrous toluene and degas the solution with argon for 40 min. Add 1.5 mL of silane coupling agent to the mixture, and stir and reflux the resulting mixture at 120 °C for 12 h under an argon atmosphere. Then centrifuge the mixture at 8000 rpm for 10 min, and repeatedly wash the precipitate with anhydrous toluene to remove ungrafted coupling agent. Finally, dry the mixture in a vacuum oven at 50 °C for 24 h, and disperse the resulting product in 5 mL of dimethyl sulfoxide. Then add 200 mg of succinic anhydride and 200 mg of triethylamine to the mixed solution, stir at 40 °C for 48 h, centrifuge to obtain the product named HTC, and wash three times with ethanol.

[0052] Step 3: First, add 10g of butyl acetate, 1g of HTC, and 1g of 7-hydroxy-4-methylcoumarin to a round-bottom flask filled with nitrogen. Reflux the reaction mixture at 70°C with stirring for 12 hours, then precipitate the product in cold ethanol. The product is named HTCH.

[0053] Step 4: HTCH (30 mg), AgNO3 (44 mg), ethanol (5 mL), anhydrous toluene (5 mL), oleic acid (OAc, 0.4 mL), and oleylamine (OAm, 0.4 mL) were added separately to 250 mL single-necked flasks and sonicated for 2 min. The resulting mixture was stirred at 55 °C for 1 min, then 100 mg of ascorbic acid was added, and the mixture was stirred at 55 °C for 25 min to obtain a dark-colored solution. The mixture was then centrifuged at 8000 rpm for 10 min. The precipitate was repeatedly washed with anhydrous ethanol / anhydrous toluene solution (volume ratio 1:1) and dried in a vacuum oven at 30 °C for 24 h. The resulting powdered product was the antifouling nanofiller, named HTHA.

[0054] Examples 2-5

[0055] The preparation methods of Examples 2-5 are the same as those of Example 1, except that the contents of halloysite nanotubes and sodium hexametaphosphate in step 1 of Examples 2-5 are different, as detailed in Table 1.

[0056] Example 6

[0057] Step 1: Weigh 250g of halloysite nanotubes into a 500mL beaker, add 400mL of deionized water, and stir mechanically for 1h. Add 3g of sodium hexametaphosphate, adjust the pH of the solution in the beaker to 9 with 10wt% sodium hydroxide solution, and continue stirring for 12h. After standing for 4h, centrifuge the supernatant (3000rpm, 15min); centrifuge the supernatant (8000rpm, 25min). The resulting solid precipitate is washed 5 times with deionized water (8000rpm, 25min). The solid precipitate is then placed in a vacuum freeze dryer for vacuum drying to obtain purified halloysite nanotubes, denoted as HNTs.

[0058] Step 2: Disperse 1.5 g of pulverized HNTs in 15 mL of anhydrous toluene and degas the solution with argon for 40 min. Add 1.5 mL of 3-aminopropyltriethoxysilane to the mixture, and stir and reflux the resulting mixture at 120 °C for 12 h under an argon atmosphere. Then centrifuge the mixture at 8000 rpm for 10 min, and repeatedly wash the precipitate with anhydrous toluene to remove ungrafted APTES. Finally, dry the mixture in a vacuum oven at 50 °C for 24 h, and disperse the resulting product in 5 mL of dimethyl sulfoxide. Then add 200 mg of succinic anhydride and 200 mg of triethylamine to the mixed solution, stir at 40 °C for 48 h, centrifuge to obtain the product named HTC, and wash three times with ethanol.

[0059] Step 3: First, add 10g butyl acetate, 10g HTC, and 1.36g 7-hydroxy-4-methylcoumarin to a round-bottom flask filled with nitrogen. Reflux the reaction mixture at 70°C with stirring for 12 hours, then precipitate the product in cold ethanol and name it HTCH.

[0060] Step 4: HTCH (30 mg), AgNO3 (44 mg), ethanol (5 mL), anhydrous toluene (5 mL), oleic acid (OAc, 0.4 mL), and oleylamine (OAm, 0.4 mL) were added separately to 250 mL single-necked flasks and sonicated for 2 min. The resulting mixture was stirred at 55 °C for 1 min, then 100 mg of ascorbic acid was added, and the mixture was stirred at 55 °C for 25 min to obtain a dark-colored solution. The mixture was then centrifuged at 8000 rpm for 10 min. The precipitate was repeatedly washed with anhydrous ethanol / anhydrous toluene (volume ratio 1:1) solution and dried in a vacuum oven at 30 °C for 24 h. The resulting powdered product was the antifouling nanofiller, named HTHA.

[0061] Examples 7-10

[0062] The preparation methods of Examples 7-10 are the same as those of Example 6, except that the contents of HNTs, silane coupling agent, HTC, 7-hydroxy-4-methylcoumarin, HTCH and silver chloride are different in steps 3, 4 and 5 of Examples 7-10, as detailed in Table 1.

[0063] The material parameters involved in Examples 1-10 are shown in Table 1. For ease of explanation, specific substances are represented by symbols in Table 1:

[0064] A1: Halloysite nanotubes;

[0065] A2: Sodium hexametaphosphate;

[0066] B1: HNTs;

[0067] B2: Silane coupling agent;

[0068] B3: HTC;

[0069] B4: 7-Hydroxy-4-methylcoumarin;

[0070] B5: HTCH.

[0071] The relevant products from the process in Example 1 were subjected to infrared, ultraviolet, particle size, zeta potential, antibacterial, SEM, and long-lasting ultraviolet-visible absorption spectroscopy tests. The results are as follows: Figure 1-8 As shown.

[0072] Table 1 Material parameters in Examples 1-10

[0073] A1 / g A2 / g B1 / g B2 / g B3 / g B4 / g B5 / g B6 / g Example 1 100 10 1.5 1.5 1 1 0.03 0.044 Example 2 200 5 1.5 1.5 1 1 0.03 0.044 Example 3 250 3 1.5 1.5 1 1 0.03 0.044 Example 4 200 2 1.5 1.5 1 1 0.03 0.044 Example 5 150 1 1.5 1.5 1 1 0.03 0.044 Example 6 250 3 2 4 10 1 0.06 0.088 Example 7 250 3 1.5 3 10 1.5 0.06 0.06 Example 8 250 3 1 2 10 0.5 0.12 0.1 Example 9 250 3 1.5 1.5 10 2 0.15 0.25 Example 10 250 3 2 2 10 2.5 0.3 0.44

[0074] Figure 1-5 The images show the infrared, ultraviolet, particle size, zeta site, and antibacterial test results for HNTs, HTCB, and HTBC in Example 1. In the infrared spectrum of 7-hydroxy-4-methylcoumarin, 3128 cm⁻¹... -1 1678cm -1 1598cm -1 The characteristic peak at this point is attributed to the OH hydrogen bond between the stretching vibration of the hydroxyl group and the CH stretching vibration of the aromatic ring. For HTCH, the carbonyl group (C=O) peaks at 1637 cm⁻¹. -1 The appearance of an asymmetric stretching vibration peak indicates that 7-hydroxy-4-methylcoumarin has been successfully introduced into HTCH. The presence of a characteristic peak of 7-hydroxy-4-methylcoumarin in the UV-Vis absorption spectrum of HTCH further confirms its successful preparation. Furthermore, the peak value observed on day 3 of the UV-Vis absorption spectrum, which stabilizes on day 13 and shows a slow upward trend up to day 28, indicates its long-lasting bactericidal effect. The increase in the Zeta potential from HNTs to HTCH, and the change in particle size from HNTs to HTCB, both demonstrate the successful preparation of HTCH. Additionally, experiments and tests, including the infrared, UV, particle size, and Zeta potential measurements of the products prepared in Examples 2-10, all confirm the successful preparation of the relevant products.

[0075] Figure 5 The image shows the bacterial growth in the culture media containing Bacillus subtilis and Pseudomonas pseudoalteromonas in Example 1, specifically HTCH and HTHA. In the control group, the solid culture medium contained a large number of both bacterial groups. The bacterial count in the HTCH solid culture medium was relatively lower than the control group, while the bacterial count in the HTHA solid culture medium was significantly lower than the control group, indicating an effective loading of the antifouling and bactericidal agents. After 24 hours of further storage, sampling revealed no significant bacterial growth in the HTCH solid culture medium. Therefore, the HTHA antifouling nanofiller finally prepared in this example exhibits excellent bactericidal effects.

[0076] The HTHA powder from Example 1 was observed under a SEM electron microscope, and the results are as follows: Figure 6 As shown, compared with the antifouling nanofillers obtained in the existing literature (Deng Yajun. Preparation and performance study of composite anticorrosive and antifouling organic coatings [D]. Xiamen University, 2022.DOI:10.27424 / d.cnki.gxmdu.2022.000119.), the bactericide loading of the HTHA powder in Example 1 is significantly improved compared with the bactericide loading of the products in the existing literature.

[0077] An ethanol solution of HTCH from Example 1 was taken and subjected to UV testing on days 0, 1, 3, 7, 13, 21, and 28. The results are as follows. Figure 8 As shown, a clear upward trend can still be observed in its curve on day 28, proving the long-lasting effect of its intelligent response sterilization function.

[0078] In summary, the antifouling nanofiller provided in this disclosure has low raw material costs and is environmentally friendly; the grafting of organic compounds onto natural nanomaterials gives it long-lasting bactericidal properties, while loading bactericides further enhances its bactericidal ability.

[0079] The above description is merely an example of this disclosure and is not intended to limit this disclosure in any way. Although this disclosure is presented above with preferred embodiments, it is not intended to limit this disclosure. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solutions disclosed herein are equivalent to equivalent implementation cases and are all within the scope of the technical solutions disclosed herein.

Claims

1. An antifouling nanofiller, the raw materials of which include nanocarrier materials and antifouling bactericides; characterized in that, The nanocarrier material includes a nanocarrier material grafted with natural organic compounds, wherein the natural organic compounds include at least one of natural antibacterial alcohols or phenolic compounds and their derivatives. The nanocarrier material is halloysite nanotubes; The natural organic compounds include at least one of 7-hydroxy-4-methylcoumarin, catechin, resveratrol, and lavenderol.

2. A method for preparing an antifouling nanofiller, characterized in that, Including steps 1 through 4: Step 1: Purify the nanocarrier material; Step 2: Modify the purified nanocarrier material; Step 3: Graft the modified purified nanocarrier material with natural organic compounds; Step 4: Load the product obtained in Step 3 with an antifouling and bactericidal agent to prepare antifouling nanofiller; The natural organic compounds include at least one of natural antibacterial alcohols or phenolic compounds and their derivatives; The nanocarrier material is halloysite nanotubes; The natural organic compounds include at least one of 7-hydroxy-4-methylcoumarin, catechin, resveratrol, and lavenderol; In step 2, the modification process is achieved by reacting materials including purified halloysite nanotubes, 3-aminopropyltriethoxysilane, dimethyl sulfoxide, and succinic anhydride in an organic solvent.

3. The method for preparing antifouling nanofillers according to claim 2, characterized in that, In step 1, the purified nanocarrier material is obtained through a reaction of substances including halloysite nanotubes, deionized water, and sodium hexametaphosphate.

4. The method for preparing antifouling nanofillers according to claim 2, characterized in that, Step 1 is as follows: the nanocarrier material is dispersed in deionized water to form dispersion 1, sodium hexametaphosphate is added to dispersion 1, the pH of dispersion 1 is adjusted to 8-11, and the mixture is stirred for 12-24 h; then it is allowed to stand for 4-8 h; then the supernatant is collected by centrifugation; then the supernatant is collected by further centrifugation until the solution is neutral, and the solid precipitate is obtained by freeze drying, which is the purified nanocarrier material.

5. The method for preparing antifouling nanofillers according to claim 2, characterized in that, Step 2 is as follows: the purified nanocarrier material is dispersed in anhydrous toluene to form mixture 1, and mixture 1 is degassed with argon for 40-60 min; a silane coupling agent is added to mixture 1 to form mixture 2, and mixture 2 is stirred and refluxed at 100-120 °C for 12-24 h in an argon atmosphere to obtain mixture 3; mixture 3 is centrifuged and dried to obtain a precipitate; the precipitate is dispersed in dimethyl sulfoxide, and then succinic anhydride and triethylamine are added, and the mixture is stirred at 40-80 °C for 48-60 h, and centrifuged to obtain the modified product.

6. The method for preparing antifouling nanofillers according to claim 2, characterized in that, Step 3 is as follows: butyl acetate, modified nanocarrier material grafting, and natural organic compound are added to a three-necked flask. Nitrogen gas is filled into the three-necked flask to maintain the reaction in a nitrogen atmosphere. The reaction is refluxed and stirred at 60~100℃ for 12~24 h. Then, the product is precipitated in cold ethanol to obtain the grafted product.

7. The method for preparing antifouling nanofillers according to claim 2, characterized in that, Step 4 involves adding the grafting product obtained in step 3, antifouling and bactericidal agent, ethanol, anhydrous toluene, oleic acid, and oleylamine into a container to form a mixture. Ascorbic acid is then added, and the mixture is stirred continuously at 50-80°C for 30-60 minutes to obtain a dark-colored solution. The solution is then centrifuged, washed, and dried to obtain the antifouling nanofiller.

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