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 loaded on the nano carrier material; in some embodiments, the nano carrier material comprises a natural nano material grafted with an organic zinc compound. The preparation method of the antifouling nano filler comprises the following steps: preparing an organic zinc compound; purifying a natural nano material; modifying the purified nano material; grafting the modified purified nano material with the organic zinc compound; and loading the obtained product with an antifouling bactericide to obtain the antifouling nano filler. The antifouling nano filler prepared by the method of the present disclosure has good intelligent response effect, and when applied to a coating, can enhance the bactericidal property and antibacterial property of the coating, highlighting the antifouling advantage.

Description

Technical Field

[0001] This disclosure relates to the field of antifouling, specifically to the field of nanomaterials and coating materials, and more 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 undesirable accumulation of bacteria, algae, barnacles, and other marine organisms on the surface of underwater facilities, leading to continuous accumulation of dirt on building surfaces, causing pipeline blockages, increasing the drag and fuel consumption of ships, and accelerating corrosion. All of these factors can cause huge economic losses to the marine industry and generate serious environmental pollution problems.

[0003] The most effective and convenient way to prevent marine fouling is through coatings that release toxic molecules at a controlled rate to reduce or inhibit the growth of adhering organisms such as bacteria, algae, and mollusks. However, this method is highly likely to cause marine environmental pollution, affecting the growth and survival of other marine life. 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. Polymer capsules can be used to encapsulate antifouling agents that hydrolyze or rupture under external stimuli, thereby controlling their release. However, the addition of capsules increases surface energy and modulus, and the preparation of hollow capsules is relatively complex, making large-scale application difficult. Summary of the Invention

[0005] To address the problems existing in the background art, this disclosure provides an antifouling nanofiller and its preparation method, wherein the antifouling nanofiller can improve the antifouling ability of the coating.

[0006] The method for preparing antifouling nanofillers disclosed herein includes steps 1 to 5: Step 1: preparing an organozinc compound; Step 2: purifying natural nanomaterials; Step 3: modifying the purified nanomaterials; Step 4: grafting the modified purified nanomaterials with the organozinc compound; Step 5: loading the product obtained in Step 4 with an antifouling and bactericidal agent to obtain antifouling nanofillers.

[0007] In some embodiments, the natural nanomaterial includes at least one of nano-silica, halloysite nanotubes, and nano-titanium dioxide.

[0008] In some embodiments, the antifouling and bactericidal agent includes at least one of copper chloride, zinc chloride, copper sulfate, and zinc sulfate.

[0009] In some embodiments, in step 1, the organozinc compound is obtained by reacting a substance including zinc chloride and p-hydroxycinnamic acid in an organic solvent.

[0010] In some embodiments, step 1 is as follows: dissolving p-hydroxycinnamic acid in deionized water to form solution 1, then dissolving sodium hydroxide in solution 1 to form solution 2, subsequently adding zinc chloride to solution 2 to form solution 3 and stirring; finally adding sodium hydroxide solution to solution 3, stirring and heating to 50-100°C to react, to obtain an organozinc compound.

[0011] In some embodiments, in step 2, the purified natural nanomaterial is obtained by reacting substances including halloysite nanotubes, deionized water, and sodium hexametaphosphate.

[0012] In some embodiments, step 2 is as follows: dispersing natural nanomaterials 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 hours; taking the upper layer solution and centrifuging to obtain a solid precipitate, which is the purified natural nanomaterials.

[0013] In some embodiments, in step 3, the modification process is achieved by reacting materials including purified halloysite nanotubes, 3-aminopropyltriethoxysilane, dimethyl sulfoxide, and succinic anhydride in an organic solvent.

[0014] In some embodiments, step 3 is as follows: the purified natural nanomaterials are 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.

[0015] In some embodiments, step 4 is as follows: adding butyl acetate, modified purified nanomaterials, and organozinc compound to a container filled with nitrogen, refluxing and stirring at 60–100°C for 12–24 h, and then precipitating in cold ethanol to obtain the grafted product.

[0016] In some embodiments, step 5 is as follows: the grafting product obtained in step 4, 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.

[0017] This disclosure includes at least the following beneficial effects: low raw material cost and environmentally friendly; the antifouling nanofiller prepared by the method described in this disclosure has good intelligent response effect, and when applied to coatings, it can enhance the bactericidal and antibacterial properties of the coatings, highlighting its antifouling advantages. Attached Figure Description

[0018] Figure 1 The images show the infrared spectra of different products prepared in Example 1.

[0019] Figure 2 The images show the UV-Vis absorption spectra of different products prepared in Example 1.

[0020] Figure 3 The particle size distribution of different products during the preparation process of Example 1 is shown in the diagram.

[0021] Figure 4 The image shows the zeta potential diagrams of different products during the preparation process of Example 1.

[0022] Figure 5 The diagram shows the antibacterial effects of different products during the preparation process of Example 1. Detailed Implementation

[0023] 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.

[0024] 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.

[0025] The following describes the antifouling nanofiller and its preparation method.

[0026] The main concept of this disclosure is to prepare an antifouling filler by reacting an organozinc compound as a modifier with carboxylated nanomaterials. The antifouling filler not only has the advantages of broad bactericidal activity, low toxicity, and diverse antibacterial mechanisms, but also has a smart response function. It uses the aquatic environment as a stimulating factor to promote the slow and smart release of bactericides, thereby achieving a long-term effective bactericidal effect.

[0027] [Anti-fouling nanofiller]

[0028] The antifouling nanofiller described in this disclosure includes a nanocarrier material and an antifouling and bactericidal agent loaded on the nanocarrier material; in some embodiments, the nanocarrier material includes a natural nanomaterial grafted with an organozinc compound. In some embodiments, the organozinc compound is obtained by reacting a substance including zinc chloride and p-hydroxycinnamic acid in an organic solvent.

[0029] In some embodiments, the natural nanomaterials include at least one of tubular nanomaterials, sheet-like nanomaterials, and spherical nanomaterials. In some embodiments, the natural nanomaterials include at least one of nano-silica, halloysite nanotubes, and nano-titanium dioxide, preferably halloysite nanotubes. Halloysite nanotubes are a type of tubular aluminosilicate clay with a large specific surface area, nanotube structure, and good biocompatibility; using them as a carrier for antifouling agents can achieve slow release of the antifouling agent, extending the service life of the antifouling filler; simultaneously, due to the chemical composition of its inner and outer surfaces, functional drugs can be grafted onto it after modification and alteration to enhance its antifouling efficacy.

[0030] In some embodiments, the antifouling and bactericidal agent includes at least one of copper chloride, zinc chloride, copper sulfate, and zinc sulfate.

[0031] In some embodiments, for the tubular nanomaterial, an organozinc compound is grafted onto the inner and / or outer walls of the tubular nanomaterial. In some embodiments, for the sheet-like nanomaterial, an organozinc compound is grafted onto at least one side of the sheet-like nanomaterial. In some embodiments, for the spherical nanomaterial, an organozinc compound is grafted onto the inner and / or outer sides of the spherical nanomaterial.

[0032] [Preparation method of antifouling nanofillers]

[0033] In some embodiments, the method for preparing nanofillers provided in this disclosure includes steps 1 to 5:

[0034] Step 1: Preparation of organozinc compounds;

[0035] Step 2: Purify natural nanomaterials;

[0036] Step 3: Modify the purified nanomaterials;

[0037] Step 4: Graft the modified purified nanomaterials with the organozinc compound;

[0038] Step 5: Load the product obtained in Step 4 with an antifouling and bactericidal agent; prepare antifouling nanofiller.

[0039] In some embodiments, in step 1, the organozinc compound is obtained by reacting a substance including zinc chloride and p-hydroxycinnamic acid in an organic solvent.

[0040] In some embodiments, step 1 is as follows: dissolving p-hydroxycinnamic acid in deionized water to form solution 1, then dissolving sodium hydroxide in solution 1 to form solution 2, subsequently adding zinc chloride to solution 2 to form solution 3 and stirring; finally adding sodium hydroxide solution to solution 3, stirring and heating to 50-100°C to react, to obtain an organozinc compound.

[0041] In some embodiments, in step 2, 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 a large specific surface area, nanotube structure, and good biocompatibility. As a carrier for antifouling agents, they enable the slow release of antifouling agents, extending the service life of antifouling fillers. Furthermore, due to the chemical composition of their inner and outer surfaces, they can be modified and grafted with functional drugs to enhance their antifouling efficacy.

[0042] In some embodiments, in step 2, the purified natural nanomaterial is obtained by reacting substances including halloysite nanotubes, deionized water, and sodium hexametaphosphate.

[0043] In some embodiments, step 2 is as follows: dispersing natural nanomaterials 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 hours; taking the upper layer solution and centrifuging to obtain a solid precipitate, which is the purified natural nanomaterials.

[0044] In some embodiments, in step 3, the modification process is achieved by reacting materials including purified halloysite nanotubes, 3-aminopropyltriethoxysilane, dimethyl sulfoxide, and succinic anhydride in an organic solvent.

[0045] In some embodiments, step 3 comprises: dispersing the purified natural nanomaterials 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.

[0046] In some embodiments, step 4 is as follows: adding butyl acetate, modified purified nanomaterials, and organozinc compound to a container filled with nitrogen, refluxing and stirring at 60–100°C for 12–24 h, and then precipitating in cold ethanol to obtain the grafted product.

[0047] In some embodiments, in step 5, the antifouling and bactericidal agent includes at least one of copper chloride, zinc chloride, copper sulfate, and zinc sulfate.

[0048] In some embodiments, step 5 is as follows: the grafting product obtained in step 4, 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.

[0049] 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.

[0050] Example 1

[0051] Step 1: While stirring continuously at 70°C, completely dissolve 1.38 g of p-hydroxycinnamic acid in 500 mL of deionized water. Then, dissolve 1.7 g of sodium hydroxide in the aqueous solution of p-hydroxycinnamic acid. Next, add 1.1 g of zinc chloride and stir for 30 min. Finally, add the sodium hydroxide solution (formed by dissolving 1.7 g of sodium hydroxide in 100 mL of deionized water) to the reaction system and maintain the temperature at 70°C for 2 h to obtain the desired organozinc compound (denoted as BZH). Precipitate BZH, wash five times with deionized water, and then freeze-dry.

[0052] Step 2: 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).

[0053] Step 3: Disperse the pulverized HNTs (1.5 g) in anhydrous toluene (15 mL) 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 dimethyl sulfoxide (5 mL). Then add succinic anhydride (200 mg) and triethylamine (200 mg) to the mixed solution, stir at 40 °C for 48 h, centrifuge to obtain the product named HTC, and wash three times with ethanol.

[0054] Step 4: First, add 10g of butyl acetate, 1g of HTC, and 1g of BZH 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 HTCB.

[0055] Step 5: Add HTCB (30 mg), CuCl2 (44 mg), ethanol (5 mL), anhydrous toluene (5 mL), oleic acid (OAc, 0.4 mL), and oleylamine (OAm, 0.4 mL) to separate 250 mL single-necked flasks and sonicate for 2 min. Stir the resulting mixture at 55 °C for 1 min, then add 100 mg of ascorbic acid and continue stirring at 55 °C for 25 min to obtain a dark-colored solution. Centrifuge the mixture at 8000 rpm for 10 min. Wash the precipitate repeatedly with anhydrous ethanol / anhydrous toluene solution (volume ratio 1:1) and dry in a vacuum oven at 30 °C for 24 h. The resulting powder product is the antifouling nanofiller, named HTBC.

[0056] Examples 2-5

[0057] The preparation methods of Examples 2-5 are the same as those of Example 1, except that the contents of halloysite nanotubes, sodium hexametaphosphate, p-hydroxycinnamic acid, and zinc chloride are different in steps 1 and 2 of Examples 2-5 (see Table 1).

[0058] Example 6

[0059] Step 1: Dissolve 1.38 g of p-hydroxycinnamic acid completely in 500 mL of deionized water while stirring continuously at 70 °C. Then, dissolve 1.7 g of sodium hydroxide in the aqueous solution of p-hydroxycinnamic acid. Next, add 1.1 g of zinc chloride and stir for 30 min. Finally, slowly add the sodium hydroxide solution (formed by dissolving 1.7 g of sodium hydroxide in 100 mL of deionized water) to the solution and maintain the temperature at 70 °C for 2 h to obtain the desired organozinc compound (denoted as BZH). Precipitate BZH, wash five times with deionized water, and then freeze-dry.

[0060] Step 2: 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) to obtain a solid precipitate, and wash it 5 times with deionized water (8000rpm, 25min). Take the solid precipitate and place it in a vacuum freeze dryer for vacuum drying to obtain purified halloysite nanotubes, denoted as HNTs.

[0061] Step 3: Disperse the pulverized HNTs (1.5 g) in anhydrous toluene (15 mL) 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 dimethyl sulfoxide (5 mL). Then add succinic anhydride (200 mg) and triethylamine (200 mg) to the mixed solution, stir at 40 °C for 48 h, centrifuge to obtain the product named HTC, and wash three times with ethanol.

[0062] Step 4: First, add 10g of butyl acetate, 10g of HTC, and 1.36g of BZH 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 HTCB.

[0063] Step 5: Add HTCB (30 mg), copper chloride (44 mg), ethanol (5 mL), anhydrous toluene (5 mL), oleic acid (OAc, 0.4 mL), and oleylamine (OAm, 0.4 mL) to separate 250 mL single-necked flasks and sonicate for 2 min. Stir the resulting mixture at 55 °C for 1 min, then add 100 mg of ascorbic acid and continue stirring at 55 °C for 25 min to obtain a dark-colored solution. Centrifuge the mixture at 8000 rpm for 10 min. Wash the precipitate repeatedly with anhydrous ethanol / anhydrous toluene (1:1 volume ratio) solution and dry in a vacuum oven at 30 °C for 24 h. The resulting powder product is the antifouling nanofiller, named HTBC.

[0064] Examples 7-10

[0065] 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, BZH, HTCB and copper chloride are different in steps 3, 4 and 5 of Examples 7-10 (see Table 1).

[0066] 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:

[0067] A1: Halloysite nanotubes

[0068] A2: Sodium hexametaphosphate

[0069] A3: p-Hydroxycinnamic acid

[0070] A4: Zinc chloride

[0071] B1: HNTs

[0072] B2: Silane coupling agent

[0073] B3: HTC

[0074] B4: BZH

[0075] B5: HTCB

[0076] B6: Copper chloride

[0077] The HNTs, BZH, HTCB, and HTBC samples from Example 1 were subjected to infrared, ultraviolet, particle size, zeta site, and antibacterial tests, respectively. The results are as follows: Figure 1-5 As shown.

[0078] Table 1 Material parameters in Examples 1-10

[0079] <![CDATA[A1 / g]]> <![CDATA[A2 / g]]> <![CDATA[A3 / g]]> <![CDATA[A4 / g]]> <![CDATA[B1 / g]]> <![CDATA[B2 / mL]]> <![CDATA[B3 / g]]> <![CDATA[B4 / g]]> <![CDATA[B5 / g]]> <![CDATA[B6 / g]]> Example 1 100 10 1.38 1.1 1.5 1.5 1 1 0.03 0.044 Example 2 200 5 2.8 2.3 1.5 1.5 1 1 0.03 0.044 Example 3 250 3 4.2 3.4 1.5 1.5 1 1 0.03 0.044 Example 4 200 2 5.59 4.56 1.5 1.5 1 1 0.03 0.044 Example 5 150 1 6.98 5.7 1.5 1.5 1 1 0.03 0.044 Example 6 250 3 6.98 5.7 2 4 10 1 0.06 0.088 Example 7 250 3 6.98 5.7 1.5 3 10 1.5 0.06 0.06 Example 8 250 3 6.98 5.7 1 2 10 0.5 0.12 0.1 Example 9 250 3 6.98 5.7 1.5 1.5 10 2 0.15 0.25 Example 10 250 3 6.98 5.7 2 2 10 2.5 0.3 0.44

[0080] See the infrared spectrum ( Figure 1 For BZH, 3425cm -1 1639cm -1 1610cm -1 and 1510cm -1 The characteristic peak at this point is attributed to the OH hydrogen bond between the stretching vibrations of p-hydroxycinnamic acid, alkenes, carboxylates, and aromatic compounds; for HTCB, the carboxylate (COO-Zn-COO) peaks at 1607 cm⁻¹. -1 An asymmetric stretching vibration peak appears at this location, and its intensity is higher than that of BZH, indicating that BZH has been successfully introduced into HTCB. See the UV-Vis absorption spectrum ( Figure 2 The presence of characteristic peaks for BZH in the figure also indicates the successful preparation of HTCB. See the particle size distribution diagram (…). Figure 3 The particle size of HTCB is larger than that of HNTs; see the Zeta potential diagram. Figure 4 The fact that the zeta potential of HNTs is negative while that of HTCB is positive proves the successful preparation of HTCB.

[0081] In addition, tests showed that the infrared, ultraviolet, particle size, and zeta potential test patterns of the products prepared in Examples 2-10 were the same as those in Example 1, which all proved the successful preparation of HTCB.

[0082] The bacterial growth was observed by adding HTCB and HTBC from Example 1 to the culture media of Bacillus and Pseudomonas pseudoalteromonas, respectively. The results are as follows: Figure 5 As shown in the diagram. In the control group, the solid culture medium contained a large number of both bacterial groups. No significant bacterial groups were observed in the HTCB solid culture medium, while no bacteria were observed at all in the HTBC. After another 24 hours of incubation, sampling revealed that no significant bacterial groups appeared in the HTCB solid culture medium. Therefore, the HTBC antifouling nanofiller finally prepared in this example exhibits excellent bactericidal effects. Meanwhile, from... Figure 2 The sustained prominence of the peaks in the ultraviolet-visible absorption spectrum indicates that its bactericidal effect is long-lasting.

[0083] In summary, the antifouling nanofiller provided in this disclosure has low raw material costs and is environmentally friendly; the grafting of organic zinc compounds onto natural nanomaterials gives it long-lasting bactericidal properties, and loading bactericides can further increase its bactericidal ability.

[0084] 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. A method for preparing an antifouling nanofiller, characterized in that, Including steps 1 through 5: Step 1: Preparation of organozinc compounds; Step 2: Purify natural nanomaterials; Step 3: Modify the purified nanomaterials; Step 4: Graft the modified purified nanomaterials with the organozinc compound; Step 5: Load the product obtained in Step 4 with an antifouling and bactericidal agent to obtain an antifouling nanofiller; The natural nanomaterial is halloysite nanotubes; In step 1, the organozinc compound is obtained by reacting substances including zinc chloride and p-hydroxycinnamic acid in an organic solvent; In step 3, the modification process is achieved by reacting materials including purified halloysite nanotubes, 3-aminopropyltriethoxysilane, dimethyl sulfoxide, and succinic anhydride in an organic solvent.

2. The method for preparing antifouling nanofillers according to claim 1, characterized in that, The antifouling and bactericidal agent includes at least one of copper chloride, zinc chloride, copper sulfate, and zinc sulfate.

3. The method for preparing antifouling nanofillers according to claim 1, characterized in that, Step 1 is as follows: dissolve p-hydroxycinnamic acid in deionized water to form solution 1, then dissolve sodium hydroxide in solution 1 to form solution 2, then add zinc chloride to solution 2 to form solution 3 and stir; finally, add sodium hydroxide solution to solution 3, stir and heat to 50~100℃ to react and obtain organozinc compound.

4. The method for preparing antifouling nanofiller according to claim 1, characterized in that, In step 2, the purified natural nanomaterials are obtained through a reaction of substances including halloysite nanotubes, deionized water, and sodium hexametaphosphate.

5. The method for preparing antifouling nanofiller according to claim 1, characterized in that, Step 2 is as follows: dispersing the natural nanomaterials 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 h; then letting it stand for 4 h; taking the upper layer solution and centrifuging to obtain a solid precipitate, which is the purified natural nanomaterials.

6. The method for preparing antifouling nanofillers according to claim 1, characterized in that, Step 3 is as follows: the purified natural nanomaterials are 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 in an argon atmosphere for 12-24 h 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.

7. The method for preparing antifouling nanofiller according to claim 1, characterized in that, Step 4 involves adding butyl acetate, the modified purified nanomaterial, and an organozinc compound to a container filled with nitrogen. The mixture is then refluxed and stirred at 60-100°C for 12-24 hours. Finally, the mixture is precipitated in cold ethanol to obtain the grafted product.

8. The method for preparing antifouling nanofiller according to claim 1, characterized in that, Step 5 is as follows: the grafting product obtained in step 4, antifouling and bactericidal agent, ethanol, anhydrous toluene, oleic acid, and oleylamine are added to a container to form a mixture, and then ascorbic acid is added. The mixture is stirred continuously at 50~80℃ for 30~60 min to obtain a dark-colored solution. After centrifugation, washing, and drying, the antifouling nanofiller is obtained.

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