Self-cleaning antibacterial marine antifouling coating, preparation method and application

Abstract

The present invention provides a self-cleaning, antibacterial, and marine antifouling coating, as well as a preparation method and application thereof. The ethoxy groups of APTES are activated and hydrolyzed in water, reacting with hydroxyl groups on the surfaces of 3D-NFG-BiOCl and 3D-NF-BiOCl to form Si-O-Bi bonds, thereby achieving a preliminary connection between the APTES and BiOCl. The hydrolyzed ethoxy groups then react with amino groups on the surface of a nylon material to form N-O-Si bonds, thereby enabling the APTES to graft the 3D-NFG-BiOCl and 3D-NF-BiOCl onto the nylon surface. The synergistic effect of the three substances, due to the non-toxic and excellent photocatalytic activity of BiOCl, the nano-SiO2 having a nano-spherical protruding structure and the ability to withstand extreme conditions, and the excellent properties of silicone resins such as low surface energy, hydrophobicity, antifouling resistance, and high elasticity, imparts to the nylon material properties of weather resistance, self-cleaning, super-hydrophobicity, antibacterial properties, and antifouling, thereby achieving the goal of efficient antifouling and antibacterial nylon netting.

Description

Technical Field

[0001] The present invention relates to the technical field, and in particular to a self-cleaning antibacterial marine antifouling coating, a preparation method and an application thereof. Background Art

[0002] Aquaculture nets are an important component of cage aquaculture, used to enclose a certain water space, confining aquacultured objects such as fish and shrimp to prevent them from escaping and protecting them from natural enemies. They are mainly made of nylon. Aquaculture nets that are placed in seawater for a long time are often attached and contaminated by marine organisms such as shellfish and algae. These attachments not only consume a large amount of dissolved oxygen in the seawater in the cage, but also block the mesh, causing the flow of seawater inside the cage to slow down and the water quality to become eutrophic. Ultimately, the farmed seafood may die due to lack of oxygen or environmental deterioration. In addition, the marine aquaculture industry also faces the severe challenge of pathogenic bacterial infection. Once the bacteria break out, it will spread rapidly like an avalanche, triggering a series of chain reactions and dealing a heavy blow to the aquaculture industry. The risks of marine organism attachment and bacterial infection mentioned above are important issues that cannot be ignored in marine aquaculture.

[0003] Chinese patent CN 109651940 A discloses an antifouling coating for aquaculture cages. The coating utilizes the network structure of the resin and the degradation rate of the resin to control the storage and release of the antifouling agent, thereby achieving an antifouling effect. However, to reduce the impact of biofouling on marine aquaculture, the patent uses an antifouling coating containing heavy metals (such as cuprous oxide). Although these measures are effective in the short term, the heavy metals they contain will have a long-term negative impact on the marine environment. At the same time, these antifouling coatings do not have a sterilization function. Chinese patent CN 108691030 A discloses a sterilizing and antiviral antifouling aquaculture cage. The net is made of fibers containing polymer-assembled high-efficiency sterilizing and antiviral antifouling masterbatch, which helps reduce bacterial growth on the aquaculture net and improve the safety of the aquaculture process. However, the patent uses functional fillers such as antibacterial masterbatch and polymer antifouling additives and polymer resins to construct a composite matrix material by physical blending. This composite matrix material is prone to phase separation, and the material has not been tested and verified for its antibacterial properties. Summary of the Invention

[0004] Purpose of the invention: The purpose of the present invention is to address the deficiencies in the prior art and provide a self-cleaning, antibacterial marine antifouling coating, preparation method and application, which can resist biological attachment, pathogens and environmental corrosion for a long time without relying on harmful chemicals such as heavy metals, has excellent superhydrophobicity, self-cleaning properties and photocatalytic activity, and can achieve long-term effective antifouling and antibacterial properties.

[0005] Technical solution: The antifouling coating intermediate of the present invention has a chemical formula of NH2CH2CH2CH2Si(OBiOCl)3; the structural formula of the intermediate is as follows:

[0006]

[0007] The present invention also provides a method for preparing an antifouling coating intermediate, comprising the following steps:

[0008] Step 1: Preparation of 3D-NF-BiOCl

[0009] Step 1.1: Weigh 4.85 g of Bi(NO3)3·5H2O and dissolve it in 200 mL of 1 mol / L nitric acid solution under ultrasonic dispersion conditions.

[0010] Step 1.2: After the bismuth nitrate is completely dissolved, add the prepared hydrochloric acid solution dropwise to the conical flask and stir with a magnetic stirrer for 2 hours; the concentration of the hydrochloric acid solution is 6 mol / L;

[0011] Step 1.3: The resulting suspension was centrifuged three times at 8000 rpm for a total of 10 min. The suspension was then rinsed with deionized water and dried at 60°C for 6 h to obtain three-dimensional flower-shaped BiOCl microspheres (3D-NF-BiOCl) with a diameter of 15.79 μm.

[0012] Step 2: Preparation of 3D-NFG-BiOCl

[0013] Step 2.1. Weigh 9.7014 g of Bi(NO3)3·5H2O solid and pour it into a conical flask containing 40 mL of ethylene glycol;

[0014] Step 2.2: Dissolve under ultrasonic dispersion until the solution is clear and then add 1.5910 g of potassium chloride solid;

[0015] Step 2.3: After the solution in step 2.2 is clarified, add 20 mL of deionized water dropwise to the conical flask and continue stirring for 1 h.

[0016] Step 2.4: After 1 hour, centrifuge the suspension at 8000 rpm for three times for a total of 10 minutes to separate the 3D-NFG-BiOCl from the suspension. Rinse the suspension three times with deionized water and then dry it in an oven at 60°C for 6 hours to obtain three-dimensional wrinkled BiOCl nanospheres, i.e., 3D-NFG-BiOCl.

[0017] Step 3: Preparation of antifouling coating intermediates

[0018] Step 3.1: Place 30 mL of anhydrous ethanol and 225 μL of 3-aminopropyltriethoxysilane crosslinker in a conical flask.

[0019] Step 3.2: Add 0.75 g of 3D-NF-BiOCl microspheres and 3D-NFG-BiOCl nanospheres at a mass ratio of 1:1 to a conical flask;

[0020] Step 3.3: After the 3D-NF-BiOCl microspheres and 3D-NFG-BiOCl nanospheres are evenly dispersed, the conical flask is placed in a 60° C. water bath for activation for 1 h to obtain an antifouling coating intermediate.

[0021] The ethoxy groups of 3-aminopropyltriethoxysilane (APTES), a crosslinker, react with hydroxyl groups on the surfaces of 3D-NFG-BiOCl and 3D-NF-BiOCl in water, forming Si-O-Bi bonds, thus achieving the initial link between APTES and BiOCl. The hydrolyzed ethoxy groups then react with amino groups on the nylon mesh surface to form NO-Si bonds, thus enabling the grafting of 3D-NFG-BiOCl and 3D-NF-BiOCl onto the nylon mesh surface. The synergistic effect of these three substances, due to the non-toxicity and excellent photocatalytic activity of BiOCl, the nano-SiO2 with its nano-spherical protrusions and resistance to extreme conditions, and the excellent properties of silicone resins such as low surface energy, hydrophobicity, antifouling properties, and high elasticity, imparts to the nylon mesh properties such as weather resistance, self-cleaning, superhydrophobicity, antibacterial properties, and antifouling properties, ultimately achieving the goal of highly effective antifouling and antibacterial nylon mesh.

[0022] The invention provides a self-cleaning antibacterial marine antifouling paint, the main component of which is the antifouling paint intermediate.

[0023] Furthermore, the antifouling coating further comprises polydimethylsiloxane, a curing agent and SiO2; the mass ratio of the antifouling coating intermediate, polydimethylsiloxane, curing agent and SiO2 is 1.5 to 3:2:0.2:0.7.

[0024] The invention provides a method for preparing a self-cleaning antibacterial marine antifouling coating. The method comprises the following steps: mixing an antifouling coating intermediate with 1g of polydimethylsiloxane, 0.1g of a curing agent and 0.55g of SiO2, and performing ultrasonic dispersion for 10 minutes to obtain a uniformly dispersed self-cleaning antibacterial marine antifouling coating.

[0025] A self-cleaning, antibacterial, and antifouling marine coating is applied to a nylon net. The prepared self-cleaning, antibacterial, and antifouling marine coating is poured into a spray gun and sprayed evenly onto the surface of a 50 mm x 50 mm nylon net sample (NM). After spraying, the nylon net is placed in an oven at 60°C for 1 hour, or at room temperature (25°C) for 24 hours to obtain a nylon net with self-cleaning, super-hydrophobic, antibacterial, and antifouling functions.

[0026] This study prepared two BiOCl surface morphologies (3D-NF-BiOCl and 3D-NFG-BiOCl) using two simple methods. These BiOCl surfaces were grafted onto nylon mesh surfaces using a 3-aminopropyltriethoxysilane crosslinker (APTES). Further modification with SiO2 and polydimethylsiloxane (PDMS) resulted in a superhydrophobic 3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh with photocatalytic bactericidal properties. The materials were characterized using various methods, including surface wettability and self-cleaning tests, contact angle tests, thermodynamic stability tests, chemical stability tests, and photocatalytic antibacterial tests, comprehensively examining the self-cleaning and antibacterial properties of the 3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh.

[0027] Beneficial effects: Compared with the prior art, the advantages of the present invention are:

[0028] (1) The present invention provides an antifouling coating intermediate, wherein the ethoxy group of a 3-aminopropyltriethoxysilane crosslinker is activated and hydrolyzed in water, and then reacts with the hydroxyl groups on the surfaces of 3D-NFG-BiOCl and 3D-NF-BiOCl to form Si-O-Bi bonds, thereby achieving a preliminary connection between APTES and BiOCl. Subsequently, the hydrolyzed ethoxy group continues to react with the amino groups on the surface of the nylon mesh to form N-O-Si bonds, thereby achieving the purpose of APTES grafting 3D-NFG-BiOCl and 3D-NF-BiOCl to the surface of the nylon mesh.

[0029] (2) The present invention provides a self-cleaning antibacterial marine antifouling coating, which has the properties of super-hydrophobicity, self-cleaning, corrosion resistance, stain resistance and antibacterial properties for nylon nets. It can be applied not only to the surface of nylon nets, but also to the surface of various nylon materials in seawater.

[0030] (3) The maximum contact angle (WCA) of the nylon mesh prepared by the present invention reaches 154.03°, and the water droplet can maintain a complete spherical shape on the surface of the nylon mesh;

[0031] (4) The nylon mesh prepared by the present invention has corrosion resistance. When solutions with a pH of 1 and a pH of 14 are dropped on the surface of the material, the water droplets can still maintain a complete spherical shape for a long time.

[0032] (5) The nylon mesh prepared by the present invention has antibacterial properties. Since BiOCl has a photocatalytic antibacterial function, the prepared nylon mesh has an excellent rapid antibacterial effect under the condition of 20 minutes of light irradiation, with an antibacterial effect of up to 99.7% against Staphylococcus aureus and up to 99.9% against Escherichia coli. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the synthesis process of 3D-NF-BiOCl;

[0034] Figure 2 This is the synthesis process of 3D-NFG-BiOCl;

[0035] Figure 3 This is the synthesis process of 3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh;

[0036] Figure 4 This is the reaction mechanism diagram of APTES grafted BiOCl;

[0037] Figure 5 It is a schematic diagram of the contact angle of the nylon mesh surface;

[0038] Figure 6 is the wettability of the droplet on the surface of 3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh;

[0039] Figure 7 is the wettability of the droplets at pH = 1 and pH = 14 on the surface of 3D-NF / NFG-BiOCl@SiO2@PDMS nylon material;

[0040] Figure 8 The wettability and self-cleaning properties of 3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh. DETAILED DESCRIPTION

[0041] The technical solution of the present invention is described in detail below with reference to the accompanying drawings, but the protection scope of the present invention is not limited to the embodiments.

[0042] Table 1 Chemical reagents and materials used in the examples

[0043]

[0044]

[0045] Example 1

[0046] The self-cleaning antibacterial marine antifouling coating is prepared by the following specific steps: Figure 3 and Figure 4As shown, 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), 0.75 g of 3D-NF-BiOCl microspheres, and 0.75 g of 3D-NFG-BiOCl microspheres were dispersed evenly in a conical flask and activated in a 60°C waterbath for 1 hour. After activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were added and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antibacterial, and marine antifouling coating. The prepared coating was poured into a spray gun and evenly sprayed onto the surface of a 50 mm × 50 mm nylon mesh (NM). After spraying, the mesh was placed in a 60°C oven for 1 hour to obtain a nylon mesh (3D-NF / NFG-BiOCl@SiO2@PDMS) with self-cleaning, superhydrophobic, antibacterial, and antifouling properties.

[0047] Example 2

[0048] A self-cleaning, antibacterial, and antifouling marine coating was prepared by mixing 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), and 0.75 g of 3D-NFG-BiOCl microspheres in a conical flask. The mixture was then uniformly dispersed and activated in a 60°C waterbath for 1 hour. Following activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antibacterial, and antifouling marine coating. The prepared coating was poured into a spray gun and evenly sprayed onto a 50 mm × 50 mm nylon mesh (NM). After spraying, the mesh was placed in an oven at 60°C for 1 hour to obtain a nylon mesh (3D-NF / NFG-BiOCl@SiO2@PDMS) with self-cleaning, superhydrophobic, antibacterial, and antifouling properties.

[0049] The difference between this embodiment and embodiment 1 is that only single-morphology 3D-NFG-BiOCl microspheres are added.

[0050] Example 3

[0051] A self-cleaning, antimicrobial, and antifouling marine coating was prepared by dispersing 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), 0.25 g of 3D-NF-BiOCl microspheres, and 0.75 g of 3D-NFG-BiOCl microspheres in a conical flask. The mixture was then activated in a 60°C water bath for 1 hour. After activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were weighed and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antimicrobial, and antifouling marine coating. The prepared coating was poured into a spray gun and evenly sprayed onto the surface of a 50mm×50mm nylon mesh (NM). After spraying, the nylon mesh was placed in an oven at 60°C for 1 hour to obtain a nylon mesh (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh) with self-cleaning, superhydrophobic, antibacterial and antifouling functions.

[0052] The difference between this embodiment and embodiment 1 is that the ratio of the added 3D-NF-BiOCl microspheres to the added 3D-NFG-BiOCl microspheres is 0.25:0.75.

[0053] Example 4

[0054] A self-cleaning, antimicrobial, and antifouling marine coating was prepared by dispersing 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), 0.5 g of 3D-NF-BiOCl microspheres, and 0.75 g of 3D-NFG-BiOCl microspheres in a conical flask. The mixture was then activated in a 60°C water bath for 1 hour. After activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were weighed and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antimicrobial, and antifouling marine coating. The prepared coating was poured into a spray gun and evenly sprayed onto the surface of a 50mm×50mm nylon mesh (NM). After spraying, the nylon mesh was placed in an oven at 60°C for 1 hour to obtain a nylon mesh (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh) with self-cleaning, superhydrophobic, antibacterial and antifouling functions.

[0055] The difference between this embodiment and embodiment 1 is that the ratio of the added 3D-NF-BiOCl microspheres to the added 3D-NFG-BiOCl microspheres is 0.25:0.75.

[0056] Example 5

[0057] A self-cleaning, antimicrobial, and antifouling marine coating was prepared by dispersing 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), 0.75 g of 3D-NF-BiOCl microspheres, and 0.5 g of 3D-NFG-BiOCl microspheres in a conical flask. The mixture was then activated in a 60°C water bath for 1 hour. After activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were weighed and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antimicrobial, and antifouling marine coating. The prepared coating was poured into a spray gun and evenly sprayed onto the surface of a 50mm×50mm nylon mesh (NM). After spraying, the nylon mesh was placed in an oven at 60°C for 1 hour to obtain a nylon mesh with self-cleaning, superhydrophobic, antibacterial and antifouling functions (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh).

[0058] The difference between this embodiment and embodiment 1 is that the ratio of the added 3D-NF-BiOCl microspheres to the added 3D-NFG-BiOCl microspheres is 0.75:0.5.

[0059] Example 6

[0060] A self-cleaning, antimicrobial, and antifouling marine coating was prepared by dispersing 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), 0.75 g of 3D-NF-BiOCl microspheres, and 0.25 g of 3D-NFG-BiOCl microspheres in a conical flask. The mixture was then activated in a 60°C water bath for 1 hour. After activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were weighed and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antimicrobial, and antifouling marine coating. The prepared coating was poured into a spray gun and evenly sprayed onto the surface of a 50mm×50mm nylon mesh (NM). After spraying, the nylon mesh was placed in an oven at 60°C for 1 hour to obtain a nylon mesh (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh) with self-cleaning, superhydrophobic, antibacterial and antifouling functions.

[0061] The difference between this embodiment and embodiment 1 is that the ratio of the added 3D-NF-BiOCl microspheres to the added 3D-NFG-BiOCl microspheres is 0.75:0.25.

[0062] Example 7

[0063] A self-cleaning, antibacterial, and antifouling marine coating was prepared by mixing 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), and 0.75 g of 3D-NFG-BiOCl microspheres in a conical flask. The mixture was then uniformly dispersed and activated in a 60°C waterbath for 1 hour. Following activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antibacterial, and antifouling marine coating. The prepared coating was poured into a spray gun and evenly sprayed onto the surface of a 50 mm × 50 mm nylon mesh (NM). After spraying, the mesh was placed in a 60°C oven for 1 hour to obtain a nylon mesh (3D-NF / NFG-BiOCl@SiO2@PDMS) with self-cleaning, superhydrophobic, antibacterial, and antifouling properties.

[0064] The difference between this embodiment and embodiment 1 is that only 0.75 g of 3D-NF-BiOCl microspheres are added.

[0065] Example 8

[0066] A self-cleaning, antimicrobial, and antifouling marine coating was prepared by dispersing 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), 0.75 g of 3D-NF-BiOCl microspheres, and 0.75 g of 3D-NFG-BiOCl microspheres in a conical flask. The mixture was then activated in a 60°C water bath for 1 hour. After activation, 1 g of polydimethylsiloxane (PDMS), 0.1 g of curing agent, and 0.35 g of SiO2 were weighed and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning, antimicrobial, and antifouling marine coating. The prepared coating was poured into a spray gun and evenly sprayed onto the surface of a 50mm×50mm nylon mesh (NM). After spraying, the nylon mesh was placed at room temperature (25°C) for 24 hours to obtain a nylon mesh (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh) with self-cleaning, superhydrophobic, antibacterial and antifouling functions.

[0067] The difference between this embodiment and embodiment 1 is that the nylon net after spraying is placed at room temperature (25° C.) for 24 hours.

[0068] Comparative Example 1:

[0069] Nylon netting that has not been painted with self-cleaning antimicrobial marine antifouling paint.

[0070] Test example:

[0071] 1. Superhydrophobicity: The present invention uses an SZ-CAMC11 contact angle meter to measure the static water contact angles of the surfaces of the samples of the comparative example and Examples 1 to 8, thereby investigating and studying the wetting properties of the material surfaces.

[0072] 2. Seawater corrosion resistance: Place the sample in a simulated seawater environment for 1 day, 5 days, 10 days, 20 days, 30 days, 40 days, and 50 days, and observe the surface condition of the sample. If there is no blistering, powdering, obvious loss of gloss, discoloration or other pathological phenomena, it can be evaluated as "no abnormality", referred to as "none";

[0073] 3. Resistance to marine biofouling: Referring to the national standard "Test method for shallow sea immersion of antifouling paint samples" (GB / T5370-2007), the experimental net prepared in Example 3 and a blank control were placed in a seawater environment for 1 day, 5 days, 10 days, 20 days, 30 days, 40 days, and 50 days, respectively, to test the antifouling performance of the self-cleaning antibacterial nylon net of the present invention.

[0074] 4. Antibacterial property: According to GB / T 20944 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method", antibacterial tests were conducted on the experimental net prepared in Example 3 and a blank control sample to test the antibacterial rate of the nylon net.

[0075] The super-hydrophobicity test results of Examples 1 to 8 are shown in Table 2:

[0076] Table 2 Test results of super hydrophobicity of Example 1-Example 8

[0077] sample hydrophobic angle Example 1 154.03° Example 2 146.094° Example 3 150.907° Example 4 152.543° Example 5 151.261° Example 6 149.178° Example 7 142.758° Example 8 154.03° Comparative Example 61.024°

[0078] From the above table, it can be seen that the nylon mesh of the present invention has excellent super hydrophobic properties. Figure 5 As shown, the contact angle of Example 1 is 154.03°. And by comparing the data in Table 2, it can be seen that during the spray gun coating process, room temperature curing and heating curing only affect the curing time, and do not affect the curing effect.

[0079] Table 3 Comparison of curing processes

[0080] sample hydrophobic angle Curing time (h) Example 3 154.03 1 Example 8 153.98 24

[0081] The test results of seawater corrosion resistance are shown in the following 4 tables:

[0082] Table 4 Seawater corrosion resistance test results

[0083]

[0084] As shown in Table 4 above, the nylon net of the present invention has excellent salt water corrosion resistance. After being immersed in sea water for a long time, no spots are produced on the surface of the nylon net. However, the surface of the nylon net of the comparative example is not resistant to salt water corrosion and yellow spots appear on the surface.

[0085] The test results of resistance to marine biofouling are shown in Table 5 below:

[0086] Table 5 Marine biofouling resistance test results

[0087]

[0088] As shown in Table 5 above, the nylon net of the present invention has excellent resistance to marine organism adhesion. It does not gain weight after being placed in simulated seawater for 40 days. In contrast, the nylon net of the comparative example begins to be heavily attached to marine organisms after about 20 days of use.

[0089] The antibacterial test results are shown in Table 6 below:

[0090] Table 6 Antibacterial test results

[0091]

[0092]

[0093] As shown in Table 6 above, the nylon mesh of the present invention has excellent photocatalytic antibacterial ability. Under the condition of 20 minutes of light irradiation, the antibacterial effect against Staphylococcus aureus is as high as 99.7%, and the antibacterial effect against Escherichia coli is as high as 99.9%.

[0094] Example 9 Preparation of 3D-NF-BiOCl

[0095] Process as Figure 1 As shown. 4.85g of Bi(NO₃)₃·5H₂O was weighed and dissolved in 200mL of prepared nitric acid solution (1mol / L) under ultrasonic dispersion conditions. Once the bismuth nitrate was completely dissolved, prepared hydrochloric acid solution (6mol / L) was added dropwise to the conical flask and stirred with a magnetic stirrer for 2 hours. The resulting suspension was centrifuged three times at 8000rpm (10 minutes total), rinsed with deionized water, and then dried at 60°C for 6 hours to obtain three-dimensional flower-shaped BiOCl microspheres (3D-NF-BiOCl) with a diameter of 15.79μm.

[0096] Example 10 Preparation of 3D-NFG-BiOCl

[0097] Process as Figure 2As shown. 9.7014g of Bi(NO3)3·5H2O solid was weighed and poured into a conical flask containing 40mL of ethylene glycol. After dissolving it under ultrasonic dispersion until the solution was clear, 1.5910g of potassium chloride solid was added. After the solution was clear, 20mL of deionized water was added dropwise to the conical flask and stirred continuously for 1h. After 1h, the suspension was centrifuged three times at 8000rpm to separate the 3D-NFG-BiOCl in the suspension. The suspension was then rinsed three times with deionized water and dried in an oven at 60℃ for 6h to obtain three-dimensional wrinkled BiOCl nanospheres (3D-NFG-BiOCl).

[0098] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes may be made to it in form and detail without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. A method for preparing an antifouling coating intermediate, wherein the chemical formula of the antifouling coating intermediate is NH2CH2CH2CH2Si(OBiOCl)3, characterized in that The steps include: Step 1: Preparation of 3D-NF-BiOCl Step 1.1, weigh an appropriate amount of Bi(NO3)3·5H2O and dissolve it in the prepared nitric acid solution under ultrasonic dispersion conditions; Step 1.2: After the bismuth nitrate is completely dissolved, add the prepared hydrochloric acid solution dropwise to the conical flask and stir with a magnetic stirrer for 2 hours; Step 1.3: The resulting suspension was centrifuged three times at 8000 rpm, rinsed with deionized water, and then dried at 60°C for 6 h to obtain three-dimensional flower-shaped BiOCl microspheres with a diameter of 15.79 μm, namely 3D-NF-BiOCl. Step 2: Preparation of 3D-NFG-BiOCl Step 2.

1. Weigh an appropriate amount of Bi(NO3)3·5H2O solid and pour it into a conical flask containing ethylene glycol; Step 2.2, dissolving under ultrasonic dispersion until the solution is clear, and then adding potassium chloride solid; Step 2.3: After the solution in step 2.2 is clarified, add deionized water dropwise to the conical flask and continue stirring for 1 h. Step 2.4: After 1 hour, the suspension was centrifuged three times at 8000 rpm to separate the 3D-NFG-BiOCl. The suspension was then rinsed three times with deionized water and dried in an oven at 60°C for 6 hours to obtain three-dimensional wrinkled BiOCl nanospheres, i.e., 3D-NFG-BiOCl. Step 3: Preparation of antifouling coating intermediates Step 3.1, weigh anhydrous ethanol and 3-aminopropyltriethoxysilane crosslinker into a conical flask; Step 3.2: Add 3D-NF-BiOCl microspheres and 3D-NFG-BiOCl nanospheres at a mass ratio of 1:1 into a conical flask; Step 3.3: After the 3D-NF-BiOCl microspheres and 3D-NFG-BiOCl nanospheres are evenly dispersed, the conical flask is placed in a 60° C. water bath for activation for 1 h to obtain an antifouling coating intermediate.

2. The method for preparing an antifouling coating intermediate according to claim 1, wherein: The structural formula of the intermediate is as follows:

3. A self-cleaning antibacterial marine antifouling coating, characterized by: The main component is the antifouling coating intermediate as claimed in claim 1.

4. The self-cleaning antibacterial marine antifouling coating according to claim 3, characterized in that: The antifouling coating further comprises polydimethylsiloxane, a curing agent and SiO2; the mass ratio of the antifouling coating intermediate, polydimethylsiloxane, curing agent and SiO2 is 1.5-3:2:0.2:0.

7.

5. A self-cleaning antibacterial marine antifouling coating according to claims 3 to 4, characterized in that: The antifouling coating intermediate was mixed with polydimethylsiloxane, a curing agent and SiO2, and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning antibacterial marine antifouling coating.

6. An application of the self-cleaning antibacterial marine antifouling coating according to claims 3 to 4, characterized in that: Application of the self-cleaning antibacterial marine antifouling coating sprayed on the surface of nylon material.

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