Self-cleaning antibacterial marine antifouling paint as well as preparation method and application thereof

Abstract

The invention provides a self-cleaning antibacterial marine antifouling coating as well as a preparation method and application of the self-cleaning antibacterial marine antifouling coating, ethyoxyl of APTES is activated and hydrolyzed in water and then reacts with hydroxyl groups on the surfaces of 3D-NFG-BiOCl and 3D-NF-BiOCl to generate Si-O-Bi bonds, so that preliminary connection of APTES and BiOCl is realized. The preparation method comprises the following steps: hydrolyzing an amino group on the surface of a nylon material to generate an ethyoxyl group, then continuously reacting the hydrolyzed ethyoxyl group with the amino group on the surface of the nylon material to generate an N-O-Si bond, so that the purpose that 3D-NFG-BiOCl and 3D-NF-BiOCl are grafted to the surface of the nylon material by APTES is achieved, BiOCl is non-toxic and has relatively good photocatalytic activity, and nano SiO2 has a nano spherical protruding structure and has the capability of resisting extreme conditions; the organic silicon resin has excellent properties of low surface energy, hydrophobicity, pollution resistance, high elasticity and the like, and the nylon material has the properties of weather resistance, self-cleaning, super-hydrophobicity, bacteria resistance, pollution resistance and the like through the synergistic effect of the three substances, so that the purpose of efficient pollution resistance and bacteria resistance of the nylon netting is achieved.

Description

Technical Field

[0001] The 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, which are used to surround a certain water space, confine aquaculture objects such as fish and shrimp, prevent them from escaping, and resist attacks from natural enemies. The main material is 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 tends to be eutrophic, which may eventually cause the farmed seafood to die due to lack of oxygen or environmental deterioration. In addition, the marine aquaculture industry also faces severe challenges from pathogenic bacterial infections. Once a bacterial outbreak occurs, it will spread rapidly like an avalanche, triggering a series of chain negative effects and dealing a heavy blow to the aquaculture industry. The above-mentioned risks of marine organism attachment and bacterial infection are important issues that cannot be ignored in marine aquaculture.

[0003] Chinese patent CN 109651940 A discloses an antifouling coating for aquaculture cages, which uses the network structure of the resin in the coating and the degradation rate of the resin to control the storage and release of the antifouling agent, thereby playing an antifouling role; however, in order to reduce the impact of biological fouling on the marine aquaculture industry, the patent adopts an antifouling coating containing heavy metals (cuprous oxide, etc.). Although these measures are effective in the short term, the heavy metals contained therein 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 bactericidal and antiviral antifouling aquaculture cage, and the net uses fibers containing polymer-assembled high-efficiency bactericidal and antiviral antifouling masterbatch, which helps to reduce the growth of bacteria on the aquaculture net and improve the safety of the aquaculture process. However, the patent uses functional fillers such as antibacterial masterbatch, 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 to provide a self-cleaning, antibacterial marine antifouling coating, a preparation method and an application thereof, 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, dissolve it in 200 mL of prepared nitric acid solution under ultrasonic dispersion conditions, the concentration of the nitric acid solution is 1 mol / L;

[0010] Step 1.2, after the bismuth nitrate is completely dissolved, add the prepared hydrochloric acid solution dropwise into 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 suspension obtained after the reaction was placed in a centrifuge, centrifuged three times at 8000 rpm for a total of 10 min, washed 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;

[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, dissolving under ultrasonic dispersion until the solution is clear, and then adding 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 into the conical flask and continue stirring for 1 h;

[0016] Step 2.4, after 1 hour, centrifuge at 8000 rpm for three times for a total of 10 minutes to separate the 3D-NFG-BiOCl in the suspension, rinse with deionized water three times, and then dry in an oven at 60°C for 6 hours to obtain three-dimensional wrinkled BiOCl nanospheres, namely 3D-NFG-BiOCl;

[0017] Step 3: Preparation of antifouling coating intermediates

[0018] Step 3.1, measure 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 in a mass ratio of 1:1 into 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] 3-aminopropyl triethoxysilane crosslinker, that is, the ethoxy group of APTES is activated and hydrolyzed in water to react with the hydroxyl groups on the surface of 3D-NFG-BiOCl and 3D-NF-BiOCl to form Si-O-Bi bonds, thereby achieving the initial connection between APTES and BiOCl. Then the hydrolyzed ethoxy group continues to react with the amino group on the surface of the nylon net to form NO-Si bonds, thereby achieving the purpose of APTES grafting 3D-NFG-BiOCl and 3D-NF-BiOCl onto the surface of the nylon net. Since BiOCl is non-toxic and has good photocatalytic activity, nano-SiO2 has a nano-spherical protruding structure and has the ability to resist extreme conditions, and silicone resins have excellent properties such as low surface energy, hydrophobicity, antifouling and high elasticity, the synergistic effect of these three substances makes the nylon net have weather resistance, self-cleaning, super hydrophobicity, antibacterial, antifouling and other properties, thereby achieving the purpose of high-efficiency antifouling and antibacterial nylon net.

[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 also includes polydimethylsiloxane, a curing agent and SiO2; the mass ratio of the antifouling coating intermediate, polydimethylsiloxane, a 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 antifouling coating intermediate is mixed with 1g of polydimethylsiloxane, 0.1g of a curing agent and 0.55g of SiO2, and ultrasonically dispersed for 10 minutes to obtain a uniformly dispersed self-cleaning antibacterial marine antifouling coating.

[0025] A self-cleaning antibacterial marine antifouling coating is used for spraying nylon nets. The self-cleaning antibacterial marine antifouling coating prepared above is poured into a spray gun and sprayed evenly onto the surface of a nylon net sample (NM) of 50 mm × 50 mm in size. 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] The present invention prepares two types of BiOCl (3D-NF-BiOCl and 3D-NFG-BiOCl) with two simple methods and grafts them on the surface of nylon mesh through 3-aminopropyltriethoxysilane crosslinker (APTES), and further modifies them with SiO2 and polydimethylsiloxane (PDMS) to prepare a super-hydrophobic 3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh with photocatalytic bactericidal ability. In addition, the material is characterized in many ways: surface wettability and self-cleaning test, contact angle test, thermodynamic stability test, chemical stability test and photocatalytic antibacterial test, and the self-cleaning antibacterial 3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh is comprehensively investigated.

[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 to react 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 a nylon net to form N-O-Si bonds, thereby achieving the purpose of APTES grafting 3D-NFG-BiOCl and 3D-NF-BiOCl onto the surface of a nylon net;

[0029] (2) The self-cleaning antibacterial marine antifouling coating provided by the present invention has the properties of super hydrophobicity, self-cleaning, corrosion resistance, stain resistance and antibacterial. It can be applied not only to the surface of nylon nets, but also to the surfaces 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 a solution with a pH of 1 or a pH of 14 is dropped on the surface of the material, the water drop 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, under the condition of light irradiation for 20 minutes, the prepared nylon mesh has excellent rapid antibacterial effect, 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 It is the synthesis process of 3D-NF-BiOCl;

[0034] Figure 2 It 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, 30mL of anhydrous ethanol, 225μL of 3-aminopropyltriethoxysilane crosslinker (APTES), 0.75g of 3D-NF-BiOCl microspheres and 0.75g of 3D-NFG-BiOCl microspheres were dispersed in a conical flask and activated in a water bath at 60°C for 1h. After activation, 1g of polydimethylsiloxane (PDMS), 0.1g of curing agent and 0.35g of SiO2 were weighed and ultrasonically dispersed for 10min to obtain a uniformly dispersed self-cleaning antibacterial marine antifouling 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 1h to obtain a nylon mesh with self-cleaning, superhydrophobic, antibacterial and antifouling functions (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh).

[0047] Example 2

[0048] The self-cleaning antibacterial marine antifouling coating was prepared in the following steps: 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES), and 0.75 g of 3D-NFG-BiOCl microspheres were dispersed evenly in a conical flask and activated in a water bath at 60 ° C for 1 h. 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 min to obtain a uniformly dispersed self-cleaning antibacterial marine antifouling coating. The prepared coating was poured into a spray gun and sprayed evenly onto the surface of a 50 mm × 50 mm nylon mesh (NM). After spraying, the nylon mesh was placed in an oven at 60 ° C for 1 h to obtain a nylon mesh with self-cleaning, superhydrophobic, antibacterial, and antifouling functions (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh).

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

[0050] Example 3

[0051] The self-cleaning antibacterial marine antifouling coating was prepared in the following specific steps: 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 were dispersed evenly in a conical flask and activated in a water bath at 60°C 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 antibacterial 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 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 3D-NFG-BiOCl microspheres is 0.25:0.75.

[0053] Example 4

[0054] The self-cleaning antibacterial marine antifouling coating was prepared in the following specific steps: 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 were dispersed evenly in a conical flask and activated in a water bath at 60°C 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 antibacterial 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 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 3D-NFG-BiOCl microspheres is 0.25:0.75.

[0056] Example 5

[0057] The self-cleaning antibacterial marine antifouling coating was prepared by the following specific steps: 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 were dispersed evenly in a conical flask and activated in a water bath at 60°C 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 antibacterial 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 nylon mesh was placed in an oven at 60 °C for 1 hour to obtain a nylon mesh with self-cleaning, super-hydrophobic, antibacterial and anti-fouling 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 3D-NFG-BiOCl microspheres is 0.75:0.5.

[0059] Example 6

[0060] The self-cleaning antibacterial marine antifouling coating was prepared in the following specific steps: 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 were dispersed evenly in a conical flask and activated in a water bath at 60°C 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 antibacterial 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 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] The self-cleaning antibacterial marine antifouling coating was prepared in the following steps: 30 mL of anhydrous ethanol, 225 μL of 3-aminopropyltriethoxysilane crosslinker (APTES) and 0.75 g of 3D-NFG-BiOCl microspheres were dispersed evenly in a conical flask and activated in a water bath at 60 ° C for 1 h. 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 min to obtain a uniformly dispersed self-cleaning antibacterial marine antifouling coating. The prepared coating was poured into a spray gun and sprayed evenly onto the surface of a 50 mm × 50 mm nylon mesh (NM). After spraying, the nylon mesh was placed in an oven at 60 ° C for 1 h to obtain a nylon mesh with self-cleaning, superhydrophobic, antibacterial and antifouling functions (3D-NF / NFG-BiOCl@SiO2@PDMS nylon mesh).

[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] The self-cleaning antibacterial marine antifouling coating was prepared in the following specific steps: 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 water bath at 60°C 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 antibacterial 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 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 nets not painted with self-cleaning antimicrobial marine antifouling paint.

[0070] Test example:

[0071] 1. Superhydrophobicity: The present invention uses a 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 surface.

[0072] 2. Seawater corrosion resistance: Place the samples 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 conditions of the samples. If there is no blistering, powdering, obvious loss of gloss, discoloration, or other pathological phenomena, it can be evaluated as "no abnormality", or "none" for short;

[0073] 3. Resistance to marine biological attachment: Referring to the national standard "Shallow Sea Immersion Test Method for Antifouling Paint Samples" (GB / T5370-2007), the experimental net prepared in Example 3 and the blank control group 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", the experimental net prepared in Example 3 and the blank control ratio were subjected to antibacterial test to test the antibacterial rate of the nylon net.

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

[0076] Table 2 Superhydrophobicity test results 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] It can be seen from the above table 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 through the comparison of the data in Table 2, it can be seen that in 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] It can be seen from Table 4 above that the nylon net of the present invention has excellent resistance to salt water corrosion. After being immersed in sea water for a long time, no spots are produced on the surface of the nylon net; while 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, the nylon net of the present invention has excellent resistance to marine organism attachment and does not gain weight after being placed in simulated seawater for 40 days; while the comparative example begins to be attached with a large number of marine organisms after about 20 days of use.

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

[0090] Table 6 Antibacterial test results

[0091]

[0092]

[0093] It can be seen from Table 6 above that the nylon mesh of the present invention has excellent photocatalytic antibacterial ability. Under the condition of light irradiation for 20 minutes, the antibacterial effect on Staphylococcus aureus is as high as 99.7%, and the antibacterial effect on Escherichia coli is as high as 99.9%.

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

[0095] Process Figure 1 As shown. Weigh 4.85g of Bi(NO3)3·5H2O and dissolve it in 200mL of prepared nitric acid solution (1mol / L) under ultrasonic dispersion. When bismuth nitrate is completely dissolved, add prepared hydrochloric acid solution (6mol / L) dropwise into a conical flask and stir with a magnetic stirrer for 2h. The suspension obtained after the reaction is placed in a centrifuge, centrifuged three times at 8000rpm (a total of 10min), washed with deionized water, and then dried at 60℃ for 6h 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 Figure 2As shown. Weigh 9.7014g of Bi(NO3)3·5H2O solid and pour it into a conical flask containing 40mL of ethylene glycol. Dissolve it under ultrasonic dispersion until the solution is clear, then add 1.5910g of potassium chloride solid. After the solution is clear, add 20mL of deionized water dropwise into the conical flask and stir for 1h. After 1h, centrifuge it three times at 8000rpm to separate the 3D-NFG-BiOCl in the suspension, rinse it three times with deionized water, and then dry it 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 in form and details may be made without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. An antifouling coating intermediate, characterized in that: The chemical formula of the intermediate is NH2CH2CH2CH2Si(OBiOCl)3; the structural formula of the intermediate is as follows:

2. A method for preparing an antifouling coating intermediate, 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 into the conical flask and stir with a magnetic stirrer for 2 hours; Step 1.3, the suspension obtained after the reaction was placed in a centrifuge, centrifuged three times at 8000 rpm, washed with deionized water, and then dried at 60°C for 6 hours 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 into the conical flask and continue stirring for 1 h; Step 2.4, after 1 hour, centrifuge at 8000 rpm for three times to separate the 3D-NFG-BiOCl in the suspension, rinse with deionized water three times, and then dry in an oven at 60°C for 6 hours to obtain three-dimensional wrinkled BiOCl nanospheres, namely 3D-NFG-BiOCl; Step 3: Preparation of antifouling coating intermediates Step 3.1, measure anhydrous ethanol and 3-aminopropyltriethoxysilane crosslinking agent into a conical flask; Step 3.2, adding 3D-NF-BiOCl microspheres and 3D-NFG-BiOCl nanospheres in 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.

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

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

7.

5. A method for preparing a self-cleaning antibacterial marine antifouling coating, characterized in that: The antifouling coating intermediate is 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. A self-cleaning antibacterial marine antifouling coating as claimed in claims 3 to 4, characterized in that: The application of the self-cleaning antibacterial marine antifouling coating sprayed on the surface of nylon material.

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