Self-driven composite marine antifouling coating and preparation method thereof

Abstract

The invention discloses a self-driven composite marine antifouling coating and a preparation method thereof. The self-driven composite marine antifouling coating comprises a base material, a copper electrode plate and an antifouling coating from bottom to top in sequence, the base material and the copper electrode plate form a friction nano generator; the base material is a glass base material. The preparation method comprises the following steps: respectively preparing the antifouling coating, the glass substrate and the copper electrode plate, and then sequentially adhering together; the invention has the advantages of good dispersibility and better heat-conducting property. According to the invention, the friction nano-generator is formed by the glass substrate and the copper electrode plate, the anti-fouling coating prepared in a matched manner is combined, wave energy near a waterline is collected through the friction nano-generator, and a stable double-charge layer at a contact interface of the coating and water is interfered by a variable electric field formed around the underwater electrode wire; therefore, the formation of a biological membrane in an initial stage is inhibited, and the purpose of effectively hindering the formation of biological pollution is achieved; the antifouling paint has the advantages of being good in antifouling performance and free of environmental pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of antifouling coatings, in particular to a self-driven composite marine antifouling coating and a preparation method thereof. Background Art

[0002] Marine fouling organisms attached and growing on underwater marine equipment will cause a series of adverse effects. With the development of new antifouling technologies and the increasingly strict environmental protection regulations, marine antifouling technologies are developing towards the direction of strong antifouling ability, simple process and environmental friendliness. New environmentally friendly antifouling technologies such as degradable self-polishing antifouling materials, drag-reducing antifouling materials and bionic antifouling materials based on natural antifouling agents have received more and more attention. The emergence of new antifouling technologies such as electrochemical antifouling and nanotechnology antifouling not only solves some problems of traditional marine antifouling materials such as poor broad-spectrum performance and short validity period, but also increases the types of marine antifouling coatings, and has become a breakthrough point for researching new marine antifouling coatings and an important development direction in the future.

[0003] In recent years, it has been found that voltage stimulation can generate wrinkles on the polymer surface, and the formed micro-deformations can effectively drive microorganisms to detach from the attached substrate, playing an antifouling role in the initial stage of biofouling formation. Other electrochemical methods can form irreversible pores on the cell membrane by using another high-frequency (up to 1000 Hz) strong electric field (1-100 kV / cm), so that the cells are lysed to kill microorganisms. The high electric potential (hundreds of volts) generated by a hydrodynamically driven triboelectric nanogenerator can effectively prevent the attachment of microorganisms in the electric field coverage area, demonstrating the feasibility of the self-driven anti-bioadhesion strategy by applying voltage. However, the high electric field strength and full electrode coverage in this strategy pose high requirements for electrode design and system integration.

[0004] Research shows that triboelectric nanogenerators can directly and efficiently convert mechanical energy in low-frequency random motions at the micro- and nano-scales into electrical energy, and have many advantages such as diverse material selection, low cost, and flexible device structure, and have broad application prospects in multi-disciplinary fields such as materials, information, electronics, machinery, and transportation. Someone successfully prepared a solid-liquid contact triboelectric nanogenerator by collecting the electric potential generated by water waves, providing a continuous low-frequency pulsed electric field on the substrate surface, which can destroy the inherent stable double-charge layer on the substrate surface, and inhibit the formation of the biofouling conditioning film from the source, realizing active anti-biofouling. This triboelectric nanogenerator directly uses copper wires to generate a changing electric field on the underwater substrate surface. Although it can effectively prevent the deposition of pollutants, the metal wires are prone to corrosion and other problems when immersed in water for a long time. Such anti-biofouling technologies are very effective, but due to the complexity of electrical equipment, issues such as how to achieve large-scale implementation and reduce costs remain to be solved.

[0005] Regarding the problem of marine biofouling, the prepared antifouling coatings mainly focus on preventing marine biofouling through the gradual leaching of antifouling agents in the paint film. However, the released substances have the problem of polluting the marine environment due to their ability to inhibit fouling organisms.

[0006] Therefore, developing environmentally friendly marine antifouling coatings is an urgent problem to be solved. Summary of the Invention

[0007] The purpose of the present invention is to provide a self-driven composite marine antifouling coating and a preparation method. The present invention has the advantages of good antifouling performance and no environmental pollution.

[0008] The technical solution of the present invention: A self-driven composite marine antifouling coating, which includes a substrate, a copper electrode sheet, and an antifouling coating from bottom to top in sequence; the substrate and the copper electrode sheet form a triboelectric nanogenerator; the substrate is a glass substrate.

[0009] A preparation method of a self-driven composite marine antifouling coating, the preparation steps of the antifouling coating are as follows:

[0010] A1. Dilute and dissolve to prepare raw material A with toluene. Raw material A includes butyl methacrylate, azobisisobutyronitrile, and toluene with a mass ratio of 60:1:100.

[0011] A2. Take half of the mass of raw material A, and add raw material A, isopropanol, and acetone to a 500 mL four-necked round-bottom flask with a reflux device in sequence according to a mass ratio of 3:1:6. Add methyl vinyl MQ silicone resin to the four-necked round-bottom flask and stir and react at 55 °C for 1 h; the inside of the four-necked round-bottom flask is under N2 atmosphere; the addition amount of methyl vinyl MQ silicone resin is 30%-50%.

[0012] A3. Use an LSP022B micro-injection pump to gradually add the remaining raw material A to the four-necked round-bottom flask within 30 min, and then react for 2.5 h; after the reaction ends, obtain a reaction product.

[0013] A4. Transfer the reaction product to a stoppered triangular flask and seal it at 25 °C for 24 h to obtain a statically sealed product.

[0014] A5. Take out the statically sealed product, wash it with ethanol at least three times, and after the ethanol is filtered and volatilized, obtain a white gel substance; the white gel substance is the finished acrylic-MQ silicone resin (AMQ).

[0015] In the foregoing preparation method of a self-driven composite marine antifouling coating, the preparation steps of the triboelectric nanogenerator are as follows:

[0016] B1. Use a 10 cm × 10 cm glass as the substrate, and ultrasonically clean it in acetone, absolute ethanol, and deionized water for 5 minutes in sequence. After cleaning, blow dry the moisture remaining on the substrate surface with nitrogen to obtain the glass substrate;

[0017] B2. Prepare a copper electrode sheet with a micro-nano rough surface. Ultrasonically rinse the copper sheet with acetone, alcohol, and deionized water in sequence and then dry it. Place it in an etching solution prepared with 0.5 - 3 mol / L sodium hydroxide and 0.05 - 0.5 mol / L ammonium persulfate, and soak it for 15 minutes, 30 minutes, 1 hour, 2 hours, and 4 hours respectively. Then wash the copper sheet with deionized water and dry it to obtain the copper electrode sheet;

[0018] B3. Use a magnetic stirrer to stir equal masses of acrylic-MQ silicone resin and xylene in a sealed reagent bottle at 200 rpm / min for 15 minutes. Control the stirring temperature at 50°C. Add phenylmethyl silicone oil and 2-hydroxyethyl methacrylate phosphate in sequence and stir for 15 minutes to prepare a brushable coating; the mass components of the acrylic-MQ silicone resin, phenylmethyl silicone oil, and 2-hydroxyethyl methacrylate phosphate are 80 - 120:2 - 10:1 - 4;

[0019] B4. Cut the copper electrode sheet into a size of 8 cm × 8 cm, attach one side to the glass substrate, coat the other side with the brushable coating, and use conductive adhesive to attach and lead out wires at the edge of the copper electrode sheet;

[0020] B5. Seal the edge with waterproof tape.

[0021] Compared with the prior art, the present invention forms a triboelectric nanogenerator by using a glass substrate and a copper electrode sheet, combines a prepared anti-fouling coating, collects wave energy near the waterline through the triboelectric nanogenerator, and forms a changing electric field around the underwater part of the electrode wire to interfere with the stable double electric layer at the interface between the coating and water, thereby inhibiting the formation of biofilm in the initial stage, and further achieving the purpose of effectively hindering the formation of biological fouling;

[0022] Therefore, the present invention has the advantages of good anti-fouling performance and no environmental pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic diagram of the principle structure of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] The following further illustrates the present invention in conjunction with embodiments, but it shall not be used as a basis for limiting the present invention.

[0025] Example 1. A self-driven composite marine antifouling coating, comprising a substrate, a copper electrode sheet and an antifouling coating from bottom to top in sequence; the substrate and the copper electrode sheet form a triboelectric nanogenerator; the substrate is a glass substrate.

[0026] A preparation method of a self-driven composite marine antifouling coating, and the preparation steps of the antifouling coating are as follows:

[0027] A1. Dilute and dissolve raw material A with toluene. Raw material A includes butyl methacrylate, azobisisobutyronitrile and toluene with a mass ratio of 60:1:100.

[0028] A2. Take half of the mass of raw material A, and add raw material A, isopropanol and acetone to a 500 mL four-necked round-bottom flask with a reflux device in sequence according to a mass ratio of 3:1:6. Add methyl vinyl MQ silicone resin to the four-necked round-bottom flask and stir and react at 55 °C for 1 h; the inside of the four-necked round-bottom flask is in an N2 atmosphere; methyl vinyl MQ silicone resin accounts for 40% in the whole solution system.

[0029] A3. Use an LSP022B micro-injection pump to gradually add the remaining raw material A to the four-necked round-bottom flask within 30 min, and then react for 2.5 h; after the reaction ends, obtain a reaction product.

[0030] A4. Transfer the reaction product to a stoppered Erlenmeyer flask and seal it at 25 °C for 24 h to obtain a statically sealed product.

[0031] A5. Take out the statically sealed product, wash it with ethanol at least three times, and after the ethanol is filtered and volatilized, obtain a white gel substance; the white gel substance is the finished acrylic-MQ silicone resin.

[0032] A preparation method of a self-driven composite marine antifouling coating, and the preparation steps of the triboelectric nanogenerator are as follows:

[0033] B1. Use 10 cm × 10 cm glass as the substrate, ultrasonically clean it in acetone, absolute ethanol and deionized water in sequence for 5 min, and after cleaning, dry the residual moisture on the surface of the substrate with nitrogen to obtain a glass substrate.

[0034] B2. Prepare a copper electrode sheet with a micro-nano rough surface. Ultrasonically rinse the copper sheet with acetone, alcohol and deionized water in sequence and then dry it. Place it in an etching solution prepared from 2 mol / L sodium hydroxide and 0.3 mol / L ammonium persulfate, soak it for 1 h respectively, then wash the copper sheet with deionized water and dry it to obtain a copper electrode sheet.

[0035] B3. Use a magnetic stirrer to stir equal masses of acrylic acid-MQ silicone resin and xylene in a sealed reagent bottle at 200 rpm / min for 15 min. Control the stirring temperature at 50 °C. Sequentially add benzyl silicone oil and 2-hydroxyethyl methacrylate phosphate, and stir for 15 min to obtain a brushable coating. The acrylic acid-MQ silicone resin, benzyl silicone oil, and 2-hydroxyethyl methacrylate phosphate are in a mass component ratio of 100:6:2.

[0036] B4. Cut the copper electrode sheet into a size of 8 cm × 8 cm. Attach one side to the glass substrate, coat the other side with the brushable coating, and use conductive adhesive to attach and lead out wires at the edge of the copper electrode sheet.

[0037] B5. Seal the edge with waterproof tape.

[0038] When a substance is in a natural electrolyte, a stable double-charge layer will form at the interface where the two materials contact (such as the substrate surface and the coating surface). This charge layer can adsorb organic substances in the surrounding environment through electrostatic force, thus providing a material condition basis for the successful attachment of fouling organisms such as bacteria and diatoms. Existing research has shown that an alternating electric field with low frequency and low intensity (the peak value of the electric field intensity is about 10 V / m) can effectively inhibit the formation of biological fouling.

[0039] Example 2. A method for preparing a self-driven composite marine antifouling coating, with the rest of the content being the same as in Example 1, except that the soaking time in step B2 is 15 min.

[0040] Example 3. A method for preparing a self-driven composite marine antifouling coating, with the rest of the content being the same as in Example 1, except that the soaking time in step B2 is 2 h.

[0041] Example 4. A method for preparing a self-driven composite marine antifouling coating, with the rest of the content being the same as in Example 1, except that the soaking time in step B2 is 3 h.

[0042] Example 5. A method for preparing a self-driven composite marine antifouling coating, with the rest of the content being the same as in Example 1, except that in step A2, methyl vinyl MQ silicone resin accounts for 30% in the whole solution system.

[0043] Example 6. A method for preparing a self-driven composite marine antifouling coating, with the rest of the content being the same as in Example 1, except that in step A2, methyl vinyl MQ silicone resin accounts for 50% in the whole solution system.

[0044] Comparative experiment

[0045] Prepare a comparative example sample according to the coating preparation process. The preparation steps are as follows:

[0046] 1. Dissolve the reference resin in a solvent, the solvent is xylene, and the ratio of resin to solvent is 1:2;

[0047] 2. Spray the mixed solvent onto the surface of the substrate to prepare a comparative sample.

[0048] Comparative Example 1: The comparative resin is acrylic resin.

[0049] Comparative Example 2: The comparative resin is epoxy resin.

[0050] Comparative Example 3: The comparative resin is AMQ resin.

[0051] Water contact angle test

[0052] The contact angle of the coating surface after cleaning and drying was measured using Shanghai Zhongchen JC2000 contact angle meter. The size of the water droplet was controlled to 2μL. Three points were measured for each sample. The results are shown in the following table.

[0053]

[0054] Electrical performance test

[0055] When measuring the electrical performance output, the prepared TENG (friction nanogenerator coating) was fixed on a dedicated device that applied cyclic vibration. The output voltage of the TENG was detected using an oscilloscope, while the current was measured using a low-noise current preamplifier. The electric field strength was measured by an electromagnetic detection detector.

[0056]

[0057]

[0058] Biofilm adhesion assay

[0059] The antifouling performance of the coating was evaluated by the marine bacterial biofilm adhesion test. Six samples of each coating were painted on tinplate and immersed in 800mL fresh seawater (Yellow Sea, China) for 24 hours. Among them, three samples were gently rinsed with sterile deionized water to remove unsettled bacteria; the remaining samples were rinsed with sterile deionized water at 0.1MPa for 120s using a CB8LC high-pressure water gun, and then all samples were placed in a QNCJ-LED clean bench for drying and dehydration.

[0060] After the samples were dried naturally, 6 samples were stained with 0.5 wt % crystal violet solution for 15 min, and then the stained samples were taken out and dried. Subsequently, each sample was immersed in 45 mL of 36 wt % acetic acid solution and extracted for 10 min.

[0061] The extracted supernatant was placed in a quartz cuvette with an optical path of 1 cm, and the absorption intensity (OD590) at 590 nm was measured using a UV spectrophotometer to analyze the amount of biofilm adhesion on the coating surface.

[0062] The removal rate (R) of adherent fouling organisms was calculated by formula (1). Da and Db represent the OD590 values ​​of the rinse sample and the flush sample, respectively.

[0063]

[0064] Before the biofilm adhesion test, it is necessary to ensure that the upper and lower surfaces of the tinplate are coated with the preparation coating to ensure that seawater will not corrode the exposed tinplate. In addition, for experimental samples immersed in seawater for a long time, it is necessary to use ultraviolet germicidal lamps for regular sterilization (15min / day). For the biofilm adhesion test, the sample measured after curing for 8h is the sample at the exposure time of 0 days, and the sample measured after immersion in seawater for 30 days is the sample at the exposure time of 30 days.

[0065]

Claims

1. A self-driven composite marine antifouling coating, characterized in that: It includes a substrate, a copper electrode sheet, and an anti-fouling coating from bottom to top in sequence; the substrate and the copper electrode sheet form a triboelectric nanogenerator; the substrate is a glass substrate.

2. The preparation method of a self-driven composite marine antifouling coating according to claim 1, wherein The preparation steps of the anti-fouling coating are as follows: A1. Dilute and dissolve raw material A with toluene. Raw material A includes butyl methacrylate, azobisisobutyronitrile, and toluene with a mass ratio of 60:1:

100. A2. Take half of the mass of raw material A. Add raw material A, isopropanol, and acetone to a 500 mL four-neck round-bottom flask with a reflux device in sequence according to a mass ratio of 3:1:

6. Add methyl vinyl MQ silicone resin to the four-neck round-bottom flask and stir and react at 55 °C for 1 h; the inside of the four-neck round-bottom flask is in an N2 atmosphere. The addition amount of methyl vinyl MQ silicone resin is 30%-50%. A3. Use an LSP022B micro-injection pump to gradually drop the remaining raw material A into the four-neck round-bottom flask within 30 min, and then react for 2.5 h; after the reaction ends, obtain a reaction product. A4. Transfer the reaction product to a stoppered Erlenmeyer flask and seal it at 25 °C for 24 h to obtain a statically sealed product. A5. Take out the statically sealed product, wash it with ethanol at least three times, and after the ethanol is filtered and volatilized, obtain a white gel substance; the white gel substance is the finished acrylic-MQ silicone resin.

3. The preparation method of a self-driven composite marine antifouling coating according to claim 2, wherein The preparation steps of the triboelectric nanogenerator are as follows: B1. Use a 10 cm × 10 cm glass as the substrate, ultrasonically clean it in acetone, absolute ethanol, and deionized water for 5 min in sequence. After cleaning, blow dry the moisture remaining on the surface of the substrate with nitrogen to obtain a glass substrate. B2. Prepare a copper electrode sheet with a micro-nano rough surface. Ultrasonically rinse the copper sheet with acetone, alcohol, and deionized water in sequence and then dry it. Place it in an etching solution prepared from 0.5-3 mol / L sodium hydroxide and 0.05-0.5 mol / L ammonium persulfate, and soak it for 15 min, 30 min, 1 h, 2 h, 4 h respectively. Then wash the copper sheet with deionized water and dry it to obtain a copper electrode sheet. B3. Use a magnetic stirrer to stir equal masses of acrylic-MQ silicone resin and xylene in a sealed reagent bottle at 200 rpm / min for 15 min. Control the stirring temperature at 50 °C. Add benzyl silicone oil and 2-hydroxyethyl methacrylate phosphate in sequence and stir for 15 min to prepare a brushable coating; the acrylic-MQ silicone resin, benzyl silicone oil, and 2-hydroxyethyl methacrylate phosphate are in a mass component ratio of 80-120:2-10:1-4. B4. Cut the copper electrode sheet into a size of 8 cm × 8 cm, attach one side to the glass substrate, coat the other side with the brushable coating, and use conductive adhesive to attach it to the edge of the copper electrode sheet to lead out a wire. B5. Seal the edge with waterproof tape.

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