Multi-stage functional marine antifouling material, preparation method and application of multi-stage functional marine antifouling material to underwater monitoring equipment

Abstract

The invention relates to the technical field of marine antifouling materials, in particular to a multi-stage functional marine antifouling material, a preparation method and application of the multi-stage functional marine antifouling material to underwater monitoring equipment. The preparation method of the multistage functional marine antifouling material comprises the following steps: S1, ultrasonically dispersing a hydrophobic polymer particle material in an organic solvent, adding an alcohol-water mixed solvent, and ultrasonically forming a dispersion liquid; and S2, adding polyvinylpyrrolidone, polyvinyl alcohol and metal salt into the dispersion liquid, uniformly stirring, dropwise adding an acetamide solution, adding an alkaline solution, adding a reducing agent to obtain a mixed solution, continuously stirring at 50-80 DEG C for more than 2 hours, filtering, washing, drying in vacuum, and grinding to obtain the multi-stage functional marine antifouling material. According to the scheme, the hydrophobic polymer particle material is used as a matrix, the cuprous oxide-containing polyvinyl pyrrolidone-polyvinyl alcohol cross-linked polymer hydrogel is synthesized in situ on the surface, and the antifouling property and the stability of the material are improved by utilizing the synergistic effect of multiple components.

Description

Technical Field

[0001] The present invention relates to the technical field of marine antifouling materials, and particularly relates to a multi-functional marine antifouling material, a preparation method thereof, and an application thereof on underwater monitoring equipment. Background Art

[0002] Marine organisms are prone to attaching in large numbers on marine ships and underwater equipment, seriously affecting the ship's navigation and equipment performance, and it is necessary to regularly remove the marine organisms attached to the surface.

[0003] In addition to physical cleaning and electrochemistry antifouling, coating the outer surface of the ship and the surface of the equipment with an antifouling coating for preventing marine organisms is a simple and effective means. Among many marine antifouling coatings, hydrophobic materials and hydrophilic hydrogel materials both have effective antifouling properties. Due to the low surface energy of the material, the hydrophobic coating can reduce the adhesion ability of marine organisms and their secretions, and is easy to desorb under the influence of external forces, achieving an antifouling effect, but the antifouling performance for the surface of static equipment is not ideal. The hydrogel coating inhibits the adhesion of marine organisms on the surface of the equipment to achieve an antifouling effect by forming a dense water molecule layer on the surface. The limitation is that its water absorption and swelling reduce the mechanical stability of the coating. To achieve long-term and effective marine organism antifouling, it is urgent to develop a more efficient and stable marine antifouling coating. Summary of the Invention

[0004] The main object of the present invention is to provide a multi-functional marine antifouling material, a preparation method thereof, and an application thereof on underwater monitoring equipment, aiming to improve the technical problems that the static antifouling performance of the existing marine antifouling coatings is not ideal, or the mechanical stability of the coating is poor.

[0005] To achieve the above object, the present invention provides a preparation method of a multi-functional marine antifouling material, including the following steps:

[0006] S1. Ultrasonically disperse the hydrophobic polymer particle material in an organic solvent, then add an alcohol-water mixed solvent, and ultrasonically form a dispersion;

[0007] S2. Add polyvinylpyrrolidone, polyvinyl alcohol, and metal salt into the dispersion obtained in step S1 respectively, stir evenly, then dropwise add an acetamide solution, then add an alkaline solution and stir evenly, and then add a reducing agent to obtain a mixed solution. The mixed solution is continuously stirred at 50-80°C for more than 2 hours, and finally, after filtration, washing, vacuum drying, and grinding, the multi-functional marine antifouling material is obtained.

[0008] Preferably, by mass percentage, the raw materials of the multi-functional marine antifouling material include: 10-60% of the hydrophobic polymer particle material, 10-70% of polyvinylpyrrolidone, 1-10% of polyvinyl alcohol, and 0.05-40% of the metal salt;

[0009] Moreover, the molar ratio of the polyvinylpyrrolidone to the polyvinyl alcohol is 9:1 to 1:9, the molar ratio of the acetamide to the metal salt is 0.5:1 to 10:1, and the molar ratio of the total amount of the polyvinylpyrrolidone and the polyvinyl alcohol to the metal salt is 0.5:1 to 20:1.

[0010] Preferably, the hydrophobic polymer particle material includes at least one of polyethylene, polypropylene, and their modified polymers.

[0011] Preferably, the metal salt is a copper metal salt; or, the metal salt is a mixed salt of a copper metal salt, a silver metal salt, or a zinc metal salt; the copper metal salt is at least one of copper acetate, copper nitrate, or copper chloride, the silver metal salt is silver nitrate, and the zinc metal salt is at least one of zinc acetate, zinc nitrate, or zinc chloride.

[0012] Preferably, the particle size of the hydrophobic polymer particle material is ≥100 nm.

[0013] Preferably, the reducing agent includes at least one of ascorbic acid, citric acid, ethylene glycol, or hydroxylamine hydrochloride.

[0014] Preferably, the organic solvent is at least one of chloroform, dichloromethane, or N,N-dimethylformamide.

[0015] Preferably, the alcohol-water mixed solvent is a mixed solution of an alcohol solvent miscible with the organic solvent and water.

[0016] Preferably, the alkaline solution is at least one of a sodium hydroxide solution or an ammonia water solution.

[0017] In addition, the present invention also provides a multi-stage functional marine antifouling material prepared by the above-mentioned preparation method of the multi-stage functional marine antifouling material.

[0018] In addition, the present invention also provides an application of the multi-stage functional marine antifouling material in underwater monitoring equipment.

[0019] Compared with the prior art, the multi-functional marine antifouling material and its preparation method of the present invention have the following beneficial effects: The present invention provides a multi-functional marine antifouling material and its preparation method. Using hydrophobic polymer particle materials as the matrix, a polyvinylpyrrolidone-polyvinyl alcohol (PVP-PVA) cross-linked polymer hydrogel containing cuprous oxide is in-situ synthesized on the surface. Through process regulation, a composite structure material is obtained, which contains hydrophobic components, hydrophilic hydrogel components and antifouling active components, forming a multi-functional marine antifouling material. Different from the conventional physical mixing methods such as melting for preparing hydrophobic composite materials, the present invention forms a specific multi-functional structure through in-situ surface and interface regulation, and utilizes the synergistic effect of multi-components to improve the antifouling performance and stability of the material. The above preparation method is simple in operation, easy to control and adjustable in process, and has wide applicability. The prepared multi-functional material can be applied to the marine biological antifouling of underwater monitoring equipment and coatings in other antifouling application fields, and has good antifouling effect. Description of the Drawings

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other relevant drawings can also be obtained based on these drawings.

[0021] Figure 1 It is a scanning electron microscope image of the multi-functional marine antifouling material of the present invention.

[0022] The realization of the purpose of the present application, functional characteristics and advantages will be further described in combination with the embodiments with reference to the drawings. Detailed Embodiments

[0023] The following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0024] In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that those of ordinary skill in the art can achieve it. When the combination of technical solutions appears to be contradictory or unable to be realized, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0025] A preparation method of a multi-functional marine antifouling material includes the following steps:

[0026] S1. Ultrasonically disperse the hydrophobic polymer particle material in an organic solvent (a solvent that has a certain dissolving ability for the hydrophobic polymer particle material), then add an alcohol-water mixed solvent, and ultrasonically form a dispersion.

[0027] S2. After adding polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and metal salt into the dispersion and stirring evenly, add an acetamide solution and stir, then add an alkaline solution and stir evenly, and then add a reducing agent (a conventional reducing agent for chemically synthesizing metal oxides) to obtain a mixed solution. The mixed solution is continuously stirred at 50 - 80 °C for more than 2 hours. After the obtained product is filtered, washed, vacuum dried, and ground, the multi-functional marine antifouling material is obtained.

[0028] By mass percentage, the raw materials of the multi-functional marine antifouling material include: 10 - 60% of the hydrophobic polymer particle material, 10 - 70% of polyvinylpyrrolidone, 1 - 10% of polyvinyl alcohol, and 0.05 - 40% of the metal salt; and the molar ratio of polyvinylpyrrolidone to polyvinyl alcohol is 9:1 - 1:9, the molar ratio of acetamide to the metal salt is 0.5:1 - 10:1, and the molar ratio of the total amount of polyvinylpyrrolidone and polyvinyl alcohol to the metal salt is 0.5:1 - 20:1.

[0029] Among them, the hydrophobic polymer particle material includes at least one of polyethylene (PE) or polypropylene (PP) and their modified polymers. The metal salt is a copper metal salt, or the metal salt is a mixed salt of a copper metal salt, a silver metal salt, or a zinc metal salt; the copper metal salt is at least one of copper acetate, copper nitrate, or copper chloride, the silver metal salt is silver nitrate, and the zinc metal salt is at least one of zinc acetate, zinc nitrate, or zinc chloride. The reducing agent includes at least one of ascorbic acid, citric acid, ethylene glycol, or hydroxylamine hydrochloride. The organic solvent is at least one of chloroform, dichloromethane, or N,N-dimethylformamide. The alkaline solution is at least one of sodium hydroxide solution or ammonia water solution.

[0030] The particle size of the hydrophobic polymer particle material ≥ 100 nm. Usually, the hydrophobic polymer particle material is nano-scale or micro-scale particles. The alcohol-water mixed solvent is a mixed solution of an alcohol solvent that is miscible with the organic solvent and water, such as methanol, ethanol, etc., where the volume ratio of the alcohol solvent to water is 9:1 - 1:9.

[0031] During the preparation process, acetamide and metal salts have a regulatory effect on the formation of PVP-PVA cross-linked polymer hydrogel and cuprous oxide. The multi-functional marine antifouling material prepared by the above preparation method is a composite structural material. The specific structure is a core-shell structure in which the surface of the hydrophobic polymer particle material is completely covered by the cross-linked polymer hydrogel or a composite structure in which the surface is partially covered by the cross-linked polymer hydrogel. The antifouling active component cuprous oxide exists in the cross-linked polymer hydrogel. The multi-functional marine antifouling material has a multi-level synergistic antifouling effect of fouling desorption type antifouling of low surface energy hydrophobic materials, fouling impedance type antifouling of forming a dense water molecule layer on the hydrogel surface, and cuprous oxide antifouling effect.

[0032] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0033] Example 1

[0034] A preparation method of a multi-functional marine antifouling material includes the following steps:

[0035] S1. Weigh 0.80 grams of polyethylene PE (average particle size is about 100 nanometers) into a round-bottom flask, add 20 milliliters of chloroform, after ultrasonic treatment for 5 minutes, add 156 milliliters of ethanol-water mixed solvent (volume ratio 1:9), and after ultrasonic treatment for 10 minutes, a dispersion is formed;

[0036] S2. Add 6.00 grams of polyvinylpyrrolidone (PVP), 0.26 grams of polyvinyl alcohol (PVA), and 0.51 grams of copper dichloride dihydrate to the dispersion in sequence. After stirring for 30 minutes, add 1.77 grams of acetamide, stir for 10 minutes, add 20 milliliters of sodium hydroxide (6mol·L -1 ) aqueous solution and 4.0 milliliters of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 grams of ascorbic acid to obtain a mixed solution. The mixed solution is continuously stirred at 50 °C for 3 hours. The obtained product is filtered, washed with deionized water, vacuum dried at 60 °C, and ground to obtain a solid powder, which is the multi-functional marine antifouling material (PE / PVP-PVA / Cu2O composite material).

[0037] Example 2

[0038] A preparation method of a multi-functional marine antifouling material includes the following steps:

[0039] S1. Weigh 7.20 grams of polyethylene PE (average particle size is about 700 nanometers) into a round-bottom flask, add 40 milliliters of chloroform, after ultrasonic treatment for 5 minutes, add 112 milliliters of ethanol-water mixed solvent (volume ratio 1:9), and after ultrasonic treatment for 10 minutes, a dispersion is formed;

[0040] S2. Add 6.00 g of polyvinylpyrrolidone (PVP), 0.26 g of polyvinyl alcohol (PVA), and 0.51 g of copper(II) chloride dihydrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 1.77 g of acetamide, stir for 10 minutes, add 40 mL of sodium hydroxide (6 mol·L -1 ) aqueous solution and 8.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid. The mixed solution is continuously stirred at 50 °C for 4 hours. The obtained product is filtered, washed with deionized water, dried in vacuum at 60 °C, and ground to obtain a solid powder, which is the multi-functional marine antifouling material (PE / PVP-PVA / Cu2O composite material).

[0041] Example 3

[0042] A preparation method of a multi-functional marine antifouling material, comprising the following steps:

[0043] S1. Weigh 0.67 g of polyethylene PE (average particle size is about 30 microns) into a round-bottom flask, add 20 mL of chloroform, ultrasonicate for 5 minutes, then add 156 mL of ethanol-water mixed solvent (volume ratio 9:1), and ultrasonicate for 10 minutes to form a dispersion liquid;

[0044] S2. Add 0.10 polyethylene pyrrolidone (PVP), 0.36 g of polyvinyl alcohol (PVA), and 0.72 g of copper(II) nitrate trihydrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 0.09 g of acetamide, stir for 10 minutes, add 20 mL of sodium hydroxide (6 mol·L -1 ) aqueous solution and 4.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid. The mixed solution is continuously stirred at 50 °C for 2 hours. The obtained product is filtered, washed with deionized water, dried in vacuum at 60 °C, and ground to obtain a solid powder, which is the multi-functional marine antifouling material (PE / PVP-PVA / Cu2O composite material).

[0045] Example 4

[0046] A preparation method of a multi-functional marine antifouling material, comprising the following steps:

[0047] S1. Weigh 0.67 g of polypropylene PP (average particle size is about 10 microns) into a round-bottom flask, add 20 mL of N,N-dimethylformamide, ultrasonicate for 5 minutes, then add 156 mL of ethanol-water mixed solvent (volume ratio 9:1), and ultrasonicate for 10 minutes to form a dispersion liquid;

[0048] S2. Add 0.10 g of polyvinylpyrrolidone (PVP), 0.36 g of polyvinyl alcohol (PVA), and 0.72 g of copper nitrate trihydrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 0.09 g of acetamide and stir for 10 minutes. Then add 20 mL of sodium hydroxide (6 mol·L -1 ) aqueous solution and 4.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 1.25 g of hydroxylamine hydrochloride. The mixture is continuously stirred at 80 °C for 2 hours. The obtained product is filtered, washed with deionized water, and vacuum dried at 60 °C. After grinding, a solid powder is obtained, which is the multi-functional marine antifouling material (PP / PVP-PVA / Cu2O composite material).

[0049] Example 5

[0050] A preparation method of a multi-functional marine antifouling material includes the following steps:

[0051] S1. Weigh 3.00 g of polyethylene PE (average particle size is about 100 nm) and 3.00 g of polyethylene PE (average particle size is about 500 nm) into a round-bottom flask, add 40 mL of chloroform, and after ultrasonic treatment for 5 minutes, add 124 mL of ethanol-water mixed solvent (volume ratio 1:9). After ultrasonic treatment for 10 minutes, a dispersion liquid is formed;

[0052] S2. Add 6.00 g of polyvinylpyrrolidone (PVP), 0.26 g of polyvinyl alcohol (PVA), and 0.51 g of copper chloride dihydrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 1.77 g of acetamide and stir for 10 minutes. Then add 30 mL of sodium hydroxide (6 mol·L -1 ) aqueous solution and 6.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 5.28 g of ascorbic acid. The mixture is continuously stirred at 50 °C for 4 hours. The obtained product is filtered, washed with deionized water, and vacuum dried at 60 °C. After grinding, a solid powder is obtained, which is the multi-functional marine antifouling material (PE / PVP-PVA / Cu2O composite material).

[0053] Example 6

[0054] A preparation method of a multi-functional marine antifouling material includes the following steps:

[0055] S1. Weigh 0.38 g of polyethylene PE (average particle size is about 30 μm) into a round-bottom flask, add 20 mL of chloroform, and after ultrasonic treatment for 5 minutes, add 156 mL of ethanol-water mixed solvent (volume ratio 9:1). After ultrasonic treatment for 10 minutes, a dispersion liquid is formed;

[0056] S2. Add 0.05 g of polyvinylpyrrolidone (PVP), 0.18 g of polyvinyl alcohol (PVA), and 2.51 g of copper nitrate trihydrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 0.09 g of acetamide and stir for 10 minutes. Then add 20 mL of sodium hydroxide (6 mol·L -1 ) aqueous solution and 4.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 2.59 g of ascorbic acid. The mixed solution is continuously stirred at 50 °C for 2 hours. The obtained product is filtered, washed with deionized water, and dried in vacuum at 60 °C. After grinding, a solid powder is obtained, which is the multi-functional marine antifouling material (PE / PVP-PVA / Cu2O composite material).

[0057] Example 7

[0058] A preparation method of a multi-functional marine antifouling material includes the following steps:

[0059] S1. Weigh 7.20 g of polyethylene PE (average particle size is about 700 nm) into a round-bottom flask, add 40 mL of chloroform, and after ultrasonic treatment for 5 minutes, add 112 mL of ethanol-water mixed solvent (volume ratio 1:9). After ultrasonic treatment for 10 minutes, a dispersion liquid is formed;

[0060] S2. Add 6.00 g of polyvinylpyrrolidone (PVP), 0.26 g of polyvinyl alcohol (PVA), 0.34 g of copper chloride dihydrate, and 0.17 g of zinc chloride dihydrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 1.77 g of acetamide and stir for 10 minutes. Then add 40 mL of sodium hydroxide (6 mol·L -1 ) aqueous solution and 8.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid. The mixed solution is continuously stirred at 50 °C for 4 hours. The obtained product is filtered, washed with deionized water, and dried in vacuum at 60 °C. After grinding, a solid powder is obtained, which is the multi-functional marine antifouling material (PE / PVP-PVA / Cu2O-ZnO composite material).

[0061] Example 8

[0062] A preparation method of a multi-functional marine antifouling material includes the following steps:

[0063] S1. Weigh 7.20 g of polyethylene PE (average particle size is about 700 nm) into a round-bottom flask, add 40 mL of chloroform, and after ultrasonic treatment for 5 minutes, add 112 mL of ethanol-water mixed solvent (volume ratio 1:9). After ultrasonic treatment for 10 minutes, a dispersion liquid is formed;

[0064] S2. Add 6.00 g of polyvinylpyrrolidone (PVP), 0.26 g of polyvinyl alcohol (PVA), 0.34 g of copper chloride dihydrate, and 0.17 g of silver nitrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 1.77 g of acetamide and stir for 10 minutes. Then add 40 mL of sodium hydroxide (6 mol·L -1 ) aqueous solution and 8.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid. The mixed solution is continuously stirred at 50 °C for 4 hours. The obtained product is filtered, washed with deionized water, and vacuum dried at 60 °C. After grinding, a solid powder is obtained, which is a multi-functional marine antifouling material (PE / PVP-PVA / Cu2O-Ag composite material).

[0065] Comparative Example 1

[0066] Use the raw materials of Example 1 of this scheme, but prepare the antifouling material by the traditional physical melting method. The specific steps are as follows:

[0067] S1. Dissolve 6.00 g of polyvinylpyrrolidone (PVP), 0.26 g of polyvinyl alcohol (PVA), and 0.51 g of copper chloride dihydrate in 50 mL of water. After stirring for 30 minutes, add 1.77 g of acetamide and stir for 10 minutes. Then add 20 mL of sodium hydroxide (6 mol·L-1) aqueous solution and 4.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid to obtain a mixed solution. The mixed solution is continuously stirred at 50 °C for 3 hours. The obtained product is filtered, washed with deionized water, and vacuum dried at 60 °C. After grinding, a solid powder is obtained;

[0068] S2. After stirring and mixing the obtained solid powder with 0.80 g of polyethylene PE (average particle size of about 100 nm), transfer it to a porcelain boat and place it in a muffle furnace for high-temperature calcination (250 °C) to make the PE in a molten state. After 2 hours, cool it naturally to obtain the PE / PVP-PVA / Cu2O composite material prepared by the physical melting method.

[0069] Comparative Example 2

[0070] All the preparation steps and parameters in this comparative example are the same as those in Example 1, except that: Group 1: Polyvinylpyrrolidone (PVP) was not added compared with Example 1; Group 2: Polyvinyl alcohol (PVA) was not added compared with Example 1. Each group specifically includes the following steps:

[0071] Comparative Example 2-1

[0072] S1. Weigh 0.80 g of polyethylene PE (average particle size is about 100 nm) into a round-bottom flask, add 20 mL of chloroform, and after ultrasonic treatment for 5 minutes, add 156 mL of ethanol-water mixed solvent (volume ratio 1:9). After ultrasonic treatment for 10 minutes, a dispersion is formed;

[0073] S2. Add 0.26 g of polyvinyl alcohol (PVA) and 0.51 g of copper chloride dihydrate to the dispersion in sequence. After stirring for 30 minutes, add 1.77 g of acetamide and stir for 10 minutes. Then add 20 mL of sodium hydroxide (6 mol·L-1) aqueous solution and 4.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid to obtain a mixed solution. The mixed solution is continuously stirred at 50 °C for 3 hours. The obtained product is filtered, washed with deionized water, dried in vacuum at 60 °C, and ground to obtain a solid powder, which is the PE / PVA / Cu2O composite material.

[0074] Comparative Example 2-2

[0075] S1. Weigh 0.80 g of polyethylene PE (average particle size is about 100 nm) into a round-bottom flask, add 20 mL of chloroform, and after ultrasonic treatment for 5 minutes, add 156 mL of ethanol-water mixed solvent (volume ratio 1:9). After ultrasonic treatment for 10 minutes, a dispersion is formed;

[0076] S2. Add 6.00 g of polyvinylpyrrolidone (PVP) and 0.51 g of copper chloride dihydrate to the dispersion in sequence. After stirring for 30 minutes, add 1.77 g of acetamide and stir for 10 minutes. Then add 20 mL of sodium hydroxide (6 mol·L-1) aqueous solution and 4.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid to obtain a mixed solution. The mixed solution is continuously stirred at 50 °C for 3 hours. The obtained product is filtered, washed with deionized water, dried in vacuum at 60 °C, and ground to obtain a solid powder, which is the PE / PVP / Cu2O composite material.

[0077] Comparative Example 3

[0078] All the preparation steps and parameters in this comparative example are the same as those in Example 1, except that: acetamide is not added. It includes the following steps:

[0079] S1. Weigh 0.80 g of polyethylene PE (average particle size is about 100 nm) into a round-bottom flask, add 20 mL of chloroform, and after ultrasonic treatment for 5 minutes, add 156 mL of ethanol-water mixed solvent (volume ratio 1:9). After ultrasonic treatment for 10 minutes, a dispersion is formed;

[0080] S2. Add 6.00 g of polyvinylpyrrolidone (PVP), 0.26 g of polyvinyl alcohol (PVA), and 0.51 g of copper chloride dihydrate to the dispersion liquid in sequence. After stirring for 30 minutes, add 20 mL of sodium hydroxide (6 mol·L-1) aqueous solution and 4.0 mL of ammonia water solution (25%). After stirring for 15 minutes, add 3.17 g of ascorbic acid to obtain a mixed solution. The mixed solution is continuously stirred at 50 °C for 3 hours. The obtained product is filtered, washed with deionized water, dried in vacuum at 60 °C, and ground to obtain a solid powder, which is the PE / PVP-PVA / Cu2O composite material.

[0081] Mix the antifouling materials prepared in Examples 1-8 and Comparative Examples 1-3 above with epoxy primer respectively (where the mass percentage of the antifouling material is 30%), and uniformly coat them on the stainless steel surface of the underwater monitoring equipment. Use the epoxy primer without adding the antifouling material as the blank control group for the underwater test. The specific test results are shown in the following table.

[0082]

[0083]

[0084] It can be seen from the results in the above table that the multi-functional marine antifouling materials prepared in Examples 1-8 of this scheme can all show good underwater antifouling performance within 6 to 12 months.

[0085] It can be seen from the test results of Comparative Example 1 and Example 1 that compared with the traditional physical melting preparation method, the multi-functional marine antifouling materials prepared by the preparation process of this scheme have better antifouling performance.

[0086] It can be seen from the test results of Comparative Examples 2 to 3 and Example 1 that when polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), or acetamide is not added to the raw materials, the antifouling performance of the prepared multi-functional marine antifouling materials will all decrease to varying degrees.

[0087] In addition, this scheme also conducted multiple experiments and determined that the preferred molar ratio of polyvinylpyrrolidone to polyvinyl alcohol is 2:3 to 3:2, the molar ratio of acetamide to metal salt is 4:1 to 6:1, and the total molar ratio of polyvinylpyrrolidone and polyvinyl alcohol to metal salt is 5:1 to 8:1. Under the above preferred range, the antifouling performance of the prepared multi-functional marine antifouling materials is further improved. According to the record, in the underwater test, the fouling organism coverage rate on the stainless steel surface of the monitoring equipment can also be maintained at <0.1% after 18 months.

[0088] The above embodiments are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. The multi-level functional marine antifouling materials mentioned in the present invention are not limited to the above several kinds. Therefore, the above embodiments cannot be regarded as a limitation on the protection scope of the present invention. Any equivalent structural transformation made by using the content of the specification of the present invention under the inventive concept of the present invention, or any direct / indirect application in other related technical fields is included in the patent protection scope of the present invention.

Claims

1. A method for preparing a multi-stage functional marine antifouling material, characterized in that: The following steps are involved: S1. Ultrasonic dispersion of a hydrophobic polymer particle material in an organic solvent, and then adding an alcohol-water mixed solvent, ultrasonically forming a dispersion; S2. Add polyvinyl pyrrolidone, polyvinyl alcohol and metal salt to the dispersion respectively and stir evenly, add acetamide solution dropwise, add alkaline solution and stir evenly, then add reducing agent to obtain a mixed solution, continue to stir the mixed solution at 50-80°C for more than 2 hours, and finally filter, wash, vacuum dry and grind to obtain the multi-stage functional marine antifouling material.

2. A method for preparing a multi-level functional marine antifouling material according to claim 1, characterized in that: The raw materials of the multi-stage functional marine antifouling material include, by mass percentage: 10-60% of hydrophobic polymer particulate material, 10-70% of polyvinyl pyrrolidone, 1-10% of polyvinyl alcohol, and 0.05-40% of metal salt; The molar ratio of the polyvinyl pyrrolidone to the polyvinyl alcohol is 9:1-1:9, the molar ratio of the acetamide to the metal salt is 0.5:1-10:1, and the molar ratio of the total amount of the polyvinyl pyrrolidone and the polyvinyl alcohol to the metal salt is 0.5:1-20:

1.

3. The method for preparing a multi-level functional marine antifouling material according to claim 1, characterized in that: The hydrophobic polymer particle material comprises at least one of polyethylene or polypropylene and modified polymers thereof.

4. The method for preparing a multi-level functional marine antifouling material according to claim 1, characterized in that: The metal salt is a copper metal salt; or, the metal salt is a mixed salt of a copper metal salt, a silver metal salt or a zinc metal salt; The copper metal salt is at least one of copper acetate, copper nitrate or copper chloride, the silver metal salt is silver nitrate, and the zinc metal salt is at least one of zinc acetate, zinc nitrate or zinc chloride.

5. A method for preparing a multi-stage functional marine antifouling material according to claim 1 or 3, characterized in that: The particle size of the hydrophobic polymer particulate material is ≥100 nm.

6. The method for preparing a multi-level functional marine antifouling material according to claim 1, characterized in that: The reducing agent includes at least one of ascorbic acid, citric acid, ethylene glycol or hydroxylamine hydrochloride.

7. The method for preparing a multi-level functional marine antifouling material according to claim 1, characterized in that: The organic solvent is at least one of chloroform, dichloromethane or N,N-dimethylformamide.

8. The method for preparing a multi-level functional marine antifouling material according to claim 1, characterized in that: The alcohol-water mixed solvent is a mixed solution of an alcohol solvent miscible with the organic solvent and water; the alkaline solution is at least one of a sodium hydroxide solution or an ammonia solution.

9. A multi-level functional marine antifouling material, characterized in that: The multi-stage functional marine antifouling material is prepared by the preparation method of any one of claims 1 to 8.

10. Use of the multi-stage functional marine antifouling material as claimed in claim 9 in underwater monitoring equipment.

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