A net material with both anti-adhesion, self-cleaning and toughness and its application

Abstract

The present invention provides a net material that is both anti-adhesive, self-cleaning, and tough, belonging to the technical field of net materials for aquaculture. The net material that is both anti-adhesive, self-cleaning, and tough provided by the present invention comprises an antibacterial polyethylene core layer, an ultra-thin strong magnetic film, and an epoxy resin layer with an H-SiO2@CIP silane microstructure on the surface; the antibacterial polyethylene core layer can release antibacterial substances that prevent marine bacteria or attached microorganisms, and the ultra-thin strong magnetic film can slowly penetrate the antibacterial substances into the outermost layer; the hydrophobically modified silica-coated nano-iron particle-silane microstructure constructed on the outer surface of the epoxy resin coating has high hydrophobicity and anti-adhesion properties, imparting self-cleaning and anti-fouling effects, and further slowly penetrates the antibacterial molecules released by the antibacterial polyethylene core layer to the outside to avoid waste.

Description

Technical Field

[0001] The present invention relates to the technical field of net materials for aquaculture, and in particular to a net material with the characteristics of anti-adhesion, self-cleaning and toughness and application thereof. Background Art

[0002] In the marine aquaculture industry, fish are usually cultured in cages, and the net material is the key basic material for making the cages. Traditional net materials are made of synthetic fibers such as nylon, polyethylene, and polypropylene. Although synthetic fibers have good corrosion resistance and toughness, traditional net materials have the following defects: 1. Marine biofouling; 2. Poor resistance to wind and waves and erosion; 3. Short service life of the net (about 1 year); 4. Synthetic fibers cannot be recycled and are not environmentally friendly. Among them, marine biofouling refers to the accumulation of microorganisms, plant organisms, and animal organisms in the ocean on artificial surfaces. When deep-sea cages used for aquaculture are attached by a large number of marine organisms, the mesh is blocked, the convection of seawater inside and outside the cage is reduced, and the dissolved oxygen content and food supply are reduced, causing the farmed seafood to develop poorly or even die, seriously affecting the output and quality of seafood.

[0003] Currently, the marine aquaculture industry commonly uses methods such as physical removal, antifouling agents, and biological control to control biofouling. Physical removal methods typically address net fouling through regular net changes, mechanical cleaning, antifouling or cage rotation, and chemical control agents. These processes are cumbersome and labor-intensive, time-consuming, and labor-intensive, requiring frequent repetitions, damaging cages, and impacting the aquaculture cycle of seafood. Using biological control technologies to address marine biofouling has enormous potential, but high costs limit their application in the marine aquaculture industry. Using net antifouling coatings is the current mainstream antifouling method, typically applied to fishing nets via dip coating. Marine aquaculture requires nets to maintain an antifouling effect for at least six months. However, existing net antifouling coatings lack flexibility, significantly reducing tensile and torsional strength after coating the net, impacting net function. Furthermore, due to the limited antifouling effectiveness of film-forming materials, commercially available net antifouling coatings often contain large amounts of copper antifouling agents to achieve effective antifouling, which does not meet environmental standards and poses potential risks to aquatic life. Therefore, providing an environmentally friendly aquaculture net with excellent anti-fouling effect, good flexibility, high tensile strength and high torsional strength is a technical problem that needs to be solved urgently in the existing technology. Summary of the Invention

[0004] The purpose of the present invention is to provide a net material with anti-adhesion, self-cleaning and toughness and its application. The net material with anti-adhesion, self-cleaning and toughness provided by the present invention has anti-adhesion and self-cleaning effects. The aquaculture net prepared from it has excellent anti-fouling effect, good flexibility, high tensile and torsional strength.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a mesh material that is both anti-adhesive, self-cleaning, and tough. The mesh material comprises a three-layer structure, which comprises, from the inside out, an antibacterial polyethylene core layer, an ultra-thin strong magnetic film, and an epoxy resin layer with an H-SiO2@CIP silane microstructure on the surface.

[0007] The preparation method of the net material comprises the following steps:

[0008] S1, preparing an antibacterial polyethylene core layer;

[0009] S2, coating the antibacterial polyethylene core layer obtained in step (S1) with the ultra-thin ferromagnetic film to obtain a coated antibacterial polyethylene core layer;

[0010] S3. Coating the epoxy resin mixed solution on the surface of the coated antibacterial polyethylene core layer obtained in step (S2), and drying the resulting net material to obtain a net material having both anti-adhesion, self-cleaning and toughness.

[0011] Preferably, the diameter of the antibacterial polyethylene core layer is 1 to 3.5 mm, the thickness of the ultra-thin ferromagnetic film is 2 to 400 μm, and the thickness of the epoxy resin layer with the H-SiO2@CIP silane microstructure on the surface is 80 to 260 μm.

[0012] Preferably, the method for preparing the antibacterial polyethylene core layer in step (S1) comprises the following steps:

[0013] (1) Premixing polyethylene, an antimicrobial agent, succinic anhydride, and dicumyl peroxide, and then sequentially performing blending, grafting reaction, and extrusion granulation to obtain antimicrobial polymer particles;

[0014] (2) The antibacterial polymer particles obtained in step (1) are premixed with PET resin, phenolic antioxidant, and maleic anhydride grafted polyethylene, and then kneaded and extruded into granules in sequence, and then melt-extruded from the spinneret holes of a single-screw extruder, and melt-spun and stretched to obtain an antibacterial polyethylene core layer.

[0015] Preferably, the antibacterial agent in step (1) is at least two of polyhexamethylene guanidine phosphate, polyhexamethylene biguanidine phosphate, and streptomycin.

[0016] Preferably, the step (S3) includes the following steps:

[0017] (S3-1) mixing a suspension of polydimethylsiloxane, a crosslinking agent, and hydrophobically modified silica-coated nano-iron particles, and sequentially performing a first stirring, a first vacuum degassing, and an ultrasonic treatment to obtain a mixed solution;

[0018] Adding bisphenol epoxy resin to the mixed solution, and sequentially performing a second stirring and a second vacuum defoaming to obtain an epoxy resin mixed solution;

[0019] (S3-2) coating the epoxy resin mixed solution obtained in the step (S3-1) on the surface of the coated antibacterial polyethylene core layer obtained in the step (S2), and drying the resulting mesh material to obtain a mesh material having both anti-adhesion, self-cleaning and toughness.

[0020] Preferably, the method for preparing hydrophobically modified silica-coated nano-iron particles in step (S3-1) comprises the following steps:

[0021] The silica-coated nano-iron particles are dispersed in an alkaline ethanol solution, dried, and then subjected to plasma modification to obtain activated silica-coated nano-iron particles;

[0022] The activated silica-coated nano-iron particles are mixed with dimethyldichlorosilane (DCDMS) and toluene, and then subjected to a hydrolysis reaction. A KH-560 silane coupling agent is then added to carry out a coupling reaction to obtain hydrophobically modified silica-coated nano-iron particles.

[0023] Preferably, the plasma modification treatment lasts for 2 to 5 minutes, and the concentration of oxygen in the gas used for the plasma modification treatment is 50 vt% to 70 vt%.

[0024] Preferably, in the step (S3-1), the mass ratio of polydimethylsiloxane, crosslinking agent, and hydrophobically modified silica-coated nano-iron particles is 15:(2-8):(6-12).

[0025] Preferably, the drying temperature in the step (S3-2) is 45 to 55°C, and the drying time is 16 to 20 hours.

[0026] The present invention also provides the use of the net material having both anti-adhesion, self-cleaning and toughness as described in the above technical solution in the preparation of aquaculture nets, comprising the following steps:

[0027] A plurality of strands of the net material are braided to form a net rope, and the net rope is woven to form a knotless mesh, thereby obtaining a breeding net with the characteristics of anti-adhesion, self-cleaning and toughness.

[0028] The present invention provides a mesh material with both anti-adhesion, self-cleaning and toughness, comprising a three-layer structure, which comprises, from the inside to the outside, an antibacterial polyethylene core layer, an ultra-thin strong magnetic film and an epoxy resin layer with an H-SiO2@CIP silane microstructure on the surface. The present invention utilizes an antibacterial polyethylene core layer to release antibacterial substances that prevent marine bacteria or attached microorganisms; the ultra-thin strong magnetic film, on the one hand, helps to coat the epoxy resin coating to form the outermost layer, thereby constructing a nano-iron particle-silane microstructure wrapped with hydrophobic modified silica on the outer surface, and on the other hand, slowly penetrates the antibacterial substances released by the antibacterial polyethylene core layer into the outermost layer; the hydrophobic modified silica-wrapped nano-iron particle-silane microstructure (abbreviated as H-SiO2@CIP silane microstructure) constructed on the outer surface of the epoxy resin coating has high hydrophobicity and anti-adhesion properties, imparting self-cleaning and anti-fouling effects, and further slowly penetrates the antibacterial molecules released by the antibacterial polyethylene core layer to the outside to avoid waste; the present invention utilizes a three-layer structure formed by an antibacterial polyethylene core layer, an ultra-thin strong magnetic film and an epoxy resin layer with an H-SiO2@CIP silane microstructure on the surface, thereby maintaining the flexibility of the mesh material with both anti-adhesion, self-cleaning and toughness, and improving its tensile and torsional strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 A schematic structural diagram of the net material provided by the present invention that has both anti-adhesion, self-cleaning and toughness;

[0030] Figure 2 The outer surface of the epoxy resin layer in the present invention is constructed with hydrophobically modified silica-coated nano-iron particles-silane microstructure, where the left figure is a surface microstructure diagram and the right figure is a partial magnified diagram;

[0031] Figure 3 Schematic diagram of the structure of the hydrophobically modified silica-coated nano-iron particles, i.e., H-SiO2@CIP particles, in the present invention. DETAILED DESCRIPTION

[0032] The present invention provides a mesh material that is both anti-adhesive, self-cleaning, and tough. The mesh material comprises a three-layer structure, which comprises, from the inside out, an antibacterial polyethylene core layer, an ultra-thin strong magnetic film, and an epoxy resin layer with an H-SiO2@CIP silane microstructure on the surface.

[0033] The preparation method of the net material comprises the following steps:

[0034] S1, preparing an antibacterial polyethylene core layer;

[0035] S2. Using a coating technique and an adhesive, the ultra-thin ferromagnetic film is coated on the antibacterial polyethylene core layer obtained in step (S1) to obtain a coated antibacterial polyethylene core layer;

[0036] S3. Coating the epoxy resin mixed solution on the surface of the coated antibacterial polyethylene core layer obtained in step (S2), and drying the resulting net material to obtain a net material having both anti-adhesion, self-cleaning and toughness.

[0037] In the present invention, unless otherwise specified, the raw materials used are conventional commercial products in the field.

[0038] In the present invention, the diameter of the antibacterial polyethylene core layer is preferably 1 to 3.5 mm, more preferably 1.3 to 3 mm; the thickness of the ultra-thin ferromagnetic film is preferably 2 to 400 μm, more preferably 10 to 300 μm, and the thickness of the epoxy resin layer with H-SiO2@CIP silane microstructure on the surface is preferably 80 to 260 μm, more preferably 100 to 230 μm.

[0039] In the present invention, the method for preparing the antibacterial polyethylene core layer in step (S1) comprises the following steps:

[0040] (1) Premixing polyethylene, an antimicrobial agent, succinic anhydride, and dicumyl peroxide, and then sequentially performing blending, grafting reaction, and extrusion granulation to obtain antimicrobial polymer particles;

[0041] (2) The antibacterial polymer particles obtained in step (1) are premixed with PET resin, phenolic antioxidant, and maleic anhydride grafted polyethylene, and then kneaded and extruded into granules in sequence, and then melt-extruded from the spinneret holes of a single-screw extruder, and melt-spun and stretched to obtain an antibacterial polyethylene core layer.

[0042] In the present invention, the molecular weight of the polyethylene is preferably 100,000 to 500,000, more preferably 200,000 to 400,000.

[0043] In the present invention, the antibacterial agent is at least two of polyhexamethylene monoguanidine phosphate, polyhexamethylene biguanide phosphate, and streptomycin; the antibacterial agent preferably accounts for 15% to 50% of the mass of the polyethylene, more preferably 20% to 40%; the mass of the succinic anhydride preferably accounts for 8% to 12% of the mass of the polyethylene; the mass of the diisopropyl peroxide initiator preferably accounts for 1% to 1.5% of the mass of the polyethylene.

[0044] In the present invention, the temperature of the blending is preferably 180-230°C, more preferably 200-220°C. The present invention has no special restrictions on the time of the blending, as long as the components are mixed evenly. In the present invention, the temperature of the grafting reaction is preferably 190-240°C, more preferably 200-220°C; the time of the grafting reaction is preferably 1-8h, more preferably 2-6h. The present invention controls the temperature and time of the grafting reaction within the above range to ensure that more polyhexamethylene monoguanidine phosphate / polyhexamethylene biguanidine phosphate and streptomycin are grafted onto polyethylene to obtain antibacterial polymer particles with excellent antibacterial effect.

[0045] In the present invention, the particle size of the antibacterial polymer particles is preferably 1 to 10 mm, more preferably 2 to 5 mm.

[0046] In the present invention, the mass ratio of the antibacterial polymer particles to the PET resin and the maleic anhydride grafted polyethylene is preferably 1:(1-3):(1-3), more preferably 1:(1.2-2.5):(1.2-2.5).

[0047] In the present invention, the molecular weight of the PET resin is preferably 100,000 to 180,000. In the present invention, the maleic anhydride-grafted polyethylene is maleic anhydride-grafted PE model ADDIMER 630R produced by CERONAS in Germany. In the present invention, the mass of the phenolic antioxidant accounts for 0.05% to 0.6% of the mass of the antibacterial polymer particles; the phenolic antioxidant is one or more of 2,6-di-tert-butyl-4-methylphenol, β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate, tert-butylphenol hydroxybenzoate, p-hydroxybenzoate, and tri-tert-butylhydroxybenzoate.

[0048] In the present invention, the kneading time is preferably 1 to 3 hours.

[0049] In the present invention, the pore diameter of the spinneret is preferably 1.00 mm to 3.00 mm; the process conditions of the melt spinning and stretching treatment are preferably: the spinning temperature is 230 to 360°C, the spinning speed is 3 to 25 m / min, the stretching treatment multiple is 2 to 55 times, and the stretching treatment temperature is 60 to 150°C.

[0050] In the present invention, the preparation method of the ultra-thin ferromagnetic film preferably includes: mixing 40 to 80 parts of resin particles, 20 to 40 parts of magnetic powder and 1 to 10 parts of dispersant to obtain surface pretreated particles; extruding and granulating the surface pretreated particles in a twin-screw extruder to obtain masterbatches; and processing the masterbatches through a blow molding machine to obtain an ultra-thin ferromagnetic film.

[0051] In the present invention, the magnetic powder has a diameter of 1 to 20 nm and is preferably at least one of barium ferrite, cobalt ferrite, ferroferric oxide, gamma iron oxide, carbonyl iron powder, manganese zinc ferrite, nickel oxide, cobalt oxide, and iron powder. In the present invention, the resin particles are preferably one or more of polyethylene, polyvinyl chloride, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer. In the present invention, the dispersant is preferably at least one of KH-560 silane coupling agent, KH-570 silane coupling agent, KH-151 silane coupling agent, and KH-171 silane coupling agent.

[0052] In the present invention, the parameters of the twin-screw extruder are preferably: a heating temperature of 120 to 190° C., a screw speed of 180 to 330 r / min, and a feeding speed of 40 to 55 r / min.

[0053] In the present invention, the parameters of the blow molding machine are preferably: heating temperature of 120-210° C., screw speed of 80-120 r / min, blow-up ratio of 1:(1-3), and traction speed of 4-8 m / min.

[0054] In the present invention, the coating method is preferably to use coating technology and adhesive to tightly adhere the ultra-thin strong magnetic film to the surface of the antibacterial polyethylene core layer.

[0055] The present invention has no particular limitation on the laminating technology, and any technical solution known in the art can be used. In the present invention, the adhesive is preferably at least one of polyurethane emulsion, vinyl polyurethane emulsion, polyisocyanate emulsion, and blocked polyurethane emulsion.

[0056] In the present invention, the epoxy resin mixed solution is coated on the surface of the coated antibacterial polyethylene core layer, and then dried to obtain a net material having both anti-adhesion, self-cleaning and toughness, which preferably includes the following steps:

[0057] (S1) mixing a suspension of polydimethylsiloxane, a cross-linking agent, and hydrophobically modified silica-coated nano-iron particles, and sequentially performing a first stirring, a first vacuum degassing, and an ultrasonic treatment to obtain a mixed solution;

[0058] Adding bisphenol epoxy resin to the mixed solution, and sequentially performing a second stirring and a second vacuum defoaming to obtain an epoxy resin mixed solution;

[0059] (S2) coating the epoxy resin mixed solution obtained in step (S2) on the surface of the coated antibacterial polyethylene core layer, and drying the resulting double-layer membrane structure.

[0060] In the present invention, the molecular weight of the polydimethylsiloxane is preferably 1500 to 8000, more preferably 2000 to 6000. In the present invention, the crosslinking agent is preferably at least one of methyltri(methoxy)silane, vinyltrimethoxysilane, and 3-aminopropyltrimethoxysilane.

[0061] In the present invention, the ethyl acetate suspension of the hydrophobically modified silica-coated nano-iron particles is preferably obtained by mixing the hydrophobically modified silica-coated nano-iron particles with ethyl acetate and then subjecting the mixture to ultrasound.

[0062] In the present invention, the mass ratio of the polydimethylsiloxane, the crosslinking agent, and the hydrophobically modified silica-coated nano-iron particles is preferably 15:(2-8):(6-12), more preferably 15:(3-6):(8-11).

[0063] The present invention has no particular limitation on the first stirring method, as long as the ethyl acetate is fully volatilized. In the present invention, the ultrasonic time is preferably 10 to 20 minutes.

[0064] In the present invention, the concentration of the bisphenol epoxy resin in the epoxy resin mixed solution is preferably 50wt% to 70wt%; the bisphenol epoxy resin is preferably at least one of bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, and bisphenol A novolac epoxy resin.

[0065] In the present invention, the second stirring time is preferably 30 to 50 minutes.

[0066] In the present invention, the coating method is preferably spin coating; the coating thickness is preferably 130 to 250 μm, more preferably 150 to 230 μm.

[0067] In the present invention, the drying temperature is preferably 45 to 55° C., and the drying time is 16 to 20 hours.

[0068] In the present invention, the method for preparing the hydrophobically modified silica-coated nano-iron particles preferably comprises the following steps:

[0069] drying the alkaline ethanol solution of the silica-coated nano-iron particles and then performing plasma modification treatment to obtain activated silica-coated nano-iron particles;

[0070] The activated silica-wrapped nano-iron particles are mixed with dimethyldichlorosilane and toluene, and then subjected to a hydrolysis reaction. A KH-560 silane coupling agent is then added to carry out a coupling reaction to obtain hydrophobically modified silica-wrapped nano-iron particles.

[0071] In the present invention, the pH of the alkaline ethanol solution of the silica-encapsulated nano-iron particles is ≥8.5; the concentration of the silica-encapsulated nano-iron particles in the alkaline ethanol solution of the silica-encapsulated nano-iron particles is preferably 0.040-0.10 g / mL, more preferably 0.067 g / mL.

[0072] In the present invention, the conditions for the plasma modification treatment are preferably: the equipment is a plasma processor, the voltage is 30-45KV, the temperature is 80-90°C, the frequency is 300Hz, the time is 2-5min, the concentration of oxygen in the gas used is preferably 50vt%-70vt%, and the gas flow rate used is 2-10L / min.

[0073] In the present invention, the temperature of the hydrolysis reaction is preferably 70-100°C, more preferably 75-95°C; the time of the hydrolysis reaction is preferably 3-7 hours, more preferably 4-5 hours. Through the hydrolysis reaction, the Si-Cl bonds in dimethyldichlorosilane (DCDMS) and the Si-(OH) bonds in the silica-coated nano-iron particles fully react in toluene to ultimately form a long chain structure with Si-O-Si bonds as the main link.

[0074] In the present invention, the mass ratio of the activated silica-coated nano-iron particles, dimethyldichlorosilane and KH-560 type silane coupling agent is preferably (20-80):100:(2-30), more preferably (30-70):100:(10-26).

[0075] In the present invention, the temperature of the coupling reaction is preferably 50 to 70° C.; the time of the coupling reaction is preferably 6 to 10 h.

[0076] After the coupling reaction is completed, the product of the coupling reaction is washed with toluene to obtain hydrophobically modified silica-coated nano-iron particles, referred to as H-SiO2@CIP particles.

[0077] In the present invention, the silicon dioxide-coated nano-iron particles are preferably purchased from the market or prepared in-house.

[0078] In the present invention, the method for preparing the silica-coated nano-iron particles preferably comprises the following steps:

[0079] (T1) After pure water and carbonyl iron powder are stirred and mixed, a first turbid solution is obtained by ultrasonication;

[0080] Mixing anhydrous ethanol, ethyl tetrasilicate and KH-560 silane coupling agent to obtain a second turbid liquid;

[0081] (T2) mixing the first turbid liquid and the second turbid liquid obtained in step (T1), adding L-lysine catalyst, and heat treating under stirring to obtain a mixture;

[0082] (T3) The mixture obtained in step (T2) is allowed to stand for stratification, the upper clear liquid is poured out, and the lower precipitate is washed 2 to 4 times with a 75% ethanol solution, followed by magnetic enrichment, vacuum drying, and grinding to obtain SiO2@CIP particles, i.e., silica-coated nano-iron particles.

[0083] In the present invention, the ultrasonication time is preferably 150 to 220 seconds. The present invention has no specific limitation on the ultrasonication time, as long as the components are uniformly mixed. In the present invention, the concentration of the carbonyl iron powder in the first turbid solution is preferably 4 wt% to 15 wt%, more preferably 5 wt% to 10 wt%.

[0084] In the present invention, the concentration of ethyl tetrasilicate in the second turbid liquid is preferably 0.5wt% to 2wt%, more preferably 0.7wt% to 1.5wt%; the concentration of KH-560 silane coupling agent in the second turbid liquid is preferably 0.5wt% to 2wt%, more preferably 0.8wt% to 1.6wt%.

[0085] In the present invention, the L-lysine catalyst preferably accounts for 0.2 wt% to 1 wt% of the first and second turbid liquids, more preferably 0.5 wt% to 0.8 wt%. In the present invention, the heat treatment temperature is preferably 43 to 58°C, more preferably 45 to 55°C; and the heat treatment time is preferably 2 to 7 hours, more preferably 3 to 5 hours.

[0086] In the present invention, the vacuum drying temperature is preferably 70-80°C, and the vacuum drying time is preferably 18-25 hours, more preferably 20 hours. In the present invention, the particle size of the silica-coated nano-iron particles is preferably 10-200 nm, more preferably 20-150 μm.

[0087] The present invention also provides the use of the net material having both anti-adhesion, self-cleaning and toughness as described in the above technical solution in the preparation of aquaculture nets, comprising the following steps:

[0088] A plurality of strands of the net material are braided to form a net rope, and the net rope is woven to form a knotless mesh, thereby obtaining a breeding net with the characteristics of anti-adhesion, self-cleaning and toughness.

[0089] In the present invention, the net material is preferably used as a monofilament in a net rope; the net rope is preferably braided from three, six, or eight strands of the net material. Braiding the net rope avoids the friction between the monofilaments that can occur with twisting, which can damage the double-layer membrane structure on the anti-adhesion surface of the monofilaments.

[0090] In the present invention, the mesh of the aquaculture net with both anti-adhesion, self-cleaning and toughness is preferably one or more of square, rhombus and regular hexagon.

[0091] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0092] Some of the raw materials used in the examples and comparative examples of the present invention are as follows:

[0093] Polyethylene with a molecular weight of 250,000, produced by Guangzhou Yangu Trading Co., Ltd.

[0094] PET resin with a molecular weight of 130,000, produced by DuPont in the United States;

[0095] The maleic anhydride grafted polyethylene is maleic anhydride grafted PE of model ADDIMER 630R produced by CERONAS of Germany.

[0096] Example 1

[0097] A mesh material that is both anti-adhesive, self-cleaning, and tough, comprising a three-layer structure, from the inside out, comprising an antibacterial polyethylene core layer, an ultra-thin strong magnetic film, and epoxy resin;

[0098] The diameter of the antibacterial polyethylene core layer is 1.5 mm, the thickness of the ultra-thin ferromagnetic film is 100 μm, and the thickness of the epoxy resin layer with H-SiO2@CIP silane microstructure on the surface is 170 μm;

[0099] The preparation method of the net material comprises the following steps:

[0100] S1, preparing an antibacterial polyethylene core layer;

[0101] S2, using a coating machine and a polyurethane emulsion adhesive, tightly covering the surface of the antibacterial polyethylene core layer obtained in step (S1) with an ultra-thin strong magnetic film, and hot pressing at 150° C. for 1 min to obtain a coated antibacterial polyethylene core layer;

[0102] S3. Coating the epoxy resin mixed solution on the surface of the coated antibacterial polyethylene core layer obtained in step (S2), and drying the resulting net material to obtain a net material having both anti-adhesion, self-cleaning and toughness.

[0103] The method for preparing the antibacterial polyethylene core layer in step (S1) comprises the following steps:

[0104] (1) Polyethylene, polyhexamethylene guanidine phosphate, streptomycin, succinic anhydride, and dicumyl peroxide were premixed, and then uniformly blended by rapid mechanical stirring in a water bath at 180°C. Then, a grafting reaction was carried out at 200°C for 4 hours, and then extrusion granulation was performed to obtain antibacterial polymer particles with a particle size of 2 mm;

[0105] The total mass of the polyhexamethylene guanidine phosphate and streptomycin accounts for 20% of the mass of the polyethylene; the mass of the succinic anhydride accounts for 10% of the mass of the polyethylene; and the mass of the dicumyl peroxide initiator accounts for 1.2% of the mass of the polyolefin;

[0106] (2) premixing the antibacterial polymer particles obtained in step (1) with a PET resin having a molecular weight of 300,000, a phenolic antioxidant, and maleic anhydride-grafted polyethylene, kneading at high speed for 1 hour, extruding into granules, and melt-extruded from the spinneret holes of a single-screw extruder, and melt-spinning and stretching to obtain an antibacterial high-molecular polyethylene monofilament core body;

[0107] The mass ratio of the antibacterial polymer particles to the PET resin and maleic anhydride-grafted polyethylene is preferably 1:1.6:1.6; the mass of the phenolic antioxidant 2,6-di-tert-butyl-4-methylphenol accounts for 0.008% of the mass of the antibacterial polymer particles; the diameter of the spinneret is 1.5 mm; and the process conditions for the melt spinning and stretching treatment are: a spinning temperature of 40°C, a spinning speed of 10 m / min, a stretching magnification of 30 times, and a stretching temperature of 100°C.

[0108] The method for preparing the ultrathin ferromagnetic film in step (S2) comprises the following steps: uniformly mixing 60 parts of polyethylene particles, 30 parts of carbonyl iron powder with a diameter of 3 nm, and 3 parts of KH-560 silane coupling agent to obtain surface pretreated particles; extruding the surface pretreated particles in a twin-screw extruder to obtain master batches; and processing the master batches through a blow molding machine to obtain an ultrathin ferromagnetic film.

[0109] The parameters of the twin-screw extruder are preferably: heating temperature of 120-190°C, screw speed of 240 r / min, and feeding speed of 55 r / min; the parameters of the blow molding machine are preferably: heating temperature of 120-210°C, screw speed of 110 r / min, blow-up ratio of 1:2, and traction speed of 6 m / min;

[0110] The step (S3) is specifically as follows:

[0111] (S3-1) 10 g of H-SiO2@CIP was placed in 100 mL of ethyl acetate as a diluent and subjected to ultrasonic treatment to form an ethyl acetate suspension of hydrophobically modified silica-coated nano-iron particles;

[0112] PDMS with a molecular weight of 3000, a methyltri(methoxy)silane crosslinker, and an ethyl acetate suspension of the hydrophobically modified silica-coated nano-iron particles were mixed and stirred in a fume hood to allow the ethyl acetate to fully evaporate. The mixture was then vacuum-defoamed and ultrasonically treated for 15 minutes to obtain a mixed solution.

[0113] The mass ratio of the polydimethylsiloxane, methyltri(methoxy)silane crosslinking agent, and hydrophobically modified silica-coated nano-iron particles is 15:5:10;

[0114] The mixed solution and bisphenol A epoxy resin are mixed, stirred by a single-screw machine for 45 minutes, and then subjected to vacuum defoaming treatment to obtain a mixed solution containing bisphenol A epoxy resin;

[0115] The concentration of bisphenol A epoxy resin in the mixed solution containing bisphenol A epoxy resin is 60wt%;

[0116] (S3-2) spin-coating the mixed solution containing the bisphenol epoxy resin obtained in step (S3-1) onto the surface of the coated antibacterial polyethylene core layer obtained in step (S2) to form a 180 μm coating, and drying the coating in a ventilated drying oven at 50° C. for 18 hours to obtain a mesh material having both anti-adhesion, self-cleaning and toughness;

[0117] The preparation method of the hydrophobically modified silica-coated nano-iron particles (i.e., H-SiO2@CIP) in step (S3-1) comprises the following steps:

[0118] First, prepare silica-coated nano-iron particles, namely SiO2@CIP particles, as follows:

[0119] (T1) adding carbonyl iron powder to pure water, stirring and mixing, and then sonicating for 180 seconds to obtain a first turbid solution;

[0120] The concentration of carbonyl iron powder in the first turbid liquid is 7 wt %;

[0121] Adding ethyl tetrasilicate and KH-560 silane coupling agent into anhydrous ethanol and mixing to obtain a second turbid liquid;

[0122] The concentration of ethyl tetrasilicate in the second turbid liquid is 1 wt %; the concentration of KH-560 silane coupling agent in the second turbid liquid is 1.5 wt %;

[0123] (T2) mixing the first turbid liquid and the second turbid liquid obtained in step (T1), adding L-lysine as a catalyst, stirring with a magnetic stirrer, and heat treating in a constant temperature water bath at 48° C. for 4 h to obtain a mixture;

[0124] The L-lysine catalyst accounts for 0.5 wt% of the total amount of the first turbid liquid and the second turbid liquid;

[0125] (T3) the mixture obtained in step (T2) was allowed to stand for stratification, the supernatant was poured out, the lower precipitate was washed four times with a 75% ethanol solution, magnetically concentrated using a block magnet, and then vacuum dried at 80° C. for 20 h. SiO2@CIP particles with a particle size of 20 μm were obtained by grinding;

[0126] 3 g of SiO2@CIP particles prepared by the above method were mixed with 45 mL of alkaline ethanol solution with a pH of 9 to allow sufficient hydroxyl groups to be obtained on the surface of the SiO2 particles.

[0127] After drying in a fume hood, the SiO2@CIP was then plasma-modified to generate active hydroxyl functional groups on its surface, resulting in activated silica-coated nano-iron particles.

[0128] The conditions of the plasma modification treatment are preferably: the equipment is a plasma treatment machine, the voltage is 36KV, the temperature is 90°C, the frequency is 300Hz, the time is 3min, the oxygen concentration in the gas used is preferably 60vt%, and the gas flow rate is 4L / min;

[0129] The activated silica-coated nano-iron particles were mixed with toluene and DCDMS, and hydrolyzed at 80°C for 5 hours. 0.2 mL of KH-560 was added using a pipette, and then a coupling reaction was carried out at 60°C for 8 hours to promote the coupling of the long-chain structure on the SiO2@CIP surface. The reaction residues were repeatedly rinsed with toluene solution to finally obtain H-SiO2@CIP particles.

[0130] Example 2

[0131] A mesh material with both anti-adhesion, self-cleaning and toughness, which differs from Example 1 in that: in the step (S3-2), the mixed liquid containing bisphenol epoxy resin obtained in the step (S1) is spin-coated on the surface of the coated antibacterial polyethylene core layer to form a 150 μm coating.

[0132] Example 3

[0133] A mesh material with both anti-adhesion, self-cleaning and toughness, which differs from Example 1 in that: in the step (S3-2), the mixed liquid containing bisphenol epoxy resin obtained in the step (S1) is spin-coated on the surface of the coated antibacterial polyethylene core layer to form a 200 μm coating.

[0134] Application Example 1

[0135] A net for aquaculture is prepared by using the net material with both anti-adhesion, self-cleaning and toughness prepared in Example 1 as a monofilament, and the steps are as follows:

[0136] The six strands of the monofilaments are braided to form a net rope, and the net rope is woven to form a knotless mesh with regular hexagonal meshes, thereby obtaining a breeding net with both anti-adhesion, self-cleaning and toughness.

[0137] Application Example 2

[0138] A net for aquaculture is prepared by using the net material with both anti-adhesion, self-cleaning and toughness prepared in Example 2 as a monofilament, and the steps are as follows:

[0139] The six strands of the monofilaments are braided to form a net rope, and the net rope is woven to form a knotless mesh with regular hexagonal meshes, thereby obtaining a breeding net with both anti-adhesion, self-cleaning and toughness.

[0140] Application Example 3

[0141] A net for aquaculture is prepared by using the net material with both anti-adhesion, self-cleaning and toughness prepared in Example 3 as a monofilament, and the steps are as follows:

[0142] The six strands of the monofilaments are braided to form a net rope, and the net rope is woven to form a knotless mesh with regular hexagonal meshes, thereby obtaining a breeding net with both anti-adhesion, self-cleaning and toughness.

[0143] Comparative Example 1

[0144] A net material, which differs from Example 1 in that it only has an antimicrobial polyethylene core layer;

[0145] Then, the net material is used to prepare a breeding net according to the method of Application Example 1.

[0146] Comparative Example 2

[0147] A net material, which differs from Example 1 in that it only has an antibacterial polyethylene core layer and an ultra-thin strong magnetic film;

[0148] Then, the net material is used to prepare a breeding net according to the method of Application Example 1.

[0149] Comparative Example 3

[0150] A mesh material, which differs from Example 1 in that: the outer surface of the epoxy resin layer does not have a hydrophobically modified silica-coated nano-iron particle-silane microstructure, that is, the hydrophobically modified silica-coated nano-iron particles H-SiO2@CIP are not added when preparing the epoxy resin mixed solution;

[0151] Then, the net material is used to prepare a breeding net according to the method of Application Example 1.

[0152] The breaking strength of the aquaculture nets with both anti-adhesion, self-cleaning and toughness prepared in Application Examples 1 to 3 and the aquaculture nets prepared in Comparative Examples 1 to 3 was tested; and the antifouling performance was evaluated after hanging the nets in the actual sea. Among them, if the area of ​​marine fouling attached to the net is less than 10%, the antifouling coating is considered effective. The test results are shown in Table 1.

[0153]

[0154]

[0155] As shown in Table 1, the anti-adhesion and self-cleaning products prepared in Application Examples 1 to 3 of the present invention have an anti-fouling effect of up to 26 months, a corrosion rate as low as 3.3 μm / month, and a breaking strength of 9.7 g / D.

[0156] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A net material with both anti-adhesion, self-cleaning and toughness, characterized in that: It consists of three layers: an antibacterial polyethylene core layer, an ultra-thin strong magnetic film, and an epoxy resin layer with H-SiO2@CIP silane microstructure on the surface. The preparation method of the net material comprises the following steps: S1, preparing an antibacterial polyethylene core layer; S2, coating the antibacterial polyethylene core layer obtained in step S1 with the ultra-thin ferromagnetic film to obtain a coated antibacterial polyethylene core layer; The thickness of the ultra-thin ferromagnetic film is 2-400 μm; The preparation method of the ultra-thin strong magnetic film comprises: mixing resin particles, magnetic powder and a dispersant to obtain surface pre-treated particles; extruding the surface pre-treated particles in a twin-screw extruder to obtain master batches; and processing the master batches through a blow molding machine to obtain the ultra-thin strong magnetic film. S3, coating the epoxy resin mixed solution on the surface of the coated antibacterial polyethylene core layer obtained in step S2, and drying the resulting net material to obtain a net material having both anti-adhesion, self-cleaning and toughness; The step S3 comprises the following steps: (S3-1) mixing a suspension of polydimethylsiloxane, a crosslinking agent, and hydrophobically modified silica-coated nano-iron particles, and sequentially performing a first stirring, a first vacuum degassing, and an ultrasonic treatment to obtain a mixed solution; Adding bisphenol epoxy resin to the mixed solution, and sequentially performing a second stirring and a second vacuum defoaming to obtain an epoxy resin mixed solution; (S3-2) coating the epoxy resin mixed solution obtained in step (S3-1) on the surface of the coated antibacterial polyethylene core layer obtained in step S2, and drying the resulting net material to obtain a net material having both anti-adhesion, self-cleaning and toughness; The method for preparing the hydrophobically modified silica-coated nano-iron particles in step (S3-1) comprises the following steps: The silica-coated nano-iron particles are dispersed in an alkaline ethanol solution, dried, and then subjected to plasma modification to obtain activated silica-coated nano-iron particles; The activated silica-wrapped nano-iron particles are mixed with dimethyldichlorosilane and toluene, and then subjected to a hydrolysis reaction. A KH-560 silane coupling agent is then added to carry out a coupling reaction to obtain hydrophobically modified silica-wrapped nano-iron particles.

2. The net material with both anti-adhesion, self-cleaning and toughness according to claim 1, characterized in that: The diameter of the antibacterial polyethylene core layer is 1-3.5 mm, the thickness of the ultra-thin ferromagnetic film is 2-400 μm, and the thickness of the epoxy resin layer with H-SiO2@CIP silane microstructure on the surface is 80-260 μm.

3. The net material with both anti-adhesion, self-cleaning and toughness according to claim 1 or 2, characterized in that: The method for preparing the antibacterial polyethylene core layer in step S1 comprises the following steps: (1) Premixing polyethylene, an antimicrobial agent, succinic anhydride, and dicumyl peroxide, followed by blending, grafting reaction, and extrusion granulation to obtain antimicrobial polymer particles; (2) The antibacterial polymer particles obtained in step (1) are premixed with PET resin, phenolic antioxidant, and maleic anhydride grafted polyethylene, and then kneaded and extruded into granules in sequence. The mixture is then melt-extruded from the spinneret holes on a single-screw extruder, and subjected to melt spinning and stretching treatment to obtain an antibacterial polyethylene core layer.

4. The net material with both anti-adhesion, self-cleaning and toughness according to claim 3, characterized in that: In the step (1), the antibacterial agent is at least two of polyhexamethylene guanidine phosphate, polyhexamethylene biguanidine phosphate, and streptomycin.

5. The net material with both anti-adhesion, self-cleaning and toughness according to claim 1, characterized in that: The plasma modification treatment lasts for 2 to 5 minutes, and the concentration of oxygen in the gas used for the plasma modification treatment is 50 vt% to 70 vt%.

6. The net material with both anti-adhesion, self-cleaning and toughness according to claim 1, characterized in that: In the step (S3-1), the mass ratio of polydimethylsiloxane, crosslinking agent, and hydrophobically modified silica-wrapped nano-iron particles is 15:(2-8):(6-12).

7. The net material with both anti-adhesion, self-cleaning and toughness according to claim 1, characterized in that: The drying temperature in the step (S3-2) is 45-55°C, and the drying time is 16-20 hours.

8. Use of the net material having both anti-adhesion, self-cleaning and toughness according to any one of claims 1 to 7 in the preparation of aquaculture nets, characterized in that: The following steps are involved: A plurality of strands of the net material are braided to form a net rope, and the net rope is woven to form a knotless mesh, thereby obtaining a breeding net with the characteristics of anti-adhesion, self-cleaning and toughness.

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