A ship hull barnacle protection net

Abstract

The present application provides a kind of ship hull barnacle protection net.The support layer of the protection net is nanofiber membrane with micron pit array formed by laser etching, the inside is attached to the adhesive made of modified dopamine-acrylate copolymer, nano-silica, calcium alginate microspheres, chitosan, chitin nanofiber, lanolin and antioxidant, and the outside is compounded with stainless steel wire mesh.The present application realizes long-term inhibition of barnacles through the physical barrier of the hydrophobic support layer and the synergistic effect of the antifouling components in the adhesive without adding toxic antifouling agents, and has the characteristics of firm bonding, excellent mechanical properties, environmental protection and non-toxicity, effectively solves the problems of poor antifouling effect, insufficient bonding reliability and poor environmental protection of existing protection materials, and is suitable for barnacle protection of underwater parts of ship hull.

Description

Technical Field

[0001] This invention relates to the field of ship protection technology, specifically a barnacle protection net for ship hulls. Background Technology

[0002] Ships navigate in the marine environment for extended periods, making their underwater hulls highly susceptible to the adhesion of marine fouling organisms such as barnacles. This significantly increases drag, fuel consumption, and accelerates hull corrosion, directly impacting navigation efficiency, operational safety, and economic costs. Therefore, barnacle protection has become an indispensable and critical aspect of ship maintenance. Current antifouling methods primarily utilize antifouling paints, which contain toxic materials that can pollute the marine environment. Furthermore, these paints have short maintenance cycles and high overall costs, failing to meet the requirements of green ship development. Existing barnacle-proof netting technologies generally suffer from poor material compatibility, unclear process parameters, weak practicality in installation and maintenance, and a lack of quantifiable standards for protective effectiveness, making it difficult to achieve long-term and stable barnacle protection for ship hulls.

[0003] Existing patent CN202120331169.0 discloses a barnacle-proof net cage that inhibits barnacle attachment by ultraviolet irradiation. However, it uses a constant light or simple light control mode and cannot dynamically adjust the ultraviolet dose. This not only results in high energy consumption, but excessive ultraviolet irradiation also accelerates the aging of the netting material, leading to a rapid decline in the mechanical properties of the netting and a significant reduction in its service life.

[0004] Patent CN202511373146.5 discloses a biomimetic self-cleaning and anti-fouling aquaculture net cage material, which relies on glutaraldehyde cross-linking to modify chitosan and photocatalysis to achieve antifouling. Its antifouling effect is highly dependent on the content of cross-linking agent. Once the aldehyde group is exhausted, the anti-barnacle efficiency will drop sharply, and it cannot maintain long-term stability, making it difficult to apply on a large scale.

[0005] In summary, existing barnacle protection technologies for ship hulls generally suffer from core defects such as short protection life, easy material aging, unstable antifouling effect, poor replacement and recycling, and difficulty in balancing environmental protection and economy. The industry urgently needs an environmentally friendly, non-toxic, long-lasting antifouling, aging-resistant, and easy-to-replace barnacle protection technology for ship hulls to address the shortcomings of existing technologies. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a barnacle protection net for ship hulls, solving the technical problem that "existing protection nets need to be replaced frequently due to their short lifespan, but their recyclability is poor during replacement, making it impossible to achieve long-term and stable anti-fouling through simple replacement".

[0007] To achieve the above objectives, the present invention is implemented using the following technical solution: This invention provides a method for preparing a barnacle protection net for a ship's hull, comprising the following steps: (1) A polymer blend is obtained by melt blending polymeric materials and nanocellulose, which is then formulated into a spinning solution and electrospun to obtain a nanofiber membrane; the surface of the nanofiber membrane is laser etched to form a micron pit array to obtain a hydrophobic support layer. (2) 3-Methacrylamide dopamine was copolymerized with acrylate monomers and N-vinylpyrrolidone monomers under the action of an initiator to obtain a modified dopamine-acrylate copolymer; (3) Add pH adjuster to sodium alginate aqueous solution to obtain a mixture, drop the mixture into calcium chloride aqueous solution, let stand for cross-linking, filter and wash to obtain calcium alginate microspheres; (4) The above-mentioned modified dopamine-acrylate copolymer, nano silica, calcium alginate microspheres, chitosan, chitin nanofibers, lanolin and antioxidant are blended to prepare an adhesive; (5) The above adhesive is applied to the hydrophobic support layer as the substrate and cured to obtain the adhesive tape; stainless steel wire mesh is laminated on the outside of the adhesive tape to obtain the barnacle protection net for the hull.

[0008] In this invention, the polymeric material is polylactic acid-glycolic acid copolymer and polycaprolactone. The polymeric blend comprises, by mass percentage, 55-65% polylactic acid-glycolic acid copolymer, 25-35% polycaprolactone, and 6-12% nanocellulose.

[0009] A polymer blend and solvent are mixed to form a spinning solution of 10-15 wt%, and electrospinning is performed using a voltage of 15-20 kV, a receiving distance of 12-17 cm, and a flow rate of 1-2.5 mL / h to obtain a nanofiber membrane with a thickness of 0.15-0.25 mm. The surface of the nanofiber membrane is then laser-etched to form an array of micron-sized pits with a diameter of 40-60 μm and a depth of 20-40 μm, thus obtaining a hydrophobic support layer.

[0010] Specifically, the acrylate monomer is butyl acrylate.

[0011] Specifically, the initiator is AIBN.

[0012] Specifically, the pH adjuster is glucono-δ-lactone.

[0013] Specifically, the sodium alginate aqueous solution has a mass concentration of 1-3 wt%, the pH adjuster is added at 4-5.5% of the mass of sodium alginate, and the calcium chloride aqueous solution has a concentration of 0.4-0.6 mol / L.

[0014] Specifically, the adhesive comprises, by weight, 35-45 parts of modified dopamine-acrylate copolymer, 10-20 parts of nano-silica, 15-25 parts of calcium alginate microspheres, 9-12 parts of chitosan, 4-6 parts of chitin nanofibers, 7-10 parts of lanolin, and 1.5-2.5 parts of tea polyphenol antioxidant.

[0015] Specifically, the coating speed is 2 to 3.5 m / min, the coating thickness is 100 to 150 μm, the curing temperature is 40 to 60 °C, and the curing time is 4 to 6 min.

[0016] Specifically, the stainless steel wire mesh is 316L stainless steel wire mesh with a wire diameter of 0.1 to 0.3 mm and a mesh count of 20 to 50.

[0017] Compared with the prior art, the beneficial effects achieved by the present invention are: (1) This invention optimizes the preparation process of the hydrophobic support layer, combines nanofiber structure and micron pit array, and uses modified dopamine-acrylate copolymer adhesive to achieve a firm bond between the protective net and the hull, while avoiding residual adhesive after use, thus balancing bonding reliability and subsequent cleaning convenience.

[0018] (2) This invention uses chitosan as the core antifouling component, combined with the slow-release effect of calcium alginate microspheres, without the need to add toxic antifouling agents. It achieves long-term inhibition of fouling organisms such as barnacles, meets marine environmental protection requirements, and reduces pollution to the marine environment.

[0019] (3) The preparation process of the present invention is simple and controllable, and the parameters of each step are precisely matched. From polymer blending and electrospinning to adhesive preparation and composite molding, no complicated equipment is required, and it can be mass-produced. Moreover, the prepared protective net has both excellent mechanical properties and antifouling stability, long service life, and is suitable for the complex marine environment of the ship. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the overall structure of the barnacle protection net on the hull of the present invention. Detailed Implementation

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0022] This invention addresses the shortcomings of existing barnacle protection technologies for ship hulls, such as poor antifouling effect, rapid degradation of mechanical properties, and inconvenient replacement due to excessive adhesive residue after bonding. It provides a long-lasting, stable, and easily removable barnacle protection net for ship hulls. Its core technical principle is as follows: using a hydrophobic support layer as the mechanical base, a nanofiber structure is constructed through electrospinning and combined with a laser-etched array of micron-sized pits to form a high-roughness, low-surface-energy physical anti-adhesion interface, reducing barnacle adhesion sites at the source. A modified dopamine-acrylate copolymer is used as the main adhesive, combined with calcium alginate microspheres, chitosan, chitin nanofibers, and nano-silica components to form a synergistic system of chemical antifouling and interface enhancement, achieving strong adhesion, moderate cohesion, and no adhesive residue upon peeling. Simultaneously, tea polyphenol antioxidants and lanolin are introduced to improve aging and hydrolysis resistance, and the outer composite 316L stainless steel wire mesh ensures overall mechanical strength and service life. This invention achieves low barnacle adhesion rate, high mechanical retention rate, high bonding reliability, and low residual adhesive rate without using toxic antifouling agents or relying on ultraviolet irradiation, effectively solving the problems of short lifespan, poor replaceability and recyclability, and inability to provide long-term stable antifouling protection for protective nets.

[0023] This invention involves mixing 55-65% polylactic-co-glycolic acid copolymer (PLGA), 25-35% polycaprolactone (PCL), and 6-12% nanocellulose by weight percentage, and then melt-blending them at 175-185°C and -0.08MPa vacuum for 40-50 minutes to obtain a polymer blend. This blend is then mixed with dichloromethane to prepare a 10-15wt% spinning solution. Electrospinning is performed using a voltage of 15-20kV, a receiving distance of 12-17cm, and a flow rate of 1-2.5mL / h to obtain a nanofiber membrane with a thickness of 0.15-0.25mm. Laser etching is then performed on the surface of the nanofiber membrane to form an array of micron-sized pits with a diameter of 40-60μm and a depth of 20-40μm, thus obtaining a hydrophobic support layer.

[0024] PLGA provides biodegradability and a certain degree of rigidity, PCL imparts flexibility, and nanocellulose serves as a reinforcing phase, together improving the strength and thermal stability of the fiber membrane. During electrospinning, a high-voltage electric field stretches the spinning solution to form fibers with diameters in the nanometer range, which are then stacked into a three-dimensional porous nanofiber membrane. This structure has extremely high specific surface area and roughness, which physically reduces the attachment sites of barnacle larvae.

[0025] This invention involves mixing 3-methacrylamide dopamine, butyl acrylate, and N-vinylpyrrolidone in a molar ratio of 1:(2~2.2):(1.05~1.1), adding 0.3~0.8wt% AIBN based on the total mass of the three monomers, using DMF / water = 7:3 as the solvent, and polymerizing under nitrogen protection at 55~65℃ for 8~12h to obtain a modified dopamine-acrylate copolymer; preparing a 1~3wt% sodium alginate aqueous solution, and adding 4~5.5% of glucose by weight of sodium alginate to it. A mixture of gluconic acid and δ-lactone was obtained. The mixture was then added dropwise to a 0.4-0.6 mol / L calcium chloride aqueous solution, allowed to stand for crosslinking for 30 min, filtered and washed to obtain calcium alginate microspheres. An adhesive was prepared by weighing 35-45 parts of modified dopamine-acrylate copolymer, 10-20 parts of nano-silica, 15-25 parts of calcium alginate microspheres, 9-12 parts of chitosan, 4-6 parts of chitin nanofibers, 7-10 parts of lanolin, and 1.5-2.5 parts of tea polyphenol antioxidant.

[0026] A copolymer of 3-methacrylamide, butyl acrylate, and N-vinylpyrrolidone was obtained, exhibiting strong adhesion, flexibility, and hydrophilicity regulation. The catechol groups formed strong coordination bonds with the steel plate surface of the ship hull, achieving strong underwater adhesion. Simultaneously, calcium alginate microspheres were prepared using a slow acidification method with gluconate-δ-lactone, serving as both a slow-release carrier and cohesive sacrificial particles to reduce residual adhesive. This copolymer was then blended with nano-silica, calcium alginate microspheres, chitosan, chitin nanofibers, lanolin, and tea polyphenols. Chitosan and chitin fibers formed a polysaccharide antifouling network, interfering with barnacle adhesion. Nano-silica enhanced mechanical properties, lanolin reduced surface energy, and tea polyphenols provided anti-aging benefits. The components synergistically achieved strong adhesion, low residual adhesive, and long-lasting barnacle inhibition.

[0027] This invention uses a hydrophobic support layer as a substrate, coats it with the adhesive prepared above, at a coating speed of 2~3.5m / min and a coating thickness of 100~150μm, and cures it at 40~60℃ for 4~6min to obtain an adhesive cloth. Then, a 316L stainless steel wire mesh is laminated to the outer side of the adhesive cloth by hot rolling at a temperature of 50~70℃ and a pressure of 0.3~0.5MPa to obtain a barnacle protection net for the ship hull.

[0028] In this embodiment of the invention, the stainless steel wire mesh is 316L stainless steel wire mesh with a wire diameter of 0.1 to 0.3 mm and a mesh count of 20 to 50.

[0029] Example 1; (1) By mass percentage, 55% polylactic acid-glycolic acid copolymer, 33% polycaprolactone and 12% nanocellulose were mixed and melt-blended at 175℃ and -0.08MPa vacuum for 40 min; electrospinning was performed at a voltage of 15kV, a receiving distance of 12cm and a flow rate of 1mL / h to obtain a nanofiber membrane with a thickness of 0.15mm; laser etching was performed on the surface of the nanofiber membrane to form a micron pit array with a diameter of 40μm and a depth of 20μm, thus obtaining a hydrophobic support layer; (2) 3-methacrylamide dopamine, butyl acrylate and N-vinylpyrrolidone were mixed in a molar ratio of 1:2:1.05. 0.3wt% AIBN was added based on the total mass of the three monomers. DMF / water = 7:3 was used as the solvent. The mixture was polymerized at 55°C for 8 hours under nitrogen protection to obtain the modified dopamine-acrylate copolymer. (3) Prepare a 1wt% sodium alginate aqueous solution, add 4% gluconate-δ-lactone (based on the mass of sodium alginate) to it to obtain a mixture, drop the mixture into a 0.4mol / L calcium chloride aqueous solution, let it stand for cross-linking for 30min, filter and wash to obtain calcium alginate microspheres; (4) Weigh 35 parts of modified dopamine-acrylate copolymer, 10 parts of nano silica, 15 parts of calcium alginate microspheres, 9 parts of chitosan, 4 parts of chitin nanofibers, 7 parts of lanolin and 1.5 parts of tea polyphenol antioxidant by weight and mix them to prepare an adhesive. (5) Using the hydrophobic support layer as the substrate, the adhesive prepared above is coated at a coating speed of 2m / min and a coating thickness of 100μm. The adhesive is cured at 40℃ for 4min to obtain the adhesive cloth. The 316L stainless steel wire mesh with a wire diameter of 0.1mm and a mesh size of 20 is combined with the outer side of the adhesive cloth by hot rolling. The temperature of the hot rolling is 50℃ and the pressure is 0.3MPa to obtain the barnacle protection net for the ship hull.

[0030] Example 2; (1) By mass percentage, 60% polylactic acid-glycolic acid copolymer, 30% polycaprolactone and 10% nanocellulose were mixed and melt-blended at 180℃ and -0.08MPa vacuum for 45 min; electrospinning was performed using a voltage of 17kV, a receiving distance of 15cm and a flow rate of 1.5ml / h to obtain a nanofiber membrane with a thickness of 0.2mm; laser etching was performed on the surface of the nanofiber membrane to form a micron pit array with a diameter of 50μm and a depth of 30μm, thus obtaining a hydrophobic support layer; (2) Mix 3-methacrylamide, butyl acrylate and N-vinylpyrrolidone in a molar ratio of 1:2:1, add 0.5wt% AIBN based on the total mass of the three monomers, use DMF / water = 7:3 as solvent, and polymerize at 60℃ for 10h under nitrogen protection to obtain modified dopamine-acrylate copolymer. (3) Prepare a 1.5wt% sodium alginate aqueous solution, add 5% gluconate-δ-lactone by mass of sodium alginate to obtain a mixture, drop the mixture into a 0.5mol / L calcium chloride aqueous solution, let it stand for cross-linking for 30min, filter and wash to obtain calcium alginate microspheres; (4) Weigh 40 parts of modified dopamine-acrylate copolymer, 15 parts of nano silica, 20 parts of calcium alginate microspheres, 10 parts of chitosan, 5 parts of chitin nanofibers, 8 parts of lanolin and 2 parts of tea polyphenol antioxidant by weight and mix them to prepare an adhesive. (5) Using the hydrophobic support layer as the substrate, the adhesive prepared above is coated at a coating speed of 3m / min and a coating thickness of 120μm. The adhesive is cured at 50℃ for 5min to obtain the adhesive cloth. The 316L stainless steel wire mesh with a wire diameter of 0.2mm and a mesh size of 30 mesh is combined with the outer side of the adhesive cloth by hot rolling. The temperature of the hot rolling is 60℃ and the pressure is 0.4MPa to obtain the barnacle protection net for the hull.

[0031] Example 3; (1) By mass percentage, 65% polylactic acid-glycolic acid copolymer, 25% polycaprolactone and 10% nanocellulose were mixed and melt-blended at 185℃ and -0.08MPa vacuum for 50 min; electrospinning was performed using a voltage of 20kV, a receiving distance of 17cm and a flow rate of 2.5mL / h to obtain a nanofiber membrane with a thickness of 0.25mm; laser etching was performed on the surface of the nanofiber membrane to form a micron pit array with a diameter of 60μm and a depth of 40μm, thus obtaining a hydrophobic support layer; (2) 3-methacrylamide dopamine, butyl acrylate and N-vinylpyrrolidone were mixed in a molar ratio of 1:2.2:1.1. 0.8wt% AIBN was added based on the total mass of the three monomers. DMF / water = 7:3 was used as the solvent. The mixture was polymerized at 65°C for 12h under nitrogen protection to obtain the modified dopamine-acrylate copolymer. (3) Prepare a 3wt% sodium alginate aqueous solution, add 5.5% gluconate-δ-lactone (by mass of sodium alginate) to it to obtain a mixture, drop the mixture into a 0.6mol / L calcium chloride aqueous solution, let it stand for crosslinking for 30min, filter and wash to obtain calcium alginate microspheres; (4) Weigh 45 parts of modified dopamine-acrylate copolymer, 20 parts of nano silica, 25 parts of calcium alginate microspheres, 12 parts of chitosan, 6 parts of chitin nanofibers, 10 parts of lanolin and 2.5 parts of tea polyphenol antioxidant by weight to prepare an adhesive. (5) Using the hydrophobic support layer as the substrate, the adhesive prepared above is coated at a coating speed of 3.5 m / min and a coating thickness of 150 μm. The adhesive is cured at 60°C for 6 min to obtain the adhesive cloth. The 316L stainless steel wire mesh with a wire diameter of 0.3 mm and a mesh size of 50 mesh is combined with the outer side of the adhesive cloth by hot rolling. The temperature of the hot rolling is 70°C and the pressure is 0.5 MPa to obtain the barnacle protection net for the ship hull.

[0032] Example 4; (1) By mass percentage, 59% polylactic acid-glycolic acid copolymer, 35% polycaprolactone and 6% nanocellulose were mixed and melt-blended at 180℃ and -0.08MPa vacuum for 45 min; electrospinning was performed at a voltage of 17kV, a receiving distance of 14cm and a flow rate of 1.5mL / h to obtain a nanofiber membrane with a thickness of 0.2mm; laser etching was performed on the surface of the nanofiber membrane to form a micron pit array with a diameter of 45μm and a depth of 25μm, thus obtaining a hydrophobic support layer; (2) 3-methacrylamide dopamine, butyl acrylate and N-vinylpyrrolidone were mixed in a molar ratio of 1:2.05:1.1. 0.4wt% AIBN was added based on the total mass of the three monomers. DMF / water = 7:3 was used as the solvent. The mixture was polymerized at 60°C for 12h under nitrogen protection to obtain the modified dopamine-acrylate copolymer. (3) Prepare a 1.5wt% sodium alginate aqueous solution, add 4.5% gluconate-δ-lactone by mass of sodium alginate to it to obtain a mixture, drop the mixture into a 0.5mol / L calcium chloride aqueous solution, let it stand for cross-linking for 30min, filter and wash to obtain calcium alginate microspheres; (4) Weigh 38 parts of modified dopamine-acrylate copolymer, 15 parts of nano silica, 18 parts of calcium alginate microspheres, 11 parts of chitosan, 5 parts of chitin nanofibers, 9 parts of lanolin and 2 parts of tea polyphenol antioxidant by weight and mix them to prepare an adhesive. (5) Using the hydrophobic support layer as the substrate, the adhesive prepared above is coated at a coating speed of 2.5 m / min and a coating thickness of 110 μm. The adhesive is cured at 50°C for 5.5 min to obtain the adhesive cloth. The 316L stainless steel wire mesh with a wire diameter of 0.2 mm and a mesh size of 30 mesh is combined with the outer side of the adhesive cloth by hot rolling. The temperature of the hot rolling is 60°C and the pressure is 0.4 MPa to obtain the barnacle protection net for the hull.

[0033] Example 5; (1) By mass percentage, 63% polylactic acid-glycolic acid copolymer, 32% polycaprolactone and 11% nanocellulose were mixed and melt-blended at 180℃ and -0.08MPa vacuum for 45 min; electrospinning was performed at a voltage of 17kV, a receiving distance of 14cm and a flow rate of 1.5mL / h to obtain a nanofiber membrane with a thickness of 0.2mm; laser etching was performed on the surface of the nanofiber membrane to form a micron pit array with a diameter of 45μm and a depth of 25μm, thus obtaining a hydrophobic support layer; (2) 3-methacrylamide dopamine, butyl acrylate and N-vinylpyrrolidone were mixed in a molar ratio of 1:2.1:1.1, and 0.65wt% AIBN was added based on the total mass of the three monomers. DMF / water = 7:3 was used as the solvent. The mixture was polymerized at 60°C for 11h under nitrogen protection to obtain the modified dopamine-acrylate copolymer. (3) Prepare a 2.5wt% sodium alginate aqueous solution, add 5.2% gluconate-δ-lactone by mass of sodium alginate to it to obtain a mixture, drop the mixture into a 0.5mol / L calcium chloride aqueous solution, let it stand for cross-linking for 30min, filter and wash to obtain calcium alginate microspheres; (4) Weigh 42 parts of modified dopamine-acrylate copolymer, 18 parts of nano silica, 23 parts of calcium alginate microspheres, 10 parts of chitosan, 5 parts of chitin nanofibers, 8 parts of lanolin and 2.2 parts of tea polyphenol antioxidant by weight and mix them to prepare an adhesive. (5) Using the hydrophobic support layer as the substrate, the adhesive prepared above is coated at a coating speed of 3.2 m / min and a coating thickness of 140 μm. The adhesive is cured at 55°C for 4.5 min to obtain the adhesive cloth. The 316L stainless steel wire mesh with a wire diameter of 0.2 mm and a mesh size of 30 mesh is combined with the outer side of the adhesive cloth by hot rolling. The temperature of the hot rolling is 60°C and the pressure is 0.5 MPa to obtain the barnacle protection net for the ship hull.

[0034] Comparative Example 1; The difference between Comparative Example 1 and Example 2 lies in the different step (1). Step (1) is modified as follows: 60% polylactic acid-glycolic acid copolymer, 30% polycaprolactone, and 10% nanocellulose are mixed by mass percentage and melt-blended at 180°C and -0.08MPa vacuum for 45 min; electrospinning is performed using a voltage of 17kV, a receiving distance of 15cm, and a flow rate of 1.5ml / h to obtain a hydrophobic support layer with a thickness of 0.2mm; the remaining steps are the same as in Example 2.

[0035] Comparative Example 2; The difference between Comparative Example 2 and Example 2 is that step (2) is omitted, and step (4) is modified as follows: 15 parts by weight of nano silica, 20 parts by weight of calcium alginate microspheres, 10 parts by weight of chitosan, 5 parts by weight of chitin nanofibers, 8 parts by weight of lanolin and 2 parts by weight of tea polyphenol antioxidant are weighed and mixed to prepare an adhesive; the remaining steps are the same as in Example 2.

[0036] Comparative Example 3; The difference between Comparative Example 3 and Example 2 is that step (3) is omitted, and step (4) is changed to: weigh 40 parts of modified dopamine-acrylate copolymer, 15 parts of nano silica, 10 parts of chitosan, 5 parts of chitin nanofiber, 8 parts of lanolin and 2 parts of tea polyphenol antioxidant by weight and mix them to prepare an adhesive; the remaining steps are the same as in Example 2.

[0037] like Figure 1 As shown, the barnacle protection net for the hull of the present invention comprises, from the inside out, an adhesive sheet and a stainless steel wire mesh laminated to the outside of the adhesive sheet. The adhesive sheet is adhered to the surface of the hull for installation and use, while the stainless steel wire mesh serves as an outer reinforcing structure to enhance the overall tear resistance and impact resistance of the protection net, thus jointly preventing barnacles from attaching.

[0038] Test and Results Analysis Barnacle adhesion rate: Referring to GB / T5370-2007 "Test method for shallow sea immersion of antifouling paint samples", the samples (300mm×300mm in size) covered with barnacle protective netting of each embodiment and comparative example were immersed in artificial seawater for 6 months and then taken out. The proportion of barnacle and large fouling organisms covering the total area of ​​the sample was counted, and the barnacle adhesion rate was calculated.

[0039] Peel strength: Referring to GB / T2792-2014 "Test method for peel strength of adhesive tape", the protective net tape was flatly attached to a 300mm×300mm steel plate sample. After being placed at room temperature for 24 hours, the test was carried out using a universal testing machine in 180° peel mode and peel speed of 300mm / min. The average force during the peeling process was recorded, and the 180° peel strength between the tape and the steel plate was calculated.

[0040] Tensile strength retention rate: The samples (300mm×300mm) covered with the barnacle protection netting of each embodiment and comparative example were soaked in artificial seawater for 6 months and then taken out to test the tensile strength and calculate the ratio with the initial strength.

[0041] Surface contact angle: The contact angle was measured using a contact angle measuring instrument. The test medium was deionized water with a droplet volume of 5 μL. Under the conditions of 25°C and 50% humidity, three test points were randomly selected on the surface of the adhesive tape of each embodiment and comparative example for measurement. The average value was taken as the surface water contact angle of the sample.

[0042] Residual adhesive rate: The samples (300mm×300mm) covered with the barnacle protection netting of each embodiment and comparative example were soaked in artificial seawater for 30 days. After removal, the adhesive was manually peeled off at a speed of 0.3m / min. After peeling, the surface of the steel plate was photographed with a high-definition camera, and the percentage of the area of ​​adhesive residue was calculated using ImageJ image processing software. The specific results are shown in Table 1.

[0043] Table 1

[0044] Examples 1-5 show barnacles with low adhesion rate, high peel strength, high tensile strength retention rate, large surface contact angle, and low residual adhesive rate, exhibiting excellent overall performance. This demonstrates that the present invention achieves efficient antifouling, strong adhesion, mechanical stability, hydrophobic anti-adhesion, and low peel residue through the synergistic effect of laser-etched hydrophobic structure, modified dopamine-acrylate copolymer, calcium alginate microspheres, chitosan, and nano-reinforcing components.

[0045] Comparative Example 1, which did not undergo laser etching of the micron-shaped pit array, resulted in poor surface hydrophobicity, weak bonding strength at the interface, and reduced anti-fouling effect, indicating that laser etching of the microstructure is the key to improving hydrophobicity and interfacial bonding strength.

[0046] In Comparative Example 2, without the preparation or addition of the modified dopamine-acrylate copolymer, the adhesive bonding performance and interfacial anti-adhesion ability were significantly reduced, the barnacle adhesion rate increased, and the residual adhesive rate increased, indicating that the modified dopamine-acrylate copolymer is the core component that ensures bonding strength, low surface energy, and low residual adhesive.

[0047] Comparative Example 3, without the preparation or addition of calcium alginate microspheres, showed uneven release of antifouling components and imbalance of adhesive cohesion, resulting in poorer antifouling effect and mechanical stability. This indicates that calcium alginate microspheres can stabilize the antifouling effect and optimize the interfacial properties of the adhesive.

[0048] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A method for preparing a barnacle protection net for a ship's hull, characterized in that, Includes the following steps: (1) A polymer blend is obtained by melt blending polymeric materials and nanocellulose, which is then formulated into a spinning solution and electrospun to obtain a nanofiber membrane; the surface of the nanofiber membrane is laser etched to form a micron pit array to obtain a hydrophobic support layer. (2) 3-Methacrylamide dopamine was copolymerized with acrylate monomers and N-vinylpyrrolidone monomers under the action of an initiator to obtain a modified dopamine-acrylate copolymer; (3) Add pH adjuster to sodium alginate aqueous solution to obtain a mixture, drop the mixture into calcium chloride aqueous solution, let stand for cross-linking, filter and wash to obtain calcium alginate microspheres; (4) The above-mentioned modified dopamine-acrylate copolymer, nano silica, calcium alginate microspheres, chitosan, chitin nanofibers, lanolin and antioxidant are blended to prepare an adhesive; (5) The above adhesive is applied to the hydrophobic support layer as the substrate and cured to obtain the adhesive tape; stainless steel wire mesh is laminated on the outside of the adhesive tape to obtain the barnacle protection net for the hull.

2. The method according to claim 1, characterized in that, The polymer blend mentioned in step (1) comprises, by mass percentage, 55-65% polylactic acid-glycolic acid copolymer, 25-35% polycaprolactone, and 6-12% nanocellulose.

3. The method according to claim 1, characterized in that, The diameter of the micron-sized pit in step (1) is 40~60μm and the depth is 20~40μm.

4. The method according to claim 1, characterized in that, The thickness of the nanofiber membrane in step (1) is 0.15~0.25 mm.

5. The method according to claim 1, characterized in that, The acrylate monomer mentioned in step (2) is butyl acrylate.

6. The method according to claim 1, characterized in that, The initiator in step (2) is AIBN.

7. The method according to claim 1, characterized in that, The pH adjuster mentioned in step (3) is gluconate-δ-lactone.

8. The method according to claim 1, characterized in that, The sodium alginate aqueous solution in step (3) has a mass concentration of 1-3 wt%, the amount of pH adjuster added is 4-5.5% of the mass of sodium alginate, and the concentration of calcium chloride aqueous solution is 0.4-0.6 mol / L.

9. The method according to claim 1, characterized in that, The adhesive components described in step (4) include, by weight, 35-45 parts of modified dopamine-acrylate copolymer, 10-20 parts of nano silica, 15-25 parts of calcium alginate microspheres, 9-12 parts of chitosan, 4-6 parts of chitin nanofibers, 7-10 parts of lanolin and 1.5-2.5 parts of tea polyphenol antioxidant.

10. The method according to claim 1, characterized in that, The coating speed in step (5) is 2 to 3.5 m / min, the coating thickness is 100 to 150 μm, the curing temperature is 40 to 60 °C, and the curing time is 4 to 6 min.

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