Production process of wear-resistant anti-aging composite material for fishing net

Abstract

The invention discloses a production process of a wear-resistant anti-aging composite material for a fishing net, and relates to the technical field of composite materials. The invention discloses a wear-resistant anti-aging composite material for a fishing net. The composite material is prepared from the following raw materials in parts by weight: 32 to 38 parts of modified polycaprolactone, 10 to 14 parts of modified nano cellulose, 18 to 22 parts of para-aramid, 6 to 9 parts of sodium carboxymethyl cellulose, 3 to 5 parts of boron nitride nanosheets, 7 to 11 parts of ultra-high molecular weight polyethylene fibers, 5 to 7 parts of anatase type nano titanium dioxide, 12 to 16 parts of cellulose acetate and 4 to 6 parts of chitosan quaternary ammonium salt. The invention relates to a high-molecular-weight composite material which is prepared from the following components in parts by weight: 5-7 parts of high-molecular-weight sodium lignin sulfonate, 9-13 parts of polyurethane acrylate, 4-6 parts of basalt continuous fibers, 3-5 parts of collagen, 7-9 parts of novolac epoxy resin, 1.2-1.8 parts of a silane coupling agent KH-560 and 0.6-1.2 parts of a hindered amine light stabilizer. The prepared fishing net composite material is reasonable in raw material ratio, and the raw materials are modified, so that the fishing net composite material has the properties of high strength, aging resistance and the like. And the production process is mature and has strong operability. The material gives consideration to performance and economic benefits and is beneficial to popularization and application in the fishery field.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, in particular to a production process of wear-resistant and aging-resistant composite materials for fishing nets. Background Art

[0002] In fishery production, the performance of fishing net materials is crucial to fishing operations and the sustainable development of the fishery industry. Traditional fishing net materials, such as ordinary nylon and polyethylene, have many drawbacks.

[0003] Traditional fishing nets have poor wear resistance and are easily damaged by the frequent friction with reefs and the seabed. For example, in coastal trawling, a medium-sized fishing vessel will need to replace its nets two or three times during a single fishing season due to severe wear. Each replacement, including materials and labor, costs thousands of yuan, significantly increasing fishing costs.

[0004] Its aging resistance is also insufficient. Long-term exposure to ultraviolet rays and seawater erosion reduces its strength and makes it brittle. In areas with strong sunlight and high salinity, fishing nets typically lose 30%-50% of their strength after six months of use. This makes them prone to breaking during fishing, resulting in lost catch and severely impacting fishing efficiency.

[0005] Traditional fishing nets are weak in marine environments. Saltwater and microorganisms accelerate corrosion, reducing the quality of the nets. For example, in tropical waters, where microorganisms are active, the mesh of the nets can become larger due to corrosion after just a few months of use, affecting fishing efficiency and necessitating early replacement.

[0006] Furthermore, traditional fishing nets lack adhesion resistance, allowing marine organisms to easily attach. Statistics show that in some waters, these organisms can increase the weight of fishing nets by 20%-50%, increasing water resistance, reducing fishing efficiency, and increasing energy consumption by fishing vessels. Removing these organisms is also an extremely laborious task, requiring significant manpower, material resources, and time.

[0007] Furthermore, traditional fishing nets are often made of non-biodegradable materials and remain in the ocean for long periods after being discarded, causing severe "white pollution." Every year, a large number of discarded fishing nets enter the ocean, severely disrupting the marine ecosystem and threatening the survival of marine life, such as by entanglement, injury, and even death.

[0008] With the modernization of fisheries and the increasing awareness of environmental protection, the development of high-performance, environmentally friendly fishing net materials is urgent. The present invention aims to solve these problems and meet the needs of modern fisheries. Summary of the Invention

[0009] In view of the deficiencies in the prior art, the present invention provides a production process for a wear-resistant and anti-aging composite material for fishing nets, which solves the above-mentioned problems.

[0010] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0011] A wear-resistant and anti-aging composite material for fishing nets comprises the following raw materials in parts by weight: 32-38 parts of modified polycaprolactone, 10-14 parts of modified nanocellulose, 18-22 parts of para-aramid, 6-9 parts of sodium carboxymethyl cellulose, 3-5 parts of boron nitride nanosheets, 7-11 parts of ultra-high molecular weight polyethylene fibers, 5-7 parts of anatase nano-titanium dioxide, 12-16 parts of cellulose acetate, 4-6 parts of chitosan quaternary ammonium salt, 5-7 parts of high molecular weight sodium lignin sulfonate, 9-13 parts of polyurethane acrylate, 4-6 parts of basalt continuous fibers, 3-5 parts of collagen, 7-9 parts of phenolic epoxy resin, 1.2-1.8 parts of silane coupling agent KH-560, and 0.6-1.2 parts of hindered amine light stabilizer.

[0012] Furthermore, the epoxy equivalent of the phenolic epoxy resin is 0.55eq / 100g; the molecular weight of the ultra-high molecular weight polyethylene fiber is ≥3 million Da; the quaternization substitution degree of the chitosan quaternary ammonium salt is ≥80%; and the hindered amine light stabilizer is one of Tinuvin 770 and Chimassorb 944.

[0013] Furthermore, the modified nanocellulose is specifically prepared in the following steps:

[0014] A1. Place nanocellulose with an average particle size of 50 nm in a reaction vessel, add deionized water, stir, and ultrasonically disperse for 60 minutes to form a uniform suspension; then add 3-aminopropyltriethoxysilane, and stir at 80°C for 3.5 hours. After the reaction, wash, centrifuge, pour off the supernatant, and precipitate and dry to obtain amino-modified nanocellulose;

[0015] A2. Add the above-mentioned amino-treated nanocellulose to a silver nitrate aqueous solution, stir evenly, and then slowly add a glucose solution dropwise at 50° C. and continue stirring for 2.5 hours. After the reaction is complete, wash with deionized water, centrifuge after each wash, pour off the supernatant, precipitate and dry to obtain nanocellulose loaded with nanosilver particles;

[0016] A3. The nanocellulose loaded with nanosilver particles was added to a Tris-HCl buffer solution, followed by addition of dopamine hydrochloride. The mixture was stirred and reacted at room temperature for 20 h. After the reaction, the mixture was washed with deionized water, centrifuged after each wash, the supernatant was poured out, and the precipitate was dried to obtain modified nanocellulose.

[0017] Furthermore, in the step A1, the ratio of nanocellulose, deionized water, and 3-aminopropyltriethoxysilane is 12 g: 80 mL: 3 g; the stirring speed is 300 r / min; the mixture is washed with deionized water 5 times, the centrifugal separation speed is 6000 r / min, and the precipitate is dried at 80°C for 18 h; in the step A2, the ratio of silver nitrate aqueous solution to glucose solution is 120 mL: 20 mL; the concentration of silver nitrate aqueous solution is 0.08 mol / L; the mass fraction of glucose solution is 10%; the stirring speed is 300 r / min; the mixture is washed with deionized water 5 times, the centrifugal separation speed is 6000 r / min, and the precipitate is dried at 80°C for 18 h. The stirring speed is 200 r / min; the mixture is repeatedly washed with deionized water 6 times, the centrifugal separation speed is 6500 r / min, and the precipitate is dried at 75°C for 14 hours; in the step A3, the amount ratio of Tris-HCl buffer solution and dopamine hydrochloride is 130 mL:5 g; the pH of the Tris-HCl buffer solution is 8.5, and the concentration is 10 mmol / L; the stirring speed is 200 r / min; the mixture is washed with deionized water 5 times, the centrifugal separation speed is 5000 r / min, and the precipitate is dried at 70°C for 12 hours.

[0018] The surface of nanocellulose is aminated to introduce amino groups, enhancing its reactivity and compatibility with other substances. Silver nanoparticles are loaded to utilize their antibacterial properties to inhibit the attachment of marine organisms to fishing nets. Polydopamine, a highly adhesive and biocompatible material, is grafted onto the surface of the material, forming a protective film that improves wear resistance and anti-aging properties while also enhancing antibacterial and anti-adhesion properties.

[0019] Furthermore, the modified polycaprolactone is specifically prepared in the following steps:

[0020] B1. Add polycaprolactone to a reactor, heat to 150° C. to melt it, then add hexamethylene diisocyanate, and stir under nitrogen for 2.5 hours. After the reaction, cool to room temperature to obtain chain-extended modified polycaprolactone;

[0021] B2. Add the chain-extended modified polycaprolactone to tetrahydrofuran, stir and dissolve, then add hydroxyethyl methacrylate and azobisisobutyronitrile, and carry out free radical polymerization at 70° C. for 5 h while maintaining the stirring speed. After the reaction is completed, transfer the reaction solution to a rotary evaporator for vacuum distillation until the tetrahydrofuran is completely evaporated, and dry the product to obtain a hydrophilically modified polycaprolactone.

[0022] B3. The hydrophilically modified polycaprolactone was added to a reactor, glycolide and stannous octoate were added, and the mixture was stirred at 130° C. for 4 h to carry out a ring-opening polymerization reaction. After the reaction, the mixture was washed with deionized water, centrifuged after each washing, the supernatant was poured out, and the precipitate was dried to obtain a modified polycaprolactone.

[0023] Furthermore, in step B1, the amount ratio of polycaprolactone and hexamethylene diisocyanate is 35g:4g; the stirring speed is 120r / min; in step B2, the amount ratio of tetrahydrofuran, hydroxyethyl methacrylate, and azobisisobutyronitrile is 120mL:5g:0.8g; the stirring speed is 300r / min; the pressure is controlled to 10kPa during reduced pressure distillation, the initial distillation temperature is set to 40°C, and the temperature is gradually increased to 60°C at a heating rate of 2°C / min; the product is dried at 65°C for 14h; in step B3, the amount ratio of glycolide and stannous octoate is 4g:0.3g; the reaction stirring speed is 200r / min; washed with deionized water 5 times, the centrifugal separation speed is 6000r / min, and the product is dried at 70°C for 12h.

[0024] During chain extension modification, hexamethylene diisocyanate reacts with polycaprolactone to increase molecular chain length, improve molecular weight, and enhance mechanical properties. Hydrophilic groups are introduced by free radical polymerization of hydroxyethyl methacrylate with polycaprolactone under the action of an initiator. This introduces hydrophilic groups into the molecular chain, enhancing water permeability and flexibility, reducing surface tension, and minimizing bioadhesion. Grafting biodegradable segments involves ring-opening polymerization of glycolide with polycaprolactone under the catalysis of stannous octoate. This introduces biodegradable segments, enhancing the material's biodegradability and enabling its gradual decomposition in the environment.

[0025] A method for preparing a wear-resistant and anti-aging composite material for fishing nets, specifically comprising the following steps:

[0026] S1. Soaking para-aramid, ultra-high molecular weight polyethylene fiber, and basalt continuous fiber in a sulfuric acid solution, then repeatedly rinsing with deionized water until neutral, and drying to complete the surface activation pretreatment of the fibers;

[0027] S2, adding sodium carboxymethyl cellulose, chitosan quaternary ammonium salt, and collagen to deionized water, heating and stirring to dissolve, and forming a uniform macromolecular solution;

[0028] S3, adding the fibers pretreated in step S1 to the macromolecular solution obtained in step S2, stirring evenly, then sequentially adding polyurethane acrylate, phenolic epoxy resin, cellulose acetate, and high molecular weight sodium lignin sulfonate, and continuing stirring to prepare a uniform mixed slurry;

[0029] S4, adding modified nanocellulose, modified polycaprolactone, boron nitride nanosheets, anatase nano-titanium dioxide, silane coupling agent KH-560, and hindered amine light stabilizer to the mixed slurry, and stirring to fully mix the raw materials;

[0030] S5. The evenly mixed material is conveyed to a twin-screw extruder for extrusion granulation, and the temperature and screw speed are set to obtain composite material particles; the composite material particles are spun through a melt spinning machine, and the spinning temperature and draft ratio are set to finally produce a wear-resistant and anti-aging composite material for fishing nets.

[0031] Furthermore, in step S1, the mass fraction of the sulfuric acid solution is 8-12%, the soaking time is 40-60 minutes, and the product is dried at 70-85° C. for 14-18 hours; in step S2, the reaction temperature is 55-75° C., and the stirring speed is 300-400 r / min.

[0032] Furthermore, in the step S3, the stirring speed is 300-400 r / min, and the stirring time is 50-80 min; in the step S4, the reaction temperature is 40-60°C, the stirring speed is 350-450 r / min, and the stirring time is 80-120 min.

[0033] Furthermore, in the step S5, the extrusion temperature is set to 150-170° C., the screw speed is controlled at 130-170 r / min, the spinning temperature is 160-180° C., and the draft ratio is 4-6 times.

[0034] The present invention provides a production process for wear-resistant and anti-aging composite materials for fishing nets, which has the following characteristics:

[0035] Beneficial effects:

[0036] 1. The present invention greatly improves the comprehensive performance of the composite material by modifying and compounding multiple raw materials such as polycaprolactone and nanocellulose. After the modified nanocellulose is treated with surface amination, loading of nanosilver particles and grafting of polydopamine, it not only enhances the compatibility with other raw materials, but also effectively reduces the attachment of marine organisms by virtue of the antibacterial property of nanosilver. At the same time, the grafting of polydopamine further improves the wear resistance and anti-aging properties of the material. The modified polycaprolactone increases the molecular weight and improves the mechanical strength through chain extension modification; the introduction of hydrophilic groups enhances the water permeability and flexibility; and the grafting of degradable segments gives the material degradable properties. The synergy of multiple raw materials makes the prepared fishing net composite material have high strength and can withstand the huge pulling force in fishing operations; the high wear resistance reduces the loss caused by friction with the outside world; the excellent anti-aging and corrosion resistance enable it to maintain stable performance under the long-term erosion of ultraviolet rays and seawater, thereby extending the service life of the fishing net.

[0037] 2. The composite material has excellent anti-adhesion and water permeability, which plays a key role in improving fishing efficiency. By reducing the adhesion of marine organisms to the fishing net, the resistance the fishing net encounters in the water is significantly reduced. In actual fishing operations, fishermen can more easily deploy and retract the fishing net, saving a considerable amount of manpower and time costs. At the same time, its excellent water permeability enables the fishing net to drain quickly during fishing, reducing the weight and resistance of the fishing net in the water, making the fishing process smoother and more efficient. For example, in purse seine fishing operations, the rapid drainage characteristics can make the fishing net close faster, increase the catch, reduce energy consumption, and improve the economic benefits of fishery production.

[0038] 3. The present invention has been optimized in terms of raw material formula and production process, achieving cost reduction while ensuring high performance. By modifying the raw materials, the performance of the materials is significantly improved, and the durability of the fishing net is greatly improved. Compared with traditional fishing nets, the replacement frequency of the fishing nets prepared by the present invention is significantly reduced. Assuming that a fishing boat originally needs to replace the traditional fishing net three times in a fishing season, after using the fishing net of the present invention, it only needs to replace it once, which greatly saves the purchase cost of the fishing net. Moreover, due to its good performance, the loss of catch caused by damage to the fishing net is reduced during the fishing process, further increasing economic benefits. In the long run, this low-cost, high-performance fishing net brings significant economic advantages to fishery production.

[0039] 4. The addition of biodegradable ingredients, such as modified polycaprolactone, is a major highlight of this invention, making the fishing nets of significant environmental significance. Traditional fishing nets are mostly made of non-degradable materials and remain in the ocean for long periods after being discarded, causing serious "white pollution" to the marine ecosystem. However, the fishing nets of this invention are able to gradually decompose in the natural environment after being discarded, reducing pollution to the marine environment. Under the influence of microorganisms and natural environmental factors, these biodegradable ingredients gradually break down into harmless substances, reducing the risk to marine life and protecting the marine ecological balance. This not only aligns with the current global concept of green development, but also provides strong support for the sustainable development of the fishery industry, helping to achieve a win-win situation for economic development and environmental protection. DETAILED DESCRIPTION

[0040] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0041] Example 1: Preparation of a wear-resistant and anti-aging composite material for fishing nets. The specific preparation steps are as follows:

[0042] S1. Soak 18 parts of para-aramid, 7 parts of ultra-high molecular weight polyethylene fiber, and 4 parts of basalt continuous fiber in an 8% by mass sulfuric acid solution for 40 minutes, then repeatedly rinse with deionized water until neutral, and dry at 70°C for 14 hours to complete the surface activation pretreatment of the fibers;

[0043] S2. Add 6 parts of sodium carboxymethyl cellulose, 4 parts of chitosan quaternary ammonium salt, and 3 parts of collagen to 120 parts of deionized water, and stir and dissolve at 55°C and 300 r / min to form a uniform macromolecular solution;

[0044] S3. Add the fibers pretreated in step S1 to the macromolecular solution obtained in step S2, and stir evenly at a speed of 300 r / min. Then, add 9 parts of polyurethane acrylate, 7 parts of phenolic epoxy resin, 12 parts of cellulose acetate, and 5 parts of high molecular weight sodium lignin sulfonate in sequence, and continue stirring for 50 minutes to prepare a uniform mixed slurry;

[0045] S4. Add 10 parts of modified nanocellulose, 32 parts of modified polycaprolactone, 3 parts of boron nitride nanosheets, and 5 parts of anatase nano-titanium dioxide to the mixed slurry. Also, add 1.2 parts of silane coupling agent KH-560 and 0.6 parts of hindered amine light stabilizer Tinuvin 770. Stir at 40° C. and 350 r / min for 80 min to fully mix the raw materials.

[0046] S5. The uniformly mixed material is conveyed to a twin-screw extruder for extrusion granulation. The extrusion temperature is set to 150° C. and the screw speed is controlled at 130 r / min to obtain composite material particles. The composite material particles are spun through a melt spinning machine at a spinning temperature of 160° C. and a drafting ratio of 4 times to finally produce a wear-resistant and anti-aging composite material for fishing nets.

[0047] Example 2: Preparation of a wear-resistant and anti-aging composite material for fishing nets. The specific preparation steps are as follows:

[0048] S1. Soak 22 parts of para-aramid fiber, 11 parts of ultra-high molecular weight polyethylene fiber, and 6 parts of basalt continuous fiber in a 12% by mass sulfuric acid solution for 60 minutes, then repeatedly rinse with deionized water until neutral, and dry at 85°C for 18 hours to complete the surface activation pretreatment of the fibers;

[0049] S2. Add 9 parts of sodium carboxymethyl cellulose, 6 parts of chitosan quaternary ammonium salt, and 5 parts of collagen to 160 parts of deionized water, and stir and dissolve at 75°C and 400 r / min to form a uniform macromolecular solution;

[0050] S3. Add the fibers pretreated in step S1 to the macromolecular solution obtained in step S2, and stir uniformly at a speed of 400 r / min. Then, add 13 parts of polyurethane acrylate, 9 parts of phenolic epoxy resin, 16 parts of cellulose acetate, and 7 parts of high molecular weight sodium lignin sulfonate in sequence, and continue stirring for 80 minutes to prepare a uniform mixed slurry;

[0051] S4. Add 14 parts of modified nanocellulose, 38 parts of modified polycaprolactone, 5 parts of boron nitride nanosheets, and 7 parts of anatase nano-titanium dioxide to the mixed slurry. At the same time, add 1.8 parts of silane coupling agent KH-560 and 1.2 parts of hindered amine light stabilizer Chimassorb 944. Stir at 450 r / min at 60°C for 120 min to fully mix the raw materials.

[0052] S5. The uniformly mixed material is conveyed to a twin-screw extruder for extrusion granulation. The extrusion temperature is set to 170° C. and the screw speed is controlled at 170 r / min to obtain composite material particles. The composite material particles are spun through a melt spinning machine at a spinning temperature of 180° C. and a drafting ratio of 6 times to finally produce a wear-resistant and anti-aging composite material for fishing nets.

[0053] Example 3: Preparation of a wear-resistant and anti-aging composite material for fishing nets. The specific preparation steps are as follows:

[0054] S1. Soak 20 parts of para-aramid, 9 parts of ultra-high molecular weight polyethylene fiber, and 5 parts of basalt continuous fiber in a 10% by mass sulfuric acid solution for 50 minutes, then repeatedly rinse with deionized water until neutral, and dry at 77°C for 16 hours to complete the surface activation pretreatment of the fibers;

[0055] S2. Add 7 parts of sodium carboxymethyl cellulose, 5 parts of chitosan quaternary ammonium salt, and 4 parts of collagen to 140 parts of deionized water, and stir and dissolve at 65°C and 350 r / min to form a uniform macromolecular solution;

[0056] S3. Add the fibers pretreated in step S1 to the macromolecular solution obtained in step S2, and stir evenly at a speed of 350 r / min. Then, add 11 parts of polyurethane acrylate, 8 parts of phenolic epoxy resin, 14 parts of cellulose acetate, and 6 parts of high molecular weight sodium lignin sulfonate in sequence, and continue stirring for 75 minutes to prepare a uniform mixed slurry;

[0057] S4. Add 12 parts of modified nanocellulose, 35 parts of modified polycaprolactone, 4 parts of boron nitride nanosheets, and 6 parts of anatase nano-titanium dioxide to the mixed slurry. Also add 1.5 parts of silane coupling agent KH-560 and 0.9 parts of hindered amine light stabilizer Chimassorb 944. Stir at 400 r / min at 50°C for 100 min to fully mix the raw materials.

[0058] S5. The uniformly mixed material is conveyed to a twin-screw extruder for extrusion granulation. The extrusion temperature is set to 160°C and the screw speed is controlled at 150 r / min to obtain composite material particles. The composite material particles are spun through a melt spinning machine at a spinning temperature of 170°C and a drafting ratio of 5 times to finally produce a wear-resistant and anti-aging composite material for fishing nets.

[0059] Example 4: Preparation of modified nanocellulose. The specific preparation steps are as follows:

[0060] A1. 12 g of nanocellulose with an average particle size of 50 nm was placed in a reaction vessel, 80 mL of deionized water was added, and the mixture was stirred at a stirring speed of 300 r / min and ultrasonically dispersed for 60 min to form a uniform suspension; 3 g of 3-aminopropyltriethoxysilane was then added, and the mixture was stirred at 80° C. for 3.5 h; after the reaction, the mixture was washed with deionized water five times, and after each wash, the mixture was centrifuged at a speed of 6000 r / min, the supernatant was poured out, and the precipitate was dried at 80° C. for 18 h to obtain amino-modified nanocellulose;

[0061] A2. The amino-modified nanocellulose was added to 120 mL of a 0.08 mol / L silver nitrate aqueous solution, stirred at 200 r / min, and then 20 mL of a 10% glucose solution was slowly added dropwise at 50° C. The mixture was stirred at 200 r / min for 2.5 h. After the reaction was completed, the mixture was washed repeatedly with deionized water 6 times, and after each washing, the mixture was centrifuged at 6500 r / min, the supernatant was poured out, and the precipitate was dried at 75° C. for 14 h to obtain nanocellulose loaded with nanosilver particles.

[0062] A3. The nanocellulose loaded with nanosilver particles was added to 130 mL of a Tris-HCl buffer solution with a pH of 8.5 and a concentration of 10 mmol / L, and then 5 g of dopamine hydrochloride was added. The mixture was stirred at 200 r / min at room temperature for 20 h. After the reaction, the mixture was washed with deionized water five times, and centrifuged at 5000 r / min after each wash. The supernatant was poured out, and the precipitate was dried at 70°C for 12 h to obtain modified nanocellulose.

[0063] Example 5, preparation of modified polycaprolactone, the specific preparation steps are as follows:

[0064] B1. Add 35 g of polycaprolactone to a reactor, heat it to 150° C. to melt it, then add 4 g of hexamethylene diisocyanate, and stir at 120 r / min under nitrogen for 2.5 h. After the reaction, cool to room temperature to obtain chain-extended modified polycaprolactone;

[0065] B2, the above-mentioned chain extension modified polycaprolactone was added to 120mL tetrahydrofuran, stirred and dissolved at a speed of 300r / min, 5g of hydroxyethyl methacrylate was added, and 0.8g of azobisisobutyronitrile was added at the same time, and the stirring speed was maintained at 70°C for free radical polymerization for 5h; after the reaction was completed, the reaction solution was transferred to a rotary evaporator for reduced pressure distillation, the pressure was controlled to 10kPa, the initial distillation temperature was set to 40°C, and the temperature was gradually increased to 60°C at a heating rate of 2°C / min until the tetrahydrofuran was completely evaporated, and the product was dried at 65°C for 14h to obtain hydrophilically modified polycaprolactone;

[0066] B3. The hydrophilically modified polycaprolactone was added to a reactor, 4 g of glycolide and 0.3 g of stannous octoate were added, and a ring-opening polymerization reaction was carried out at 130 ° C and 200 r / min for 4 h; after the reaction, the mixture was washed with deionized water 5 times, centrifuged at 6000 r / min after each washing, and dried at 70 ° C for 12 h to obtain modified polycaprolactone.

[0067] Comparative Example 1: A wear-resistant and anti-aging composite material for fishing nets was prepared. The specific preparation steps are as follows:

[0068] The remaining steps remained unchanged, except that the modified nanocellulose in Example 2 was replaced by nanocellulose without any treatment to prepare a wear-resistant and anti-aging composite material for fishing nets.

[0069] Comparative Example 2: Preparation of a wear-resistant and anti-aging composite material for fishing nets, the specific steps are as follows:

[0070] The remaining steps remained unchanged, except that the modified polycaprolactone in Example 2 was replaced by polycaprolactone without any treatment to prepare a wear-resistant and anti-aging composite material for fishing nets.

[0071] Performance Testing

[0072]

[0073]

[0074]

[0075] Performance testing reveals significant advantages for the fishing net composite materials prepared in Examples 1-3. Their tensile strengths all exceed 500 MPa, significantly exceeding those of the comparative examples. They exhibit excellent wear resistance, with minimal mass loss after 5,000 cycles of friction. They also exhibit excellent aging and corrosion resistance, with high strength retention after simulated aging and seawater immersion. They also exhibit excellent flexibility, resisting breakage upon bending. They exhibit strong adhesion resistance, reducing the adhesion of marine organisms. They also exhibit excellent water permeability and rapid drainage. Furthermore, they exhibit outstanding degradation performance, with a degradation rate exceeding 30% over six months. Comparative Examples 1 and 2, due to the lack of modification of key raw materials, are significantly inferior in all performance categories, fully demonstrating the effectiveness and superiority of the raw material modification and formulation design of this invention.

[0076] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A wear-resistant and anti-aging composite material for fishing nets, characterized by: The invention comprises the following raw materials in parts by weight: 32-38 parts of modified polycaprolactone, 10-14 parts of modified nanocellulose, 18-22 parts of para-aramid, 6-9 parts of sodium carboxymethyl cellulose, 3-5 parts of boron nitride nanosheets, 7-11 parts of ultra-high molecular weight polyethylene fiber, 5-7 parts of anatase nano-titanium dioxide, 12-16 parts of cellulose acetate, 4-6 parts of chitosan quaternary ammonium salt, 5-7 parts of high molecular weight sodium lignin sulfonate, 9-13 parts of polyurethane acrylate, 4-6 parts of basalt continuous fiber, 3-5 parts of collagen, 7-9 parts of phenolic epoxy resin, 1.2-1.8 parts of silane coupling agent KH-560, and 0.6-1.2 parts of hindered amine light stabilizer.

2. The wear-resistant and anti-aging composite material for fishing nets according to claim 1, characterized in that: The epoxy equivalent of the phenolic epoxy resin is 0.55eq / 100g; the molecular weight of the ultra-high molecular weight polyethylene fiber is ≥3 million Da; the quaternization substitution degree of the chitosan quaternary ammonium salt is ≥80%; and the hindered amine light stabilizer is one of Tinuvin 770 and Chimassorb 944.

3. The wear-resistant and anti-aging composite material for fishing nets according to claim 1, characterized in that: The modified nanocellulose is specifically prepared in the following steps: A1. Place nanocellulose with an average particle size of 50 nm in a reaction vessel, add deionized water, stir, and ultrasonically disperse for 60 minutes to form a uniform suspension; then add 3-aminopropyltriethoxysilane, and stir at 80°C for 3.5 hours. After the reaction, wash, centrifuge, pour off the supernatant, and precipitate and dry to obtain amino-modified nanocellulose; A2. Add the above-mentioned amino-treated nanocellulose to a silver nitrate aqueous solution, stir evenly, and then slowly add a glucose solution dropwise at 50° C. and continue stirring for 2.5 hours. After the reaction is complete, wash with deionized water, centrifuge after each wash, pour off the supernatant, precipitate and dry to obtain nanocellulose loaded with nanosilver particles; A3. The nanocellulose loaded with nanosilver particles was added to a Tris-HCl buffer solution, followed by addition of dopamine hydrochloride. The mixture was stirred and reacted at room temperature for 20 h. After the reaction, the mixture was washed with deionized water, centrifuged after each wash, the supernatant was poured out, and the precipitate was dried to obtain modified nanocellulose.

4. The wear-resistant and anti-aging composite material for fishing nets according to claim 3, characterized in that: In the A1 step, the ratio of nanocellulose, deionized water, and 3-aminopropyltriethoxysilane is 12 g: 80 mL: 3 g; the stirring speed is 300 r / min; the mixture is washed with deionized water 5 times, centrifuged at a speed of 6000 r / min, and the precipitate is dried at 80° C. for 18 h; in the A2 step, the ratio of silver nitrate aqueous solution to glucose solution is 120 mL: 20 mL; the concentration of silver nitrate aqueous solution is 0.08 mol / L; the mass fraction of glucose solution is 10%; the stirring speed is 300 r / min; the mixture is washed with deionized water 5 times, centrifuged at a speed of 6000 r / min, and the precipitate is dried at 80° C. for 18 h. The mixture was stirred at a speed of 200 r / min; the mixture was repeatedly washed with deionized water for 6 times, the centrifugal separation speed was 6500 r / min, and the precipitate was dried at 75°C for 14 h; in step A3, the amount ratio of Tris-HCl buffer solution to dopamine hydrochloride was 130 mL:5 g; the pH of the Tris-HCl buffer solution was 8.5, and the concentration was 10 mmol / L; the stirring speed was 200 r / min; the mixture was washed with deionized water for 5 times, the centrifugal speed was 5000 r / min, and the precipitate was dried at 70°C for 12 h.

5. The wear-resistant and anti-aging composite material for fishing nets according to claim 1, characterized in that: The modified polycaprolactone is specifically prepared in the following steps: B1. Add polycaprolactone to a reactor, heat to 150° C. to melt it, then add hexamethylene diisocyanate, and stir under nitrogen for 2.5 hours. After the reaction, cool to room temperature to obtain chain-extended modified polycaprolactone; B2. Add the chain-extended modified polycaprolactone to tetrahydrofuran, stir and dissolve, then add hydroxyethyl methacrylate and azobisisobutyronitrile, and carry out free radical polymerization at 70° C. for 5 h while maintaining the stirring speed. After the reaction is completed, transfer the reaction solution to a rotary evaporator for vacuum distillation until the tetrahydrofuran is completely evaporated, and dry the product to obtain a hydrophilically modified polycaprolactone. B3. The hydrophilically modified polycaprolactone was added to a reactor, glycolide and stannous octoate were added, and the mixture was stirred at 130° C. for 4 h to carry out a ring-opening polymerization reaction. After the reaction, the mixture was washed with deionized water, centrifuged after each washing, the supernatant was poured out, and the precipitate was dried to obtain a modified polycaprolactone.

6. The wear-resistant and anti-aging composite material for fishing nets according to claim 5, characterized in that: In the step B1, the amount ratio of polycaprolactone and hexamethylene diisocyanate is 35g:4g; the stirring speed is 120r / min; in the step B2, the amount ratio of tetrahydrofuran, hydroxyethyl methacrylate, and azobisisobutyronitrile is 120mL:5g:0.8g; the stirring speed is 300r / min; the pressure during reduced pressure distillation is controlled to 10kPa, the initial distillation temperature is set to 40°C, and the temperature is gradually increased to 60°C at a heating rate of 2°C / min; the product is dried at 65°C for 14h; in the step B3, the amount ratio of glycolide and stannous octoate is 4g:0.3g; the reaction stirring speed is 200r / min; the product is washed with deionized water 5 times, the centrifugal separation speed is 6000r / min, and the product is dried at 70°C for 12h.

7. A method for preparing a wear-resistant and anti-aging composite material for fishing nets, characterized by: The specific steps include: S1. Soaking para-aramid, ultra-high molecular weight polyethylene fiber, and basalt continuous fiber in a sulfuric acid solution, then repeatedly rinsing with deionized water until neutral, and drying to complete the surface activation pretreatment of the fibers; S2, adding sodium carboxymethyl cellulose, chitosan quaternary ammonium salt, and collagen to deionized water, heating and stirring to dissolve, and forming a uniform macromolecular solution; S3, adding the fibers pretreated in step S1 to the macromolecular solution obtained in step S2, stirring evenly, then sequentially adding polyurethane acrylate, phenolic epoxy resin, cellulose acetate, and high molecular weight sodium lignin sulfonate, and continuing stirring to prepare a uniform mixed slurry; S4, adding modified nanocellulose, modified polycaprolactone, boron nitride nanosheets, anatase nano-titanium dioxide, silane coupling agent KH-560, and hindered amine light stabilizer to the mixed slurry, and stirring to fully mix the raw materials; S5. The evenly mixed material is conveyed to a twin-screw extruder for extrusion granulation, and the temperature and screw speed are set to obtain composite material particles; the composite material particles are spun through a melt spinning machine, and the spinning temperature and draft ratio are set to finally produce a wear-resistant and anti-aging composite material for fishing nets.

8. The method for preparing the wear-resistant and anti-aging composite material for fishing nets according to claim 7, characterized in that: In step S1, the mass fraction of the sulfuric acid solution is 8-12%, the soaking time is 40-60 minutes, and the product is dried at 70-85° C. for 14-18 hours; in step S2, the reaction temperature is 55-75° C., and the stirring speed is 300-400 r / min.

9. The method for preparing a wear-resistant and anti-aging composite material for fishing nets according to claim 7, characterized in that: In the step S3, the stirring speed is 300-400 r / min, and the stirring time is 50-80 min; in the step S4, the reaction temperature is 40-60°C, the stirring speed is 350-450 r / min, and the stirring time is 80-120 min.

10. The method for preparing the wear-resistant and anti-aging composite material for fishing nets according to claim 7, characterized in that: In the step S5, the extrusion temperature is set to 150-170° C., the screw speed is controlled at 130-170 r / min, the spinning temperature is 160-180° C., and the draft ratio is 4-6 times.

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