High-strength wear-resistant aquaculture net and preparation method thereof
The vacuum plasma treatment and composite coating of aquaculture nets enhance their strength and resistance to marine biofouling, addressing the durability and performance issues of traditional nets in harsh marine environments.
Patent Information
- Application Number
- CN202510022254.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-07
- Publication Date
- 2025-03-25
AI Technical Summary
Traditional water aquaculture nets made of materials like polyethylene and nylon are prone to damage from marine organisms, leading to reduced volume and increased drag, and have limited durability in harsh marine environments, affecting their lifespan and performance.
A high-strength, wear-resistant aquaculture net is developed through a method involving vacuum plasma treatment of the base net, followed by application of a composite coating comprising a mixture of silicones, polyurethanes, and nano-titanium dioxide, which enhances the net's mechanical properties and resistance to biofouling.
The treated nets exhibit improved strength, wear resistance, and water repellency, effectively extending their lifespan and maintaining performance in challenging marine conditions.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of aquaculture nets, in particular to a high-strength wear-resistant aquaculture net and a preparation method thereof. Background Art
[0002] Aquaculture is one of the fastest growing food production sectors in the world and is of great significance to food security and the supply of high-quality protein. As an important part of marine cage farming, marine cage farming has particularly strict requirements on net materials. Suitable net materials are crucial for marine aquaculture production because they directly affect the efficiency and economic benefits of aquaculture. However, traditional polyethylene and nylon nets are easily affected by fouling organisms, which attach to the nets, reduce the volume of the aquaculture cages, increase the drag strength of the anchor chain, and even cause the cages to rupture in severe cases. In addition, the wear resistance of aquaculture nets is crucial to their service life and performance in harsh marine environments.
[0003] Therefore, in order to solve the above problems, it is of great significance to prepare a high-strength wear-resistant aquaculture net. Summary of the invention
[0004] The object of the present invention is to provide a high-strength wear-resistant aquaculture net and a preparation method thereof, so as to solve the problems raised in the prior art.
[0005] To achieve the above object, the present invention provides the following technical solutions: A method for preparing a high-strength wear-resistant aquaculture net comprises the following steps: Step 1: subjecting the basic breeding net to vacuum plasma treatment to obtain a modified breeding net; Step 2: Mix the composite copolymer, curing agent, dispersant, defoamer, organotin catalyst and dichloromethane, and stir evenly to obtain a reinforced coating; Step 3: Coat the surface of the modified aquaculture net with a reinforcing coating and cure it at room temperature to obtain a high-strength and wear-resistant aquaculture net.
[0006] More optimally, the enhanced coating comprises the following components: by weight, 10-12 parts of a composite copolymer, 2-4 parts of a curing agent, 0.1-0.2 parts of a dispersant, 0.1-0.15 parts of a defoaming agent, 0.05-0.1 parts of an organic tin catalyst, and 120-125 parts of dichloromethane.
[0007] More optimally: the material of the basic breeding net is polyethylene; the process parameters of the vacuum plasma treatment are: power 10-90w, time 1-2min, pressure 30-40Pa.
[0008] More optimally: the preparation process of the composite copolymer is: S1: distill the hydroxy silicone oil under reduced pressure at 120-130°C for 2-3h, then add dibutyltin dilaurate and diphenylmethane diisocyanate, stir and react at 80-85°C for 1-2h, then add bishydroxyaminoindole and continue to react for 1-2h to obtain a prepolymer; S2: Mix the prepolymer, 1,4-butanediol, toluene diisocyanate, and dibutyltin dilaurate, heat to 80-90°C, and react for 3-4 hours; then add triethanolamine and modified nano-titanium dioxide, continue to react for 1-2 hours, cool to room temperature, and obtain a composite copolymer.
[0009] More optimally: the prepolymer comprises the following substances: by weight, 55-58 parts of hydroxy silicone oil, 75-76 parts of diphenylmethane diisocyanate, 32-33 parts of bishydroxyaminoindole, and 0.1-0.2 parts of dibutyltin dilaurate; The composite copolymer comprises the following substances: by weight, 10-15 parts of prepolymer, 0.5-0.7 parts of 1,4-butanediol, 20-22 parts of toluene diisocyanate, 0.15-0.2 parts of dibutyltin dilaurate, and 1-2 parts of modified nano titanium dioxide.
[0010] More optimally: the preparation process of the bishydroxyaminoindole is as follows: (1) dissolving indole in acetic acid, storing at 0°C for 3-4 hours to obtain an indole solution; (2) mixing a formaldehyde aqueous solution and a dimethylamine aqueous solution, stirring and heating to 37-40°C, and reacting for 3-4 hours; after the reaction is completed, cooling to 0-5°C, adding the indole solution, continuing to stir and heating to 40-42°C, reacting for 4-5 hours, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing aminoindole, epichlorohydrin, and deionized water, heating to 30-40°C, and reacting for 4-5 hours to obtain bishydroxyaminoindole.
[0011] More optimally: in the indole solution, the ratio of indole to acetic acid is (9.3-9.5 g): 100 mL; In the aminoindole, the ratio of the formaldehyde aqueous solution, the dimethylamine aqueous solution and the indole solution is (3.9-5g): (4.5-5g): (10-12g); wherein the mass fraction of the formaldehyde aqueous solution is 33-35wt%, and the mass fraction of the dimethylamine aqueous solution is 36-40wt%; The bishydroxyaminoindole comprises the following components: by weight, 10-12 parts of aminoindole, 6-7 parts of epichlorohydrin, and 100-120 parts of deionized water.
[0012] More optimally: the preparation process of the modified nano titanium dioxide is as follows: (1) under a protective atmosphere, dihydroxyaminoindole, diphenylmethane diisocyanate and toluene are mixed, heated to 80-90°C, stirred and reacted for 1-2 hours to obtain low molecular weight polyurethane; (2) under a protective atmosphere, nano titanium dioxide is ultrasonically dispersed in N,N-dimethylformamide, low molecular weight polyurethane is added, heated to 70-75°C, stirred and reacted for 8-9 hours, cooled, filtered, washed and dried to obtain modified nano titanium dioxide.
[0013] More optimally: the low molecular weight polyurethane comprises the following components: by weight, 20-22 parts of bishydroxyaminoindole, 50-55 parts of diphenylmethane diisocyanate, and 100-120 parts of toluene; The modified nano titanium dioxide comprises the following components: by weight, 12-15 parts of nano titanium dioxide, 150-180 parts of N,N-dimethylformamide, and 30-33 parts of low molecular weight polyurethane.
[0014] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses vacuum plasma to preliminarily treat the basic breeding net, and then prepares quaternary ammonium salt-type small molecules, which are introduced into the molecular chain of the silicone oil / polyurethane composite by means of segment structure compounding, effectively improving the overall strength and wear resistance of the material, and facilitating construction operations; at the same time, after the prepared enhanced coating is cured, the hydroxy silicone oil will migrate to the surface of the coating, thereby improving the overall waterproof performance of the material. The details are as follows: (1) In the scheme, hydroxy silicone oil is used as the main chain, diphenylmethane diisocyanate is used as the hard segment, bishydroxyaminoindole and 1,4-butanediol are used as chain extenders, and triethanolamine is used as a cross-linking agent. A composite copolymer is synthesized through addition polymerization. Among them, bishydroxyaminoindole, as an organic antibacterial agent, can effectively improve the anti-fouling ability of the aquaculture net. The conjugated double bond system it contains can absorb ultraviolet radiation well and enhance the anti-aging performance of the material. At the same time, in the process of contact with water molecules, the silicone oil chain segments will migrate and enrich to the surface of the coating, so that the surface of the coating is covered with a Si-CH3 layer, making it difficult for water molecules to penetrate into the interior of the coating, thereby improving the waterproof performance of the material. (2) Nano-titanium dioxide has photocatalytic activity and has strong antibacterial and bactericidal capabilities after absorbing ultraviolet light energy, which enhances the anti-fouling ability of the aquaculture net. Due to its special optical properties, it can absorb and scatter ultraviolet rays, reducing the destructive effects of ultraviolet rays on the aquaculture net. At the same time, nano-titanium dioxide, as a reinforcing material, can improve the strength and wear resistance of the aquaculture net. In order to avoid compatibility issues, in the scheme, low molecular weight polyurethane is synthesized with dihydroxyaminoindole and diphenylmethane diisocyanate, and then grafted onto the surface of nano-titanium dioxide, so that it can be entangled with the matrix, further improving the performance of the aquaculture net. In the (3) scheme, the surface of the basic aquaculture net is first treated with vacuum plasma through physical modification. The surface of the aquaculture net after treatment contains a large number of active groups such as hydroxyl groups. During the curing process of the enhanced coating, it can combine well with the isocyanate groups, making the enhanced film connection more tightly and the corresponding physical properties are also improved. DETAILED DESCRIPTION
[0015] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall within the scope of protection of the present invention.
[0016] It should be noted that the purchase manufacturers of all raw materials involved in the present invention are not subject to any special restrictions and exemplarily include: in the following embodiments, diphenylmethane diisocyanate CAS is 101-68-8, dibutyltin dilaurate CAS is 77-58-7, indole CAS is 120-72-9; hydroxy silicone oil M=92.17 g / mol; toluene diisocyanate CAS is 91-08-7.
[0017] Embodiment 1: A method for preparing a high-strength wear-resistant aquaculture net, comprising the following steps: Step 1: Treat the basic aquaculture net with 10W vacuum plasma at 30Pa for 1min to obtain a modified aquaculture net; Step 2: 10 parts of the composite copolymer, 2 parts of the curing agent N-300, 0.1 parts of the dispersant NNO, 0.1 parts of the defoaming agent GP300, 0.05 parts of dibutyltin dilaurate, and 120 parts of dichloromethane were mixed and stirred evenly to obtain a reinforced coating; Step 3: coating the surface of the modified aquaculture net with a reinforcing coating and curing it at room temperature to obtain a high-strength and wear-resistant aquaculture net; Wherein, the preparation process of the composite copolymer is: S1: 55 parts of hydroxy silicone oil were distilled under reduced pressure at 120°C for 2 hours, then 75 parts of diphenylmethane diisocyanate and 0.1 parts of dibutyltin dilaurate were added, stirred and reacted at 80°C for 1 hour, then 32 parts of bishydroxyaminoindole were added, and the reaction was continued for 1 hour to obtain a prepolymer; S2: 10 parts of prepolymer, 0.5 parts of 1,4-butanediol, 20 parts of toluene diisocyanate, and 0.15 parts of dibutyltin dilaurate were mixed, heated to 80°C, and reacted for 3 hours; then 0.1 parts of triethanolamine and 1 part of modified nano-titanium dioxide were added, the reaction continued for 1 hour, and cooled to room temperature to obtain a composite copolymer; The preparation process of bishydroxyaminoindole is as follows: (1) dissolving 9.3 g of indole in 100 mL of acetic acid, storing at 0° C. for 3 h, and obtaining an indole solution; (2) mixing 3.9 g of 33 wt % formaldehyde aqueous solution and 4.5 g of 36 wt % dimethylamine aqueous solution, stirring and heating to 37° C., and reacting for 3 h; after the reaction is completed, cooling to 0° C., adding 10 g of indole solution, continuing stirring and heating to 40° C., and reacting for 4 h, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing 10 parts of aminoindole, 6 parts of epichlorohydrin, and 100 parts of deionized water, heating to 30° C., and reacting for 4 h to obtain bishydroxyaminoindole; The preparation process of modified nano titanium dioxide is as follows: (1) Under nitrogen, 20 parts of dihydroxyaminoindole, 50 parts of diphenylmethane diisocyanate, and 100 parts of toluene are mixed, the temperature is raised to 80°C, and the reaction is stirred for 1 hour to obtain low molecular weight polyurethane; (2) Under nitrogen, 12 parts of nano titanium dioxide are ultrasonically dispersed in 150 parts of N,N-dimethylformamide, 30 parts of low molecular weight polyurethane are added, the temperature is raised to 70°C, the reaction is stirred for 8 hours, and the modified nano titanium dioxide is obtained.
[0018] Embodiment 2: A method for preparing a high-strength wear-resistant aquaculture net, comprising the following steps: Step 1: Treat the basic breeding net with 90W vacuum plasma at 40Pa for 2min to obtain a modified breeding net; Step 2: 12 parts of the composite copolymer, 4 parts of the curing agent N-300, 0.2 parts of the dispersant NNO, 0.15 parts of the defoaming agent GP300, 0.1 parts of dibutyltin dilaurate, and 125 parts of dichloromethane were mixed and stirred evenly to obtain a reinforced coating; Step 3: coating the surface of the modified aquaculture net with a reinforcing coating and curing it at room temperature to obtain a high-strength and wear-resistant aquaculture net; Wherein, the preparation process of the composite copolymer is: S1: 58 parts of hydroxy silicone oil were distilled under reduced pressure at 130°C for 3 hours, then 0.2 parts of dibutyltin dilaurate and 76 parts of diphenylmethane diisocyanate were added, stirred and reacted at 85°C for 2 hours, then 33 parts of bishydroxyaminoindole were added, and the reaction was continued for 2 hours to obtain a prepolymer; S2: 15 parts of prepolymer, 0.7 parts of 1,4-butanediol, 22 parts of toluene diisocyanate, and 0.2 parts of dibutyltin dilaurate were mixed, heated to 90°C, and reacted for 4 hours; then 0.2 parts of triethanolamine and 2 parts of modified nano-titanium dioxide were added, the reaction continued for 2 hours, and cooled to room temperature to obtain a composite copolymer; The preparation process of bishydroxyaminoindole is as follows: (1) dissolving 9.5 g of indole in 100 mL of acetic acid, storing at 0° C. for 4 hours, and obtaining an indole solution; (2) mixing 5 g of a 35 wt % formaldehyde aqueous solution and 5 g of a 40 wt % dimethylamine aqueous solution, stirring and heating to 40° C., and reacting for 4 hours; after the reaction is completed, cooling to 5° C., adding 12 g of the indole solution, continuing to stir and heating to 42° C., reacting for 5 hours, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing 12 parts of aminoindole, 7 parts of epichlorohydrin, and 120 parts of deionized water, heating to 40° C., and reacting for 5 hours to obtain bishydroxyaminoindole; The preparation process of modified nano titanium dioxide is as follows: (1) under nitrogen, 22 parts of dihydroxyaminoindole, 55 parts of diphenylmethane diisocyanate, and 120 parts of toluene are mixed, the temperature is raised to 90°C, and the mixture is stirred for reaction for 2 hours to obtain low molecular weight polyurethane; (2) under nitrogen, 15 parts of nano titanium dioxide are ultrasonically dispersed in 180 parts of N,N-dimethylformamide, 33 parts of low molecular weight polyurethane are added, the temperature is raised to 75°C, the mixture is stirred for reaction for 9 hours, and the mixture is cooled, filtered, washed, and dried to obtain modified nano titanium dioxide.
[0019] Embodiment 3: A method for preparing a high-strength wear-resistant aquaculture net, comprising the following steps: Step 1: Treat the basic breeding net with 50W vacuum plasma at 35Pa for 1.5min to obtain a modified breeding net; Step 2: 11 parts of the composite copolymer, 3 parts of the curing agent N-300, 0.15 parts of the dispersant NNO, 0.12 parts of the defoaming agent GP300, 0.08 parts of dibutyltin dilaurate, and 122 parts of dichloromethane were mixed and stirred evenly to obtain a reinforced coating; Step 3: coating the surface of the modified aquaculture net with a reinforcing coating and curing it at room temperature to obtain a high-strength and wear-resistant aquaculture net; Wherein, the preparation process of the composite copolymer is: S1: 56 parts of hydroxy silicone oil were distilled under reduced pressure at 125°C for 2.5 hours, then 0.15 parts of dibutyltin dilaurate and 75 parts of diphenylmethane diisocyanate were added, stirred and reacted at 82°C for 1.5 hours, then 32.5 parts of bishydroxyaminoindole were added, and the reaction was continued for 1.5 hours to obtain a prepolymer; S2: 12 parts of prepolymer, 0.6 parts of 1,4-butanediol, 21 parts of toluene diisocyanate, and 0.18 parts of dibutyltin dilaurate were mixed, heated to 85°C, and reacted for 3.5 hours; then 0.15 parts of triethanolamine and 1.5 parts of modified nano-titanium dioxide were added, and the reaction was continued for 1.5 hours, and cooled to room temperature to obtain a composite copolymer; The preparation process of bishydroxyaminoindole is as follows: (1) dissolving 9.5 g of indole in 100 mL of acetic acid, storing at 0°C for 3.5 hours to obtain an indole solution; (2) mixing 4 g of a 35 wt% formaldehyde aqueous solution and 5 g of a 40 wt% dimethylamine aqueous solution, stirring and heating to 40°C, and reacting for 3.5 hours; after the reaction is completed, cooling to 3°C, adding 11 g of the indole solution, continuing to stir and heating to 41°C, reacting for 4.5 hours, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing 11 parts of aminoindole, 6.5 parts of epichlorohydrin, and 110 parts of deionized water, heating to 35°C, and reacting for 4.5 hours to obtain bishydroxyaminoindole; The preparation process of modified nano titanium dioxide is as follows: (1) under nitrogen, 21 parts of dihydroxyaminoindole, 52 parts of diphenylmethane diisocyanate, and 110 parts of toluene are mixed, the temperature is raised to 85°C, and the reaction is stirred for 1.5 hours to obtain low molecular weight polyurethane; (2) under nitrogen, 13 parts of nano titanium dioxide are ultrasonically dispersed in 160 parts of N,N-dimethylformamide, 32 parts of low molecular weight polyurethane are added, the temperature is raised to 72°C, the reaction is stirred for 8.5 hours, and the modified nano titanium dioxide is obtained.
[0020] Comparative Example 1: During the preparation of the composite copolymer, the chain extender bishydroxyaminoindole was not added, and the rest was the same as in Example 3, as follows: Step 1: Treat the basic breeding net with 50W vacuum plasma at 35Pa for 1.5min to obtain a modified breeding net; Step 2: 11 parts of the composite copolymer, 3 parts of the curing agent N-300, 0.15 parts of the dispersant NNO, 0.12 parts of the defoaming agent GP300, 0.08 parts of dibutyltin dilaurate, and 122 parts of dichloromethane were mixed and stirred evenly to obtain a reinforced coating; Step 3: coating the surface of the modified aquaculture net with a reinforcing coating and curing it at room temperature to obtain a high-strength and wear-resistant aquaculture net; Wherein, the preparation process of the composite copolymer is: S1: 56 parts of hydroxy silicone oil were distilled under reduced pressure at 125°C for 2.5 hours, and then 0.15 parts of dibutyltin dilaurate and 75 parts of diphenylmethane diisocyanate were added, and the mixture was stirred and reacted at 82°C for 1.5 hours to obtain a prepolymer; S2: 12 parts of prepolymer, 0.6 parts of 1,4-butanediol, 21 parts of toluene diisocyanate, and 0.18 parts of dibutyltin dilaurate were mixed, heated to 85°C, and reacted for 3.5 hours; then 0.15 parts of triethanolamine and 1.5 parts of modified nano-titanium dioxide were added, and the reaction was continued for 1.5 hours, and cooled to room temperature to obtain a composite copolymer; The preparation process of modified nano titanium dioxide is as follows: (1) under nitrogen, 21 parts of bishydroxyaminoindole, 52 parts of diphenylmethane diisocyanate, and 110 parts of toluene are mixed, heated to 85°C, stirred and reacted for 1.5 hours to obtain low molecular weight polyurethane; (2) under nitrogen, 13 parts of nano titanium dioxide are ultrasonically dispersed in 160 parts of N,N-dimethylformamide, 32 parts of low molecular weight polyurethane are added, the temperature is raised to 72°C, stirred and reacted for 8.5 hours, cooled, filtered, washed, and dried to obtain modified nano titanium dioxide. The preparation process of bishydroxyaminoindole is as follows: (1) 9.5 g of indole is dissolved in (1) 100 mL of acetic acid, at 0 ° C, store for 3.5 hours to obtain an indole solution; (2) 4 g of 35 wt% formaldehyde aqueous solution and 5 g of 40 wt% dimethylamine aqueous solution are mixed, stirred and heated to 40 ° C, and reacted for 3.5 hours; after the reaction is completed, cool to 3 ° C, add 11 g of indole solution, continue stirring and heat to 41 ° C, react for 4.5 hours, adjust the pH to 12, let stand, filter, wash, and dry to obtain aminoindole; (3) 11 parts of aminoindole, 6.5 parts of epichlorohydrin, and 110 parts of deionized water are mixed, heated to 35 ° C, and reacted for 4.5 hours to obtain bishydroxyaminoindole.
[0021] Comparative Example 2: No modification is performed on the nano-titanium dioxide, and the rest is the same as Example 3, specifically as follows: Step 1: Treat the basic breeding net with 50W vacuum plasma at 35Pa for 1.5min to obtain a modified breeding net; Step 2: 11 parts of the composite copolymer, 3 parts of the curing agent N-300, 0.15 parts of the dispersant NNO, 0.12 parts of the defoaming agent GP300, 0.08 parts of dibutyltin dilaurate, and 122 parts of dichloromethane were mixed and stirred evenly to obtain a reinforced coating; Step 3: coating the surface of the modified aquaculture net with a reinforcing coating and curing it at room temperature to obtain a high-strength and wear-resistant aquaculture net; Wherein, the preparation process of the composite copolymer is: S1: 56 parts of hydroxy silicone oil were distilled under reduced pressure at 125°C for 2.5 hours, then 0.15 parts of dibutyltin dilaurate and 75 parts of diphenylmethane diisocyanate were added, stirred and reacted at 82°C for 1.5 hours, then 32.5 parts of bishydroxyaminoindole were added, and the reaction was continued for 1.5 hours to obtain a prepolymer; S2: 12 parts of prepolymer, 0.6 parts of 1,4-butanediol, 21 parts of toluene diisocyanate, and 0.18 parts of dibutyltin dilaurate were mixed, heated to 85°C, and reacted for 3.5 hours; then 0.15 parts of triethanolamine and 1.5 parts of modified nano-titanium dioxide were added, and the reaction was continued for 1.5 hours, and cooled to room temperature to obtain a composite copolymer; The preparation process of bishydroxyaminoindole is as follows: (1) dissolving 9.5 g of indole in 100 mL of acetic acid, storing at 0°C for 3.5 hours to obtain an indole solution; (2) mixing 4 g of 35 wt% formaldehyde aqueous solution and 5 g of 40 wt% dimethylamine aqueous solution, stirring and heating to 40°C, and reacting for 3.5 hours; after the reaction is completed, cooling to 3°C, adding 11 g of indole solution, continuing to stir and heating to 41°C, reacting for 4.5 hours, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing 11 parts of aminoindole, 6.5 parts of epichlorohydrin, and 110 parts of deionized water, heating to 35°C, and reacting for 4.5 hours to obtain bishydroxyaminoindole.
[0022] Comparative Example 3: The basic breeding net is not modified, and the rest is the same as Example 3, as follows: Step 1: 11 parts of the composite copolymer, 3 parts of the curing agent N-300, 0.15 parts of the dispersant NNO, 0.12 parts of the defoaming agent GP300, 0.08 parts of dibutyltin dilaurate, and 122 parts of dichloromethane were mixed and stirred evenly to obtain a reinforced coating; Step 2: Coat the surface of the basic aquaculture net with a reinforcing coating and cure it at room temperature to obtain a high-strength and wear-resistant aquaculture net; Wherein, the preparation process of the composite copolymer is: S1: 56 parts of hydroxy silicone oil were distilled under reduced pressure at 125°C for 2.5 hours, then 0.15 parts of dibutyltin dilaurate and 75 parts of diphenylmethane diisocyanate were added, stirred and reacted at 82°C for 1.5 hours, then 32.5 parts of bishydroxyaminoindole were added, and the reaction was continued for 1.5 hours to obtain a prepolymer; S2: 12 parts of prepolymer, 0.6 parts of 1,4-butanediol, 21 parts of toluene diisocyanate, and 0.18 parts of dibutyltin dilaurate were mixed, heated to 85°C, and reacted for 3.5 hours; then 0.15 parts of triethanolamine and 1.5 parts of modified nano-titanium dioxide were added, and the reaction was continued for 1.5 hours, and cooled to room temperature to obtain a composite copolymer; The preparation process of bishydroxyaminoindole is as follows: (1) dissolving 9.5 g of indole in 100 mL of acetic acid, storing at 0°C for 3.5 hours to obtain an indole solution; (2) mixing 4 g of a 35 wt% formaldehyde aqueous solution and 5 g of a 40 wt% dimethylamine aqueous solution, stirring and heating to 40°C, and reacting for 3.5 hours; after the reaction is completed, cooling to 3°C, adding 11 g of the indole solution, continuing to stir and heating to 41°C, reacting for 4.5 hours, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing 11 parts of aminoindole, 6.5 parts of epichlorohydrin, and 110 parts of deionized water, heating to 35°C, and reacting for 4.5 hours to obtain bishydroxyaminoindole; The preparation process of modified nano titanium dioxide is as follows: (1) under nitrogen, 21 parts of dihydroxyaminoindole, 52 parts of diphenylmethane diisocyanate, and 110 parts of toluene are mixed, the temperature is raised to 85°C, and the reaction is stirred for 1.5 hours to obtain low molecular weight polyurethane; (2) under nitrogen, 13 parts of nano titanium dioxide are ultrasonically dispersed in 160 parts of N,N-dimethylformamide, 32 parts of low molecular weight polyurethane are added, the temperature is raised to 72°C, the reaction is stirred for 8.5 hours, and the modified nano titanium dioxide is obtained.
[0023] Comparative Example 4: Compared with Example 3, an excess amount of modified nano-titanium dioxide is added, specifically as follows: Step 1: The basic breeding net is treated with 50w vacuum plasma at 35Pa for 1.5min to obtain a modified breeding net; Step 2: 11 parts of the composite copolymer, 3 parts of the curing agent N-300, 0.15 parts of the dispersant NNO, 0.12 parts of the defoaming agent GP300, 0.08 parts of dibutyltin dilaurate, and 122 parts of dichloromethane were mixed and stirred evenly to obtain a reinforced coating; Step 3: coating the surface of the modified aquaculture net with a reinforcing coating and curing it at room temperature to obtain a high-strength and wear-resistant aquaculture net; Wherein, the preparation process of the composite copolymer is: S1: 56 parts of hydroxy silicone oil were distilled under reduced pressure at 125°C for 2.5 hours, then 0.15 parts of dibutyltin dilaurate and 75 parts of diphenylmethane diisocyanate were added, stirred and reacted at 82°C for 1.5 hours, then 32.5 parts of bishydroxyaminoindole were added, and the reaction was continued for 1.5 hours to obtain a prepolymer; S2: 12 parts of prepolymer, 0.6 parts of 1,4-butanediol, 21 parts of toluene diisocyanate, and 0.18 parts of dibutyltin dilaurate were mixed, heated to 85°C, and reacted for 3.5 hours; then 0.15 parts of triethanolamine and 10 parts of modified nano-titanium dioxide were added, the reaction continued for 1.5 hours, and cooled to room temperature to obtain a composite copolymer; The preparation process of bishydroxyaminoindole is as follows: (1) dissolving 9.5 g of indole in 100 mL of acetic acid, storing at 0°C for 3.5 hours to obtain an indole solution; (2) mixing 4 g of a 35 wt% formaldehyde aqueous solution and 5 g of a 40 wt% dimethylamine aqueous solution, stirring and heating to 40°C, and reacting for 3.5 hours; after the reaction is completed, cooling to 3°C, adding 11 g of the indole solution, continuing to stir and heating to 41°C, reacting for 4.5 hours, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing 11 parts of aminoindole, 6.5 parts of epichlorohydrin, and 110 parts of deionized water, heating to 35°C, and reacting for 4.5 hours to obtain bishydroxyaminoindole; The preparation process of modified nano titanium dioxide is as follows: (1) under nitrogen, 21 parts of dihydroxyaminoindole, 52 parts of diphenylmethane diisocyanate, and 110 parts of toluene are mixed, the temperature is raised to 85°C, and the reaction is stirred for 1.5 hours to obtain low molecular weight polyurethane; (2) under nitrogen, 13 parts of nano titanium dioxide are ultrasonically dispersed in 160 parts of N,N-dimethylformamide, 32 parts of low molecular weight polyurethane are added, the temperature is raised to 72°C, the reaction is stirred for 8.5 hours, and the modified nano titanium dioxide is obtained.
[0024] Detection experiment: (1) The aquaculture nets obtained in the examples and comparative examples were tested for fouling organism coverage in accordance with the national standard GB / T5370-2007 "Test method for shallow sea immersion of antifouling paint samples"; (2) The aging conditions were as follows: lamp type: UVA-340; irradiance (340nm): 0.76W / ㎡ / nm; black standard temperature: 60±3℃ / 50±3℃; light / condensation cycle: 480min / 240min, aging for 500h and 1000h, and measuring the maximum breaking force; (3) The wear of the aquaculture net measured according to standard DIN5251 is used to evaluate the wear resistance; (4) The aquaculture net was tested using a water contact angle tester (OCA25). The test water was homemade deionized water. The data obtained are shown in the following table:
[0025] Table 1 Conclusion: The present invention uses vacuum plasma to perform preliminary treatment on the basic breeding net, then prepares quaternary ammonium salt-type small molecules, and introduces them into the molecular chain of the silicone oil / polyurethane composite in a segment structure composite manner, which effectively improves the overall strength and wear resistance of the material; at the same time, after the prepared reinforced coating is cured, the hydroxyl silicone oil will migrate to the surface of the coating, thereby improving the overall waterproof performance of the material.
[0026] In the preparation process of the composite copolymer of Comparative Example 1, the chain extender bishydroxyaminoindole is not added. Due to the lack of quaternary ammonium salt monomer, the antifouling performance of the material is reduced, and the length of the polyurethane chain segment is reduced, thereby reducing the physical properties of the material; in Comparative Example 2, the nano titanium dioxide is not modified, and the performance is reduced; in Comparative Example 3, the basic breeding net is not modified, and the curing process lacks interaction with the reinforced coating, and the performance is reduced; in Comparative Example 4, an excessive amount of modified nano titanium dioxide is added, and the performance is reduced.
[0027] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for preparing a high-strength wear-resistant aquaculture net, characterized in that: The following steps are involved: Step 1: subjecting the basic breeding net to vacuum plasma treatment to obtain a modified breeding net; Step 2: Mix the composite copolymer, curing agent, dispersant, defoamer, organotin catalyst and dichloromethane, and stir evenly to obtain a reinforced coating; Step 3: Coat the surface of the modified aquaculture net with a reinforcing coating and cure it at room temperature to obtain a high-strength and wear-resistant aquaculture net.
2. The method for preparing a high-strength wear-resistant aquaculture net according to claim 1, characterized in that: The enhanced coating comprises the following components: by weight, 10-12 parts of a composite copolymer, 2-4 parts of a curing agent, 0.1-0.2 parts of a dispersant, 0.1-0.15 parts of a defoaming agent, 0.05-0.1 parts of an organic tin catalyst, and 120-125 parts of dichloromethane.
3. The method for preparing a high-strength wear-resistant aquaculture net according to claim 1, characterized in that: The material of the basic breeding net is polyethylene; the process parameters of the vacuum plasma treatment are: power 10-90w, time 1-2min, pressure 30-40Pa.
4. The method for preparing a high-strength wear-resistant aquaculture net according to claim 1, characterized in that: The preparation process of the composite copolymer is: S1: distill the hydroxy silicone oil under reduced pressure at 120-130°C for 2-3h, then add dibutyltin dilaurate and diphenylmethane diisocyanate, stir and react at 80-85°C for 1-2h, then add bishydroxyaminoindole and continue to react for 1-2h to obtain a prepolymer; S2: Mix the prepolymer, 1,4-butanediol, toluene diisocyanate, and dibutyltin dilaurate, heat to 80-90°C, and react for 3-4 hours; then add triethanolamine and modified nano-titanium dioxide, continue to react for 1-2 hours, cool to room temperature, and obtain a composite copolymer.
5. The method for preparing a high-strength wear-resistant aquaculture net according to claim 4, characterized in that: The prepolymer comprises the following substances: by weight, 55-58 parts of hydroxy silicone oil, 75-76 parts of diphenylmethane diisocyanate, 32-33 parts of bishydroxyaminoindole, and 0.1-0.2 parts of dibutyltin dilaurate; The composite copolymer comprises the following substances: by weight, 10-15 parts of prepolymer, 0.5-0.7 parts of 1,4-butanediol, 20-22 parts of toluene diisocyanate, 0.15-0.2 parts of dibutyltin dilaurate, and 1-2 parts of modified nano titanium dioxide.
6. The method for preparing a high-strength wear-resistant aquaculture net according to claim 4, characterized in that: The preparation process of the bishydroxyaminoindole is as follows: (1) dissolving indole in acetic acid, storing at 0°C for 3-4 hours, and obtaining an indole solution; (2) mixing a formaldehyde aqueous solution and a dimethylamine aqueous solution, stirring and heating to 37-40°C, and reacting for 3-4 hours; after the reaction is completed, cooling to 0-5°C, adding the indole solution, continuing to stir and heating to 40-42°C, reacting for 4-5 hours, adjusting the pH to 12, standing, filtering, washing, and drying to obtain aminoindole; (3) mixing aminoindole, epichlorohydrin, and deionized water, heating to 30-40°C, and reacting for 4-5 hours to obtain bishydroxyaminoindole.
7. The method for preparing a high-strength wear-resistant aquaculture net according to claim 6, characterized in that: In the indole solution, the ratio of indole to acetic acid is (9.3-9.5 g): 100 mL; In the aminoindole, the ratio of the formaldehyde aqueous solution, the dimethylamine aqueous solution and the indole solution is (3.9-5g): (4.5-5g): (10-12g); wherein the mass fraction of the formaldehyde aqueous solution is 33-35wt%, and the mass fraction of the dimethylamine aqueous solution is 36-40wt%; The bishydroxyaminoindole comprises the following components: by weight, 10-12 parts of aminoindole, 6-7 parts of epichlorohydrin, and 100-120 parts of deionized water.
8. The method for preparing a high-strength wear-resistant aquaculture net according to claim 4, characterized in that: The preparation process of the modified nano titanium dioxide is as follows: (1) under a protective atmosphere, dihydroxyaminoindole, diphenylmethane diisocyanate and toluene are mixed, the temperature is raised to 80-90° C., and the mixture is stirred for reaction for 1-2 hours to obtain low molecular weight polyurethane; (2) under a protective atmosphere, nano titanium dioxide is ultrasonically dispersed in N,N-dimethylformamide, low molecular weight polyurethane is added, the temperature is raised to 70-75° C., the mixture is stirred for reaction for 8-9 hours, and the mixture is cooled, filtered, washed and dried to obtain modified nano titanium dioxide.
9. The method for preparing a high-strength wear-resistant aquaculture net according to claim 8, characterized in that: The low molecular weight polyurethane comprises the following components: by weight, 20-22 parts of bishydroxyaminoindole, 50-55 parts of diphenylmethane diisocyanate, and 100-120 parts of toluene; The modified nano titanium dioxide comprises the following components: by weight, 12-15 parts of nano titanium dioxide, 150-180 parts of N,N-dimethylformamide, and 30-33 parts of low molecular weight polyurethane.
10. A high-strength wear-resistant aquaculture net obtained by the method for preparing a high-strength wear-resistant aquaculture net according to any one of claims 1 to 9.