Antifouling processing method for fishing net ropes and cables using hydroxy acid ester oligomer compounded antifouling agent and its product

Abstract

The present invention discloses an antifouling processing method for fishing nets and cables using a hydroxy acid ester oligomer compounded with an antifouling agent and its products. The fishing nets and cables are placed in a supercritical fluid high-pressure tank, and the hydroxy acid ester oligomer is compounded with bromofuranone and alkaloids and placed in a drug storage tank as an antifouling agent. A quantitative amount of SCF flows through the drug storage tank with a built-in antifouling agent and then enters the tank; the temperature is quickly raised to allow the system to reach the set temperature and pressure; due to the impact of the pumping pressure and the fluid stirring driven by the circulating pump, the SCF will promote the dissolution of the compound antifouling agent; then the SCF in the tank performs periodic dynamic motion, and finally the temperature and pressure are slowly lowered to balance the pressure inside and outside the tank. By using the SCF technology, the compound antifouling agent is directly fixed to the shallow surface of the fiber, which can avoid the use of resin materials as the main body of the antifouling coating, avoid coating processing, avoid the problem of uneven coating that is easily caused by coating processing, and avoid the harm of additives volatilization to employees during coating processing.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial product preparation, and relates to an antifouling processing method for fishing nets and cables by compounding an antifouling agent with a hydroxy acid ester oligomer and a product thereof. Background Art

[0002] Marine organisms (algae such as green algae, red algae and brown algae; animals such as barnacles, mussels, lime worms, sea squirts and moss worms) will attach to marine buildings (lighthouses, bridges, etc.), hulls, drilling platforms and fishery production facilities, causing rapid fouling. The net cage ropes made of fiber materials such as polypropylene filaments and polyester filaments used in large quantities in marine fishery production, as well as fiber products such as ropes used as marine buoys and ship mooring cables, can be damaged by harmful substances secreted by marine organisms after attachment. The attached algae and shellfish will affect the flow of water inside and outside the net cages, affecting the breeding environment conditions of seafood.

[0003] The attachment of marine organisms begins with the secretion of nutrients such as proteins and polysaccharides to form a basement membrane on the surface of the object being attached. Then, single-cell organisms attach to form a biofilm, followed by multicellular organisms such as diatom spores attaching and multiplying to form a mucus layer. Finally, large organisms such as barnacles and green algae attach to form a fouling layer. The entire process can be initially completed in just a few days in the summer. Unprotected ropes, hulls, and building surfaces will be completely covered by marine organisms within a few months.

[0004] There are many methods to prevent marine biofouling, such as mechanical removal, electrochemical method, ultrasonic method and antifouling coating method. Obviously, the first few methods are not suitable for fiber products. It is a common method to treat net cables with antifouling coating. The antifouling coating is composed of polymer resin, antifouling agent, etc. The antifouling agent slowly released from the resin plays a role in killing or inhibiting the attachment of marine organisms.

[0005] Early antifouling agents used toxic materials such as mercury and copper to kill marine life. In the 1950s, less toxic cuprous oxide was used, and in the 1970s, organotin antifouling paints were used. However, organotin can also accumulate in fish, shellfish and marine plants over a long period of time and enter the food chain, so it has also been banned by the International Maritime Organization since 2008. The main antifouling paints currently used are:

[0006] (1) Wuxi self-polishing antifouling materials. The so-called "self-polishing" means that during the use of antifouling coatings, the polymer material gradually degrades and detaches, gradually exposing the groups containing copper, zinc and silane esters. However, the effect is not enough, and a portion of cuprous oxide must be used in combination to play an antifouling role. Copper ions will accumulate in the ocean and cause serious environmental problems. At present, some countries have banned the use of cuprous oxide; in addition, polymer materials that play a "self-polishing" role are also one of the sources of marine plastic pollution.

[0007] (2) Fouling resistance materials. Hydrophilic polymers such as polyethylene glycol, zwitterionic polymers, and hydrogels are fixed to the surface of objects. Because the interfacial energy between the surface of these hydrophilic polymer materials and water is very low, a hydration layer can be formed on the surface. When organisms approach, they must break through the hydration layer to adhere to the surface of the substrate, thus reducing the possibility of adhesion. This type of material has poor anti-fouling spectrum and is easily ineffective after being covered by sea mud and biological decay. It is still in the laboratory research stage.

[0008] (3) Fouling-removing coating. This coating uses low-surface-energy silicone or fluorinated polymers to remove fouling organisms from the surface through ocean current flushing or mechanical removal, without releasing toxic antifouling agents. However, this coating is suitable for antifouling of large smooth surfaces such as ship hulls, but not for fiber products with complex shapes, large specific surface areas, and a large number of fine textures on the surface.

[0009] Therefore, there is still a lack of safe and effective anti-fouling methods for the problem of marine biofouling, especially for fiber products such as fishery cage ropes, marine buoy ropes, and ship mooring cables. Summary of the invention

[0010] The first object of the present invention is to provide an antifouling processing method for fishing net ropes by using hydroxy acid ester oligomer compound antifouling agent to address the deficiencies of the prior art, and to fix the antifouling agent on the shallow surface of the fishing net line by using SCF technology.

[0011] The present invention discloses a method for antifouling fishing nets and cables by using a hydroxy acid ester oligomer compounded with an antifouling agent, comprising the following steps:

[0012] Step S1: pre-winding the synthetic fiber rope for fishing fences that need to be treated with anti-fouling into a loose bobbin, and inserting the hollow core of the loose bobbin into the hollow column; the hollow column and the hollow core of the loose bobbin are both provided with a plurality of holes, and the holes of the two are of the same size and aligned with each other;

[0013] Step S2: placing the antifouling agent in the medicine storage tank, and then placing the medicine storage tank in a supercritical fluid high-pressure tank; at the same time, placing the hollow column loaded with the loose bobbin in the supercritical fluid high-pressure tank, the SCF dynamic circulation liquid outlet of the supercritical fluid high-pressure tank being located in the hollow core of the hollow column, so that the SCF fluid flowing out through the SCF dynamic circulation liquid outlet takes out the antifouling agent through the medicine storage tank and then sprays out through the holes of the hollow column, so that the rope wound thereon is in uniform contact with the SCF fluid;

[0014] Step S3: After closing the high-pressure tank, the air is evacuated, and then the temperature is increased from room temperature to 60-170°C at a rate of 4-10°C / min, and the pressure is increased to 20-30MPa at a rate of 0.7-2.5MPa / min, so that the whole system reaches a balanced state, the rope reaches a high temperature and high pressure state in a relatively short time, enters a swelling stage, and the antifouling agent is fully dissolved in the SCF;

[0015] Step S4, in a system equilibrium state, immersing the hydroxy acid ester oligomer solution and the fiber to be processed in a supercritical fluid for periodic dynamic motion for not less than 40 minutes, and the stable stage of heat preservation and pressure preservation allows the antifouling agent with high solubility to smoothly enter the shallow surface of the fiber;

[0016] The periodic dynamic motion is a combination of dynamic and static motions in one motion cycle, the dynamic cycle time accounts for 40 to 80%, and the cycle time is 1 to 3 minutes;

[0017] Step S5, after the periodic dynamic movement is completed, the temperature is first rapidly cooled to room temperature at a rate of 3-5°C / min, and then the pressure is reduced at a rate of 0.5-1.2MPa / min until the pressure in the high-pressure tank is balanced with the ambient pressure; as the supercritical fluid high-pressure tank is depressurized, the SCF is released, and the antifouling agent is fixed to the surface of the rope due to fiber shrinkage.

[0018] The antifouling agent is a composition obtained by mixing a hydroxy acid ester oligomer with one or two of brominated furanone and alkaloid;

[0019] The hydroxy acid ester oligomer is referred to CN202111137059.1, and its general structural formula is as follows (I):

[0020]

[0021] Wherein m is a natural number of 0-3; when n is a natural number of 1-3, R1 is a C1-C5 alkyl group, and R2 is a C4-C8 alkyl group; when n is a natural number of 4-8, R1 is a C1-C5 alkyl group, and R2 is a C2-C8 alkyl group;

[0022] Preferably, the SCF is supercritical CO 2 , or supercritical N 2 , more preferably CO 2 ;

[0023] Preferably, if the antifouling agent is a composition of a hydroxy acid ester oligomer and a bromofuranone, the hydroxy acid ester oligomer is 1 to 5wt% of the chemical fiber cord, preferably 3 to 4wt%, and the bromofuranone is 70 to 180wt% of the hydroxy acid ester oligomer; if the antifouling agent is a composition of a hydroxy acid ester oligomer and an alkaloid, the hydroxy acid ester oligomer is 1 to 5wt% of the chemical fiber cord, preferably 3 to 4wt%, and the alkaloid is 2 to 8wt% of the hydroxy acid ester oligomer, preferably 3 to 7wt%; if the antifouling agent is a composition of a hydroxy acid ester oligomer, a bromofuranone and an alkaloid, the hydroxy acid ester oligomer is 1 to 5wt% of the chemical fiber cord, the alkaloid is 2 to 8wt% of the hydroxy acid ester oligomer, and the bromofuranone is 70 to 180wt% of the hydroxy acid ester oligomer.

[0024] Preferably, the bromofuranone is 5-bromofuran-2(5H)-one or 4-bromofuran-2-one, wherein the 5-bromofuran-2(5H)-one (C 4 H 3 B O 2 ) is used in an amount of 70 to 150 wt % of the hydroxy acid ester oligomer, preferably 90 to 130 wt %, and the 4-bromofuran-2-one (C 4 H 3 B O 2 ) is used in an amount of 80 to 180 wt % of the hydroxy acid ester oligomer, preferably 110 to 150 wt %;

[0025] Preferably, the alkaloid is synthetic capsaicin (trans-8-methyl-N-vanillyl-6-nonenamide, C 18 H 27 NO 3 , insoluble in water), or synthetic camptothecin ((S)-4-ethyl-4-hydroxy-1H-pyrano[3',4':6,7]indolizino[1,2-b]quinoline-3,14-(4H,12H)-dione, C20H16N2O4; insoluble in water); the amount of capsaicin is 2-5wt% of the hydroxy acid ester oligomer, preferably 3-4wt%; the amount of camptothecin is 4-8wt% of the hydroxy acid ester oligomer, preferably 5-7wt%;

[0026] Preferably, an auxiliary agent may be added to the drug storage tank. The auxiliary agent is an alcohol solvent such as methanol, ethanol, glycerol, etc., which plays a role in improving the solubility of the antifouling agent in the SCF, preferably ethanol; the amount of the auxiliary agent is 50 to 200 wt% of the antifouling agent, preferably 80 to 150 wt%;

[0027] Preferably, the chemical fiber cord is one of polyolefin fiber (polyethylene PE fiber, ultra-high molecular weight polyethylene UHMWPE fiber, polypropylene PP fiber), polyester fiber, and aromatic polyamide fiber (para-aramid).

[0028] Preferably, the mass volume ratio of the chemical fiber cord to the SCF fluid is 1:11 to 1:16, preferably 1:12 to 1:14, and the unit is kg / L.

[0029] Another object of the present invention is to provide an antifouling fishing net rope, which is prepared by the above method.

[0030] The beneficial effects of the present invention are:

[0031] The present invention uses hydroxy acid ester oligomers as the main body, compounded with active substances derived from marine organisms and alkaloids derived from plants as a compounded bio-based antifouling agent, and after applying it to the shallow surface of fiber materials such as fishing nets and cables using SCF technology, it can defend against biofilms, multicellular organisms and large organisms in the process of marine biofouling formation:

[0032] (1) Using homopolymer hydroxy acid ester oligomers with broad-spectrum antibacterial and antiviral functions and a specific degree of polymerization range, and utilizing the function of hydroxy acid ester oligomers to repel single-cell organisms, kill single-cell organisms, thereby preventing them from forming biofilms on the fiber surface and eliminating the attachment conditions of multicellular organisms;

[0033] (2) Select bioactive substances with antifouling function from gorgonians in the ocean that do not produce barnacles and algae, and select substances such as bromofuranone that can be artificially synthesized, and then compound them with hydroxy acid ester oligomers and apply them to fiber materials such as fishing nets and cables using SCF technology to expel and kill multicellular organisms, prevent the formation of a mucus layer, and eliminate the attachment basis of large marine organisms such as barnacles and algae;

[0034] (3) Alkaloids that can repel large marine organisms such as barnacles and seaweeds are selected from plants, and alkaloids such as capsaicin and camptothecin that can be artificially synthesized are selected from them. After being compounded with hydroxy acid ester oligomers, brominated furanones, etc., SCF technology is used to apply them to fiber materials such as fishing nets and cables to enhance their overall defense capabilities against fouling by marine organisms, expand the anti-fouling spectrum, and improve the anti-fouling effect.

[0035] By using SCF technology, the antifouling agent is directly fixed on the shallow surface of the fiber, which can avoid the use of resin materials as the main body of the antifouling coating, avoid coating processing, avoid the problem of uneven coating that is easily caused by coating processing, and avoid the harm to employees caused by the volatilization of additives during coating processing; SCF processing does not produce pollution, does not require drying steps, does not cause thermal damage and saves energy; the antifouling material is fixed by the SCF method, and the antifouling agent is only applied to the shallow surface of the fiber, which does not waste the antifouling agent and does not affect the mechanical properties of the fiber; the antifouling agent is fixed to the antifouling agent by relying on the shrinkage ability of the fiber surface when the SCF pressure is released, and the antifouling agent has a strong binding force on the fiber surface and a strong durability of the antifouling function;

[0036] The bio-based antibacterial and antiviral material hydroxy acid ester oligomer is compounded with marine active substances and alkaloids. It is non-toxic to the ocean and fish and does not damage the strength of fishing gear. It can establish a defense mechanism at all stages of marine fouling formation and has a synergistic and broad-spectrum anti-fouling effect. DETAILED DESCRIPTION

[0037] As mentioned above, in view of the shortcomings of the prior art, the inventors of this case have proposed the technical solution of the present invention after long-term research and extensive practice, which is mainly based on at least: the present invention utilizes the function of hydroxy acid ester oligomers to repel single-cell organisms, kill single-cell organisms, thereby preventing them from forming biofilms on the fiber surface and eliminating the attachment conditions of multicellular organisms. The bio-based antibacterial and antiviral material hydroxy acid ester oligomer is compounded with marine active substances and alkaloids, which is non-toxic to the ocean and fish and does not damage the strength of fishing gear. It can establish a defense mechanism in all links of marine fouling formation, and has synergistic and broad-spectrum antifouling effects. The SCF method is used to fix the antifouling material, and the antifouling agent is only applied to the shallow surface of the fiber, which does not waste the antifouling agent and does not affect the mechanical properties of the fiber; the antifouling agent is fixed to the antifouling agent by relying on the shrinkage ability of the fiber surface when the SCF is released. The antifouling agent has a strong binding force on the fiber surface and the durability of the antifouling function is strong.

[0038] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0039] A method for fixing an antifouling agent on the shallow surface of a fishing net line using SCF technology comprises the following steps:

[0040] Step S1: Pre-wind the synthetic fiber rope for fishing fences that need to be treated for anti-fouling into a loose bobbin, and insert the hollow core of the loose bobbin into the hollow column; the hollow column and the hollow core of the loose bobbin are both provided with a plurality of holes; to prevent the rope from contacting the high temperature of the high-pressure tank wall, the edge of the bobbin does not contact the high-pressure tank, and the height of the rope wound on the bobbin does not exceed the height of the edge of the bobbin.

[0041] The chemical fiber cord is one of polyolefin fiber (polyethylene PE fiber, ultra-high molecular weight polyethylene UHMWPE fiber, polypropylene PP fiber), polyester fiber, and aromatic polyamide fiber (para-aramid).

[0042] Step S2: placing the antifouling agent in the medicine storage tank, and then placing the medicine storage tank in a supercritical fluid high-pressure tank; at the same time, placing the hollow column loaded with the loose bobbin in the supercritical fluid high-pressure tank, the SCF dynamic circulation liquid outlet of the supercritical fluid high-pressure tank being located in the hollow core of the hollow column, so that the SCF fluid flowing out through the SCF dynamic circulation liquid outlet takes out the antifouling agent through the medicine storage tank and then sprays out through the holes of the hollow column, so that the rope wound thereon is in uniform contact with the SCF fluid;

[0043] The antifouling agent is a composite of a hydroxy acid ester oligomer and one or two of brominated furanone and alkaloid;

[0044] The hydroxy acid ester oligomer is referred to CN202111137059.1, and its general structural formula is as follows (I):

[0045]

[0046] Wherein m is a natural number of 0-3; when n is a natural number of 1-3, R1 is a C1-C5 alkyl group, and R2 is a C4-C8 alkyl group; when n is a natural number of 4-8, R1 is a C1-C5 alkyl group, and R2 is a C2-C8 alkyl group.

[0047] The SCF is supercritical CO 2 , or supercritical N 2 , more preferably CO 2 ; The mass volume ratio of the chemical fiber rope to the SCF fluid is 1:11 to 1:16, preferably 1:12 to 1:14, and the unit is kg / L.

[0048] If the antifouling agent is a composition of a hydroxy acid ester oligomer and a bromofuranone, the hydroxy acid ester oligomer is 1 to 5 wt% of the chemical fiber cord, preferably 3 to 4 wt%, and the bromofuranone is 70 to 180 wt% of the hydroxy acid ester oligomer; if the antifouling agent is a composition of a hydroxy acid ester oligomer and an alkaloid, the hydroxy acid ester oligomer is 1 to 5 wt% of the chemical fiber cord, preferably 3 to 4 wt%, and the alkaloid is 2 to 8 wt% of the hydroxy acid ester oligomer, preferably 3 to 7 wt%; if the antifouling agent is a composition of a hydroxy acid ester oligomer, a bromofuranone and an alkaloid, the hydroxy acid ester oligomer is 1 to 5 wt% of the chemical fiber cord, the alkaloid is 2 to 8 wt% of the hydroxy acid ester oligomer, and the bromofuranone is 70 to 180 wt% of the hydroxy acid ester oligomer.

[0049] The bromofuranone is 5-bromofuran-2(5H)-one or 4-bromofuran-2-one, and the 5-bromofuran-2(5H)-one (C 4 H 3 B O 2 ) is used in an amount of 70 to 150 wt % of the hydroxy acid ester oligomer, preferably 90 to 130 wt %, and the 4-bromofuran-2-one (C 4 H 3 B O 2 ) is used in an amount of 80 to 180 wt % of the hydroxy acid ester oligomer, preferably 110 to 150 wt %;

[0050] The alkaloid is synthetic capsaicin (trans-8-methyl-N-vanillyl-6-nonenamide, C 18 H 27 NO 3 , insoluble in water), or synthetic camptothecin ((S)-4-ethyl-4-hydroxy-1H-pyrano[3',4':6,7]indolizino[1,2-b]quinoline-3,14-(4H,12H)-dione, C20H16N2O4; insoluble in water); the amount of capsaicin is 2-5wt% of the hydroxy acid ester oligomer, preferably 3-4wt%; the amount of camptothecin is 4-8wt% of the hydroxy acid ester oligomer, preferably 5-7wt%;

[0051] An auxiliary agent may also be added to the drug storage tank. The auxiliary agent is an alcohol solvent such as methanol, ethanol, glycerol, etc., which plays a role in improving the solubility of the antifouling agent in the SCF, preferably ethanol; the amount of the auxiliary agent is 50-200wt% of the antifouling agent, preferably 80-150wt%;

[0052] Step S3: After closing the high-pressure tank, the air is extracted, and the temperature is raised from room temperature to 60-170°C at a rate of 4-10°C / min, and the pressure is raised to 20-30MPa at a rate of 0.7-2.5MPa / min, so that the whole system reaches a balanced state, and the rope reaches a high temperature and high pressure state in a relatively short time and enters a swelling stage, so that the antifouling agent is fully dissolved in the SCF;

[0053] The temperature and pressure in the SCF processing technology are mainly determined by the swelling property of the processed fiber and the solubility of the antifouling agent in SCF. It is hoped that SCF can rapidly swell the processing object (fiber material) under appropriate temperature and pressure, and make the antifouling agent highly soluble in SCF, so that the high concentration of antifouling agent can enter the swollen surface layer, and after the processing is completed, as the SCF cools down and releases pressure to dissipate, the fiber surface shrinks, and the antifouling agent is firmly fixed on the shallow surface of the fiber. For PE and UHMWPE fibers, the temperature range is 80-95°C, preferably 85-90°C; the processing temperature of PP fibers is 90-105°C, preferably 95-100°C; the temperature range of PET fibers is 115-130°C, preferably 120-125°C; the processing temperature of para-aramid is 160-190°C, preferably 170-180°C. The processing pressure of SCF is mainly affected by equipment conditions and usually needs to be within the range of 20 to 30 MPa, preferably 22 to 26 MPa.

[0054] In order to maximize the processing efficiency and anti-fouling effect, special temperature and pressure increase procedures and pressure reduction procedures should be adopted. The purpose of the temperature and pressure increase stage is to accelerate the fiber to enter the swelling stage. The temperature increase rate is 4-10℃ / min (preferably 6-8℃ / min) and the pressure increase rate is 0.7-2.5MPa / min (preferably 1.2-2.0MPa / min), so that the fiber reaches a high temperature and high pressure state as soon as possible and enters the swelling stage; and the antifouling agent is fully dissolved in the SCF.

[0055] Step S4: in a system equilibrium state, immersing the hydroxy acid ester oligomer solution and the fiber to be processed in a supercritical fluid for periodic dynamic motion for not less than 40 minutes, and the stable stage of heat preservation and pressure preservation allows the antifouling agent with high solubility to smoothly enter the shallow surface of the fiber;

[0056] The longer the SCF processing time is, the more antifouling agents such as hydroxy acid ester oligomers will penetrate into the superficial surface of the fiber. Considering the processing efficiency, the processing time under high temperature and high pressure is preferably 40 to 60 minutes, which depends on the fiber type, specification, antibacterial and antiviral performance requirements and processing cost.

[0057] The periodic dynamic motion is a combination of dynamic and static motions in one motion cycle, the dynamic cycle time accounts for 40 to 80%, and the cycle time is 1 to 3 minutes;

[0058] After the temperature and pressure in the high-pressure tank reach the process setting value, in order to ensure that the fibers in different parts of the high-pressure tank can receive SCF with the same antifouling agent content, the SCF in the cylinder needs to be periodically moved under the action of the circulating pump. There is a part of dynamic injection time in a movement cycle, so that the fibers relatively still in various parts of the cylinder can be contacted by the moving fluid containing hydroxy acid ester oligomers and penetrate into the fiber assembly, bringing the antifouling agent to the surface of the fibers in various parts; the purpose of the SCF being in a static state is to allow the antifouling agent attached to the fiber surface to penetrate into the non-crystalline area of ​​the shallow surface of the fiber under the premise that the fiber is swollen by SCF under the promotion of concentration gradient. In a cycle, the dynamic time accounts for 40-80%, and 50-70% is more preferred; the cycle time is 1-3 minutes, preferably about 2 minutes.

[0059] Step S5: After the periodic dynamic movement is completed, the temperature is first rapidly cooled to room temperature at a rate of 3-5°C / min. Then, in order to prevent the antifouling agent from being driven out by the pressure difference between the inside and outside of the fiber due to excessive pressure release, a slower pressure reduction rate is required. The pressure is reduced at a rate of 0.5 to 1.2 MPa / min, preferably 0.8 to 1.0 MPa / min, until the pressure in the high-pressure tank is balanced with the ambient pressure; as the supercritical fluid high-pressure tank is depressurized, the SCF is released, and the antifouling agent is fixed to the surface of the rope due to fiber shrinkage.

[0060] In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0061] The 5-bromofuran-2(5H)-one and 4-bromofuran-2-one used in the following examples were purchased from Shanghai Hanxiang Biotechnology Co., Ltd.; capsaicin was purchased from Wuhan Zeshancheng Biomedical Technology Co., Ltd.; camptothecin was purchased from Shaanxi Haochen Biotechnology Co., Ltd. R-(-)-3-hydroxybutyric acid octyl ester, R-(-)-3-hydroxybutyric acid ethyl ester oligomer (n=4-8), R-(-)-3-hydroxybutyric acid hexyl ester, R-(-)3-hydroxybutyric acid pentyl ester, and R-(-)-lactate hexyl ester were provided by Zhejiang Yingmate Biotechnology Co., Ltd.

[0062] In the following example, the antifouling ropes processed by SCF are braided into a mesh with an overall size of 500mm×500mm and a mesh size of 40mm×40mm. On the sea surface, an antifouling effect test system is composed of a float, an anchor rope, three upper and lower connected rectangular frames for installing the mesh, a weight and an anchor system, and the frame size is 500mm×500mm. The three frames are installed with the mesh obtained by the same processing method of the embodiment to form three sub-samples, which are arranged at positions of 1m~1.5m, 1.5m~2.0m, and 2.0m~2.5m underwater. From the perspective of shortening the experimental time, the summer with higher air and seawater temperatures is selected for the experiment, and the experiment lasts for one month (May 10th to June 9th). After the end, a white plastic plate is used to take pictures and the image processing method is used to determine the percentage of the fouling organism coverage area to the total area (30-day attachment area rate, %) to evaluate the antifouling effect of the mesh.

[0063] Example 1: Antifouling Processing of Ultra-High Molecular Weight Polyethylene Ropes and Cables

[0064] Ultra-high molecular weight polyethylene (UHMWPE) ropes in SCF-CO 2 The bath ratio in the high-pressure tank is 1:14 (kg / L), the amount of R-(-)-3-hydroxybutyric acid octyl ester is 5.0% of the mass of UHMWPE, the amount of 5-bromofuran-2(5H)-one is 70wt% of the amount of R-(-)-3-hydroxybutyric acid octyl ester, and the amount of ethanol is 120wt% of the total amount of R-(-)-3-hydroxybutyric acid octyl ester and 5-bromofuran-2(5H)-one; the process design temperature is 90°C, the pressure is 25MPa, and the time is 45min.

[0065] The bobbin with UHMWPE rope wound around it is placed in a high-pressure tank, R-(-)-3-hydroxybutyric acid octyl ester and 5-bromofuran-2(5H)-one are pre-mixed evenly according to the set dosage and placed in the drug storage tank between the SCF storage tank and the high-pressure tank, the high-pressure tank is closed and sealed, and the air is pumped out with an air pump; the SCF-CO in the tank 2 Add the antifouling agent to the high-pressure tank through the medicine storage tank. Turn on the heater and compression pump, with a heating rate of 4°C / min and a pressure increase rate of 1.6MPa / min to reach the process design temperature and pressure; turn on the circulation pump, SCF with a cycle movement time of 2min and a dynamic injection time of 50%. After completing 45min of steady-state processing, first cool down to room temperature at a rate of 4°C / min, and then reduce the pressure at a rate of 0.8MPa / min. After the pressure in the high-pressure tank is balanced with the ambient pressure, open the sealing cover of the high-pressure tank, take out the edged bobbin, and obtain the UHMWPE cable that has been processed for antifouling. After the simulated fouling experiment in the sea, the adhesion area rate is 5.6% in 30 days.

[0066] Example 2: Antifouling Processing of Polypropylene Cable

[0067] Polypropylene (PP) ropes in SCF-CO 2 The bath ratio in the high-pressure tank is 1:13 (kg / L), the amount of R-(-)-3-hydroxybutyric acid ethyl oligomer (n=4-8) is 4.0% of the mass of PP, the amount of 5-bromofuran-2(5H)-one is 100wt% of R-(-)-3-hydroxybutyric acid ethyl oligomer (n=4-8), and the amount of capsaicin is 3.5wt% of the PP rope; the amount of ethanol is 100wt% of the amount of R-(-)-3-hydroxybutyric acid ethyl oligomer (n=4-8), capsaicin, and 5-bromofuran-2(5H)-one. The process design temperature is 100°C, the pressure is 25MPa, and the time is 40min.

[0068] The bobbin with PP rope wound around it is placed in a high-pressure tank, and the combined antifouling agent such as R-(-)-3-hydroxybutyric acid ethyl ester oligomer (n=4-8) is pre-mixed and evenly placed in the medicine storage tank between the SCF storage tank and the high-pressure tank. The high-pressure tank is closed and sealed, and the air is pumped out with an air pump; the SCF-CO in the tank is 2 Add the antifouling agent to the high-pressure tank through the medicine storage tank. Turn on the heater and compression pump, with a heating rate of 4.8℃ / min and a pressure increase rate of 1.36MPa / min to reach the process design temperature and pressure; turn on the circulation pump, SCF has a cycle movement time of 2min and a dynamic injection time of 60%. After completing 40min of steady-state processing, first cool it down to room temperature at a rate of 3℃ / min, and then reduce the pressure at a rate of 0.7MPa / min. After the pressure in the high-pressure tank is balanced with the ambient pressure, open the sealing cover of the high-pressure tank, take out the edged bobbin, and obtain the PP rope processed with antifouling. It is woven into a mesh and subjected to a simulated fouling test in the sea, with an adhesion area rate of 3.3% in 30 days.

[0069] Example 3: Antifouling Processing of 3mm Diameter Polyester Cable

[0070] 3mm diameter polyester (PET) rope in SCF-CO 2 The bath ratio in the high-pressure tank is 1:12 (kg / L), the amount of R-(-)-3-hydroxybutyric acid hexyl ester is 4.0wt% of the mass of PET, and the amount of camptothecin is 4.0wt% of the mass of R-(-)-3-hydroxybutyric acid hexyl ester; the amount of ethanol is 80wt% of the amount of R-(-)-3-hydroxybutyric acid hexyl ester and camptothecin. The process design temperature is 100°C, the pressure is 22MPa, and the time is 45min.

[0071] The bobbin with PET rope wound around it is placed in a high-pressure tank, and the combined antifouling agent such as R-(-)-3-hydroxybutyrate is pre-mixed evenly according to the set dosage and placed in the drug storage tank between the SCF storage tank and the high-pressure tank. The high-pressure tank is closed and sealed, and the air is pumped out with an air pump; the SCF-CO in the tank2 Add the antifouling agent to the high-pressure tank through the medicine storage tank. Turn on the heater and compression pump, with a heating rate of 6.8℃ / min and a pressure increase rate of 1.12MPa / min to reach the process design temperature and pressure; turn on the circulation pump, SCF according to the cycle movement time of 2min, the dynamic injection time accounts for 60%, and after completing 45min of steady-state processing, first cool down to room temperature at a rate of 4℃ / min, and then reduce the pressure at a rate of 0.6MPa / min. After the pressure in the high-pressure tank is balanced with the ambient pressure, open the sealing cover of the high-pressure tank, you can take out the edged bobbin, and get the PET rope processed with antifouling. It is woven into a mesh and subjected to a simulated fouling test in the sea. The adhesion area rate is 3.9% after 30 days.

[0072] Example 4: Antifouling Processing of 5mm Diameter Polyester Cable

[0073] 5mm diameter polyester (PET) rope in SCF-CO 2 The bath ratio in the high-pressure tank is 1:13 (kg / L), the amount of R-(-)3-hydroxybutyric acid pentyl ester is 4.0% of the mass of PET; the amount of 5-bromofuran-2(5H)-one is 120% of the mass of R-(-)3-hydroxybutyric acid pentyl ester, the amount of camptothecin is 6% of the mass of fiber; the amount of ethanol is 100% of the amount of R-(-)3-hydroxybutyric acid pentyl ester, 5-bromofuran-2(5H)-one, and camptothecin. The process design temperature is 125°C, the pressure is 22MPa, and the time is 45min.

[0074] The bobbin with PET rope wound around it is placed in a high-pressure tank, and the combined antifouling agent such as R-(-)-3-hydroxybutyrate is pre-mixed evenly according to the set dosage and placed in the medicine storage tank between the SCF storage tank and the high-pressure tank. The high-pressure tank is closed and sealed, and the air is pumped out with an air pump; the SCF-CO in the tank 2 Add the antifouling agent to the high-pressure tank through the medicine storage tank. Turn on the heater and compression pump, with a heating rate of 6.8℃ / min and a pressure increase rate of 1.12MPa / min to reach the process design temperature and pressure; turn on the circulation pump, SCF according to the cycle movement time of 2min, the dynamic injection time accounts for 60%, and after completing 45min of steady-state processing, first cool down to room temperature at a rate of 3℃ / min, and then reduce the pressure at a rate of 0.6MPa / min. After the pressure in the high-pressure tank is balanced with the ambient pressure, open the sealing cover of the high-pressure tank, you can take out the edged bobbin, and get the PET rope processed with antifouling. It is woven into a mesh and subjected to a simulated fouling test in the sea, and the adhesion area rate is 3.5% in 30 days.

[0075] Example 5: Antifouling Processing of Para-aramid Cable

[0076] Para-aramid filament ropes and cables in SCF-CO 2The bath ratio in the high-pressure tank is 1:14 (kg / L), the amount of R-(-)-hexyl lactate is 5.0% of the fiber mass; the amount of 4-bromofuran-2-one is 100% of R-(-)-hexyl lactate, the amount of capsaicin is 4% of the fiber mass; the amount of ethanol is 150% of the amount of R-(-)-hexyl lactate, 4-bromofuran-2-one, and capsaicin. The process design temperature is 170°C, the pressure is 26MPa, and the time is 60min.

[0077] The bobbin with aramid rope wound around it is placed in a high-pressure tank, and the combined antifouling agent such as R-(-)-hexyl lactate is pre-mixed evenly according to the set dosage and placed in the medicine storage tank between the SCF storage tank and the high-pressure tank. The high-pressure tank is closed and sealed, and the air is pumped out with an air pump; the SCF-CO in the tank 2 Add the antifouling agent to the high-pressure tank through the medicine storage tank. Turn on the heater and compression pump, with a heating rate of 10℃ / min and a pressure increase rate of 1.44MPa / min. After reaching the process design temperature and pressure, turn on the circulation pump. SCF has a cycle movement time of 2min and a dynamic injection time of 70%. After completing 60min of steady-state processing, first cool down to room temperature at a rate of 5℃ / min, and then reduce the pressure at a rate of 0.75MPa / min. After the pressure in the high-pressure tank is balanced with the ambient pressure, open the sealing cover of the high-pressure tank, take out the edged bobbin, and obtain the aramid rope processed with antifouling. It is woven into a mesh and subjected to a simulated fouling test in the sea. The adhesion area rate is 3.8% in 30 days.

[0078] The 30-day adhesion rate of the above examples, the ordinary PET blank sample and the conventional PET control sample treated with Wuxi self-polishing antifouling coating is listed in the following table:

[0079] sample Example 1 Example 2 Example 3 Example 4 Example 5 Blank Control 30-day adhesion area rate, % 5.61 3.32 4.93 3.57 3.84 27.8 3.72

[0080] It can be seen that the simple use of hydroxy acid ester oligomers in combination with brominated furanone and alkaloids such as capsaicin and camptothecin can achieve the level of the Wuxi self-polishing antifouling coating, which is currently widely used but has environmental pollution hazards, and is expected to achieve better antifouling effects through optimization.

Claims

1. A method for antifouling fishing nets and ropes by using a hydroxy acid ester oligomer compounded with an antifouling agent, characterized in that The method comprises the following steps: Step S1: pre-winding the synthetic fiber rope for fishing fence into a loose bobbin, inserting the hollow core of the loose bobbin into the hollow column; the hollow column and the hollow core of the loose bobbin are both provided with a plurality of holes, and the holes of the two are ensured to be aligned with each other; Step S2: placing the antifouling agent in the medicine storage tank, and then placing the medicine storage tank in a supercritical fluid high-pressure tank; at the same time, placing the hollow column loaded with the loose bobbin in the supercritical fluid high-pressure tank, the SCF dynamic circulation liquid outlet of the supercritical fluid high-pressure tank being located in the hollow core of the hollow column, so that the SCF fluid flowing out through the SCF dynamic circulation liquid outlet takes out the antifouling agent through the medicine storage tank and then sprays out through the holes of the hollow column, so that the rope wound thereon is in uniform contact with the SCF fluid; Step S3: After closing the high-pressure tank, the air is extracted, and then the temperature is increased from room temperature to 60-170°C at a rate of 4-10°C / min, and the pressure is increased to 20-30MPa at a rate of 0.7-2.5MPa / min, so that the whole system reaches a balanced state, the rope reaches a high temperature and high pressure state in a relatively short time, enters a swelling stage, and the antifouling agent is fully dissolved in the SCF; Step S4: in a system equilibrium state, immersing the hydroxy acid ester oligomer solution and the fiber to be processed in a supercritical fluid for periodic dynamic motion for not less than 40 minutes, and the antifouling agent with high solubility enters the shallow surface of the fiber during the stable stage of heat preservation and pressure preservation; In the periodic dynamic motion, a motion cycle is a combination of dynamic and static, the time in the dynamic cycle accounts for 40-80%, and the cycle time is 1-3 minutes; Step S5: After the periodic dynamic movement is completed, the temperature is first lowered to room temperature at a rate of 3-5°C / min, and then the pressure is reduced at a rate of 0.5-1.2MPa / min until the pressure in the high-pressure tank is balanced with the ambient pressure; as the supercritical fluid high-pressure tank is depressurized, the SCF is released, and the antifouling agent is fixed on the surface of the rope due to fiber shrinkage; The antifouling agent is a composition of a hydroxy acid ester oligomer and an alkaloid, or a composition of a hydroxy acid ester oligomer, a brominated furanone and an alkaloid; If the antifouling agent is a composite of hydroxy acid ester oligomer and alkaloid, the hydroxy acid ester oligomer is 1-5wt% of the chemical fiber cord, and the alkaloid is 2-8wt% of the hydroxy acid ester oligomer; If the antifouling agent is a composite of hydroxy acid ester oligomer, bromofuranone and alkaloid, the hydroxy acid ester oligomer is 1-5wt% of the chemical fiber cord, the alkaloid is 2-8wt% of the hydroxy acid ester oligomer, and the bromofuranone is 70-180wt% of the hydroxy acid ester oligomer; The general structural formula of the hydroxy acid ester oligomer is as follows (I): Formula (I) Wherein m is a natural number of 0-3; when n is a natural number of 1-3, R1 is a C1-C5 alkyl group, and R2 is a C4-C8 alkyl group; when n is a natural number of 4-8, R1 is a C1-C5 alkyl group, and R2 is a C2-C8 alkyl group; The alkaloid is trans-8-methyl-N-vanillyl-6-nonenamide, or (S)-4-ethyl-4-hydroxy-1H-pyrano[3',4':6,7]indolizino[1,2-b]quinoline-3,14-(4H,12H)-dione; The bromofuranone is 5-bromofuran-2(5H)-one or 4-bromofuran-2-one.

2. The method according to claim 1, characterized in that: The SCF is supercritical CO2 or supercritical N2.

3. The method according to claim 1, characterized in that: An auxiliary agent is also added into the drug storage tank, and the auxiliary agent is an alcohol solvent; the amount of the auxiliary agent is 50-200wt% of the antifouling agent.

4. The method according to claim 3, characterized in that: The auxiliary agent is one of methanol, ethanol and glycerol.

5. The method according to claim 1, characterized in that: The chemical fiber cord is one of polyolefin fiber, polyester fiber and aromatic polyamide fiber.

6. The method according to claim 1 or 2, characterized in that: The mass volume ratio of the chemical fiber cord to the SCF fluid is 1:11 to 1:16, and the unit is kg / L.

7. An antifouling fishing net rope prepared by the method according to any one of claims 1 to 6.

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