Fiber capable of being used for marine ranching

Abstract

The invention discloses a fiber for marine ranches, which is prepared from high molecular weight polyethylene resin, a solvent, an antioxidant and a compound anti-adhesion agent, and the compound anti-adhesion agent is prepared from an organic polymer anti-adhesion agent and an inorganic anti-adhesion agent. The breaking strength of the efficient anti-adhesion fiber capable of being used for the marine ranching is 17-43 g / D, the anti-adhesion rate / antifouling rate of the efficient anti-adhesion fiber to escherichia coli, staphylococcus aureus and candida albicans is 98% or above, and adhesion of marine fouling organisms can be remarkably reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of marine ranching, and in particular relates to a fiber that can be used in marine ranching. Background Art

[0002] High molecular weight polyethylene fiber (HMPE fiber for short) is known as one of the three high-tech fibers together with carbon fiber and aramid. It has the characteristics of high strength, high modulus, low specific gravity, strong light resistance and high wear resistance. It is also resistant to water, moisture, seawater and mildew, fatigue resistance and long flex life. It is currently the commercial high-performance fiber with the highest specific strength. It is widely used in marine ranch nets, fishing nets, high-grade ropes and other fields. However, after HMPE rope net materials are used in marine ranch nets for a period of time, they will be attached by marine fouling organisms such as bacteria, algae, and shellfish, which will cause huge economic losses and safety hazards to human marine ranch activities. In addition, HMPE fiber has a smooth surface and low surface energy, and it is difficult to effectively combine with conventional inorganic and organic anti-attachment agents, which makes the anti-attachment effect of HMPE fibers and fabrics treated by post-treatment methods such as padding and coating with anti-attachment agents poor and short-term. The intrinsic anti-adhesion method is to compound high-efficiency anti-adhesion agents suitable for spinning into special spinning raw materials to prepare composite fibers and fishing net materials with intrinsic anti-adhesion function. It can effectively simplify the anti-adhesion work of fishing nets, reduce production costs and labor intensity of workers, and improve work efficiency. At the same time, it has good anti-adhesion effect and has gradually attracted widespread attention.

[0003] The preparation of anti-attachment HMPE fibers has been explored. For example, in the patent application with publication number CN116555932A, polyhexamethylene biguanide hydrochloride graft copolymer powder was added to the HMPE spinning suspension to obtain HMPE fibers with long-lasting anti-attachment. However, the above-mentioned graft-based polymer material belongs to a contact-type anti-attachment mechanism. Once the surface is coated with attachments, its anti-attachment performance will be significantly reduced. This is because the antimicrobial activity of the graft is based on direct contact. If the surface of the material is covered with biological attachments, the contact-type anti-attachment agent cannot directly contact the microorganisms in the water, thereby losing its effectiveness and affecting its long-term anti-attachment effect. Compared with a single mechanism (contact or release), the contact-release synergistic surface provides a more promising solution for preventing initial bacterial attachment and inhibiting biofilm formation. Therefore, for anti-adhesion materials for marine ranches, the characteristics of contact anti-adhesion agents (contact type) and slow-release anti-adhesion agents (release type) are combined, and a contact-release synergistic anti-adhesion technology that integrates contact and release mechanisms is adopted. It can quickly kill or inhibit bacteria attached to the surface of fishing nets through contact, and at the same time prevent the growth and accumulation of new biological contamination through a slow release mechanism. It is expected to construct efficient and long-lasting anti-adhesion fiber materials that can be used in marine ranches.

[0004] Therefore, directly adding contact-release anti-adhesion agents during the HMPE fiber production process is expected to produce durable and efficient anti-adhesion HMPE fibers that can be used in marine ranches. Inorganic anti-adhesion agents have the advantages of good anti-adhesion and heat resistance. At the same time, there is a dissolution effect during the application process, which will continuously release the anti-adhesion agent to maintain the anti-adhesion effect. There are no reports on preparing a composite anti-adhesion agent powder by combining an organic polymer anti-adhesion agent with an inorganic anti-adhesion agent and adding it to HMPE gel spinning to prepare durable and efficient anti-adhesion HMPE fibers that can be used in marine ranches. Summary of the invention

[0005] The object of the present invention is to provide a fiber that can be used in marine ranching.

[0006] Another object of the present invention is to provide a method for preparing the fiber that can be used for marine ranching.

[0007] Another object of the present invention is to provide an application of the fiber that can be used for marine ranching in the preparation of marine ranching materials.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] In the first aspect of the present invention, a fiber that can be used in marine ranches is provided, which is prepared from high molecular weight polyethylene (HMPE) resin, solvent, antioxidant, and compound anti-adhesion agent, wherein the compound anti-adhesion agent is prepared from an organic polymer anti-adhesion agent and an inorganic anti-adhesion agent, the mass ratio of high molecular weight polyethylene (HMPE) resin to solvent is 1:2-30 (preferably 1:13.3, 1:14.4, 1:9), the mass percentage of the antioxidant to the mass percentage of the high molecular weight polyethylene (HMPE) resin is 0.1%-1.5% (preferably 0.5%), the mass percentage of the compound anti-adhesion agent to the total mass of the high molecular weight polyethylene (HMPE) resin and the compound anti-adhesion agent is 0.1-50% (preferably 10%, 15%, 20%, 30%), and the mass percentage of the inorganic anti-adhesion agent to the total mass of the organic polymer anti-adhesion agent and the inorganic anti-adhesion agent is 1-50% (preferably 2%, 20%, 50%).

[0010] The organic polymer anti-adhesion agent is selected from polyhexamethylene biguanide hydrochloride grafted polyethylene and quaternary ammonium salt grafted polyethylene.

[0011] The melt index of the polyhexamethylene biguanide hydrochloride grafted polyethylene is 3.7 g / 10 min, the grafting rate of polyhexamethylene biguanide hydrochloride is 15-20% (preferably 15%, 20%), and the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is selected from 2200J and 6084A.

[0012] The grade of polyethylene in the quaternary ammonium salt grafted polyethylene is 2200J, the melt index is 3.7 g / 10 min, and the grafting rate of the quaternary ammonium salt is 8%.

[0013] The inorganic anti-adhesion agent is selected from nano copper, nano silver, polyethylene nano zinc anti-adhesion masterbatch, polyethylene nano copper anti-adhesion masterbatch, polyethylene nano silver anti-adhesion masterbatch.

[0014] The particle size of the nano copper is selected from 1 to 100 nm (preferably 50 nm).

[0015] The particle size of the nanosilver is selected from 1 to 100 nm (preferably 20 nm).

[0016] The content of nano zinc in the polyethylene nano zinc anti-adhesion masterbatch is 1-10% (preferably 5%).

[0017] The content of nano copper in the polyethylene nano copper anti-adhesion masterbatch is 1-10% (preferably 5%).

[0018] The content of nano silver in the polyethylene nano silver anti-adhesion masterbatch is 0.1-2% (preferably 1%).

[0019] The molecular weight of the high molecular weight polyethylene (HMPE) resin is 1 million to 8 million (preferably 6 million, 7 million, 3 million), and the brand is selected from LL-X-600, LL-X-300, and LL-X-700.

[0020] The solvent is selected from at least one of white oil and decalin.

[0021] The antioxidant is selected from at least one of phenolic antioxidants and amine antioxidants, and is preferably antioxidant 1010.

[0022] The breaking strength of the fiber that can be used for marine ranching is 17-43 g / D (preferably 32.9 g / D, 28.2 g / D, 27.8 g / D, 38.5 g / D, 36.6 g / D, 25.6 g / D, 26.34 g / D, 24.08 g / D), and the breaking elongation is 3-5.5% (preferably 4.02%, 4.32%, 4.56%, 3.67%, 3.89%, 5.02%, 3.12%, 5.12%); the anti-attachment rate / anti-fouling rate against Escherichia coli, Staphylococcus aureus, and Candida albicans is above 98%.

[0023] The second aspect of the present invention provides a method for preparing the fiber that can be used for marine ranching, comprising the following steps:

[0024] High molecular weight polyethylene (HMPE) resin, solvent, antioxidant and compound anti-adhesion agent are mixed and emulsified to obtain a spinning solution, and the spinning solution is fed into a twin-screw extruder (with a diameter of 30 to 120 mm (preferably 60 mm), an aspect ratio of 56 to 72 (preferably 68)), a plasticizing temperature of 260 to 340°C (preferably 275, 280, 285°C), and an extrusion temperature of a spinning manifold of 200 to 320°C (preferably 260°C); the diameter of the spinneret hole is 0.5 to 1 mm (preferably 0.80 mm); drying and super-stretching; or, removing the solvent, drying and super-stretching; and obtaining the fiber that can be used for marine ranching.

[0025] The emulsification temperature is 70-90°C (preferably 80°C), and the emulsification time is 15-40 min (preferably 15, 30, 40 min).

[0026] The preparation method of the composite anti-adhesion agent comprises the following steps:

[0027] Premixing an organic polymer anti-adhesion agent and an inorganic anti-adhesion agent, extruding and granulating, pulverizing at high speed, and passing through a 20-100 mesh (preferably 40, 60, 80, 100 mesh) sieve to obtain a compound anti-adhesion agent;

[0028] Alternatively, the organic polymer anti-adhesion agent and the inorganic anti-adhesion agent are pulverized at high speed and passed through a 20-100 mesh (preferably 40, 60, 80, 100 mesh) sieve to obtain a compound anti-adhesion agent.

[0029] The extrusion granulation is performed by extrusion granulation through a co-rotating twin screw (with a diameter of 36 mm and an aspect ratio of 40) at a temperature of 180 to 210° C. (preferably 180 or 190° C.).

[0030] The method for removing the solvent is selected from extraction or direct volatilization of the solvent, and the extractant during extraction is selected from at least one of toluene, xylene, dichloromethane and gasoline.

[0031] The stretching temperature is 100° C. to 160° C. (preferably 130, 135, 140° C.), and the total stretching multiple is 30 to 90 times (preferably 45, 48, 50, 54 times).

[0032] The third aspect of the present invention provides a use of the fiber that can be used for marine ranching in the preparation of marine ranching materials.

[0033] The marine ranch materials are selected from marine ropes, net cages, breeding fences and the like.

[0034] Due to the adoption of the above technical solution, the present invention has the following advantages and beneficial effects:

[0035] The present invention prepares a composite anti-adhesion agent powder by combining an organic polymer anti-adhesion agent with an inorganic anti-adhesion agent, and adds the powder to HMPE gel spinning to prepare a durable and efficient anti-adhesion HMPE fiber that can be used in marine ranches. The contact anti-adhesion agent (contact type) and the slowly released anti-adhesion agent (release type) are combined with the characteristics of the contact release synergistic anti-adhesion technology or synergistic anti-fouling technology that integrates the contact and release mechanisms to prepare the efficient anti-adhesion HMPE fiber or the efficient anti-fouling HMPE fiber. Experimental verification shows that the efficient HMPE fiber prepared by the present invention has the characteristics of being easy to use, safe, and highly efficient in anti-adhesion, and the anti-adhesion rate / anti-fouling rate reaches more than 98%, and can be widely used in marine ranches such as marine ropes, cages, and aquaculture fences.

[0036] The high-efficiency anti-attachment fiber for marine ranching provided by the present invention has a breaking strength of 17-43 g / D, an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus and Candida albicans of more than 98%, and can significantly reduce the attachment of marine fouling organisms.

[0037] The fiber that can be used for marine ranching of the present invention has the effects of being easy to use, having a significant anti-attachment effect and a long service life. DETAILED DESCRIPTION

[0038] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the following specific description is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0039] Example 1

[0040] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0041] The first step is to prepare the anti-adhesion agent powder

[0042] 25 kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 2200J, the melt index is 3.7 g / 10 min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 20%. The polyhexamethylene biguanide hydrochloride grafted polyethylene is purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.) and 0.5 kg of nano copper (model: MG-Cu-50, particle size: 50 nm, Shanghai Maoguo Nano Technology Co., Ltd.) are premixed, and the mass of nano copper accounts for 2% of the total mass of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent and nano copper. The mixture is extruded and granulated at a temperature of 180°C through a co-rotating twin-screw (with a diameter of 36 mm and an aspect ratio of 40), and crushed at high speed by a pulverizer through a 40-mesh sieve to obtain 20 kg of a composite anti-adhesion agent powder.

[0043] The second step is the preparation of fibers that can be used in marine ranching.

[0044] 15 kg of high molecular weight polyethylene (HMPE) resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-600, the molecular weight of HMPE resin is 6 million.), 200 kg of white oil, 0.075 kg of antioxidant 1010, and 1.67 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80°C for 15 minutes to obtain a spinning solution, the mass ratio of HMPE resin powder to white oil was 1:13.3; the mass percentage of antioxidant 1010 to the mass percentage of HMPE resin powder was 0. .5%, the mass percentage of the mass of the compound anti-adhesion agent powder obtained in the first step accounts for 10% of the total mass of the HMPE resin powder and the compound anti-adhesion agent powder obtained in the first step, the spinning solution is fed into a twin-screw extruder (diameter 60mm, aspect ratio 68), the plasticizing temperature is 285℃, the extrusion temperature of the spinning box is 260℃; the aperture of the spinneret is 0.80mm; the solvent is removed by extraction, the extractant is dichloromethane, the mixture is dried and stretched super-multiple, the stretching temperature is 140℃, the total stretching multiple is about 50 times, and 14kg of the fiber that can be used for marine ranching is obtained.

[0045] The prepared fiber that can be used in marine ranching has a breaking strength of 32.9 g / D, a breaking elongation of 4.02%, and an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 98%.

[0046] Example 2

[0047] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0048] The first step is to prepare the anti-adhesion agent powder

[0049] 25 kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 2200J, the melt index is 3.7 g / 10 min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 20%. The polyhexamethylene biguanide hydrochloride grafted polyethylene is purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.) and 0.5 kg of nano copper (model: MG-Cu-50, particle size: 50 nm, Shanghai Maoguo Nano Technology Co., Ltd.) are premixed, and the mass of nano copper accounts for 2% of the total mass of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent and nano copper. The mixture is extruded and granulated at a temperature of 180°C through a co-rotating twin-screw (with a diameter of 36 mm and an aspect ratio of 40), and crushed at high speed by a pulverizer through a 60-mesh sieve to obtain 20 kg of a composite anti-adhesion agent powder.

[0050] The second step is the preparation of fibers that can be used in marine ranching.

[0051] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-600, molecular weight of HMPE resin is 6 million), 200 kg of white oil, 0.075 kg of antioxidant 1010, and 3.75 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80° C. for 30 min to obtain a spinning solution, wherein the mass ratio of HMPE resin powder to white oil was 1:13.3; the mass percentage of antioxidant 1010 to HMPE resin powder was 0.5% ... The mass percentage of the obtained compound anti-adhesion agent powder to the total mass of the HMPE resin powder and the compound anti-adhesion agent powder obtained in the first step is 20%. The spinning solution is fed into a twin-screw extruder (diameter 60 mm, aspect ratio 68), the plasticizing temperature is 285°C, and the extrusion temperature of the spinning box is 260°C; the diameter of the spinneret hole is 0.80 mm; the solvent is extracted and removed, the extractant is dichloromethane, the fiber is dried and stretched, the stretching temperature is 140°C, and the total stretching multiple is about 50 times, to obtain 12 kg of the fiber that can be used for marine ranching.

[0052] The prepared fiber that can be used in marine ranching has a breaking strength of 28.2 g / D, a breaking elongation of 4.32%, and an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 99%.

[0053] Example 3

[0054] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0055] The first step is to prepare the anti-adhesion agent powder

[0056] 25 kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 2200J, the melt index is 3.7 g / 10 min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 20%. The polyhexamethylene biguanide hydrochloride grafted polyethylene is purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.) and 0.5 kg of nano copper (model: MG-Cu-50, particle size: 50 nm, Shanghai Maoguo Nano Technology Co., Ltd.) are premixed, and the mass of nano copper accounts for 2% of the total mass of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent and nano copper. The mixture is extruded and granulated at a temperature of 180°C through a co-rotating twin-screw (with a diameter of 36 mm and an aspect ratio of 40), and crushed at high speed by a pulverizer through an 80-mesh sieve to obtain 20 kg of a composite anti-adhesion agent powder.

[0057] The second step is the preparation of fibers that can be used in marine ranching.

[0058] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-600, molecular weight of HMPE resin is 6 million), 200 kg of white oil, 0.075 kg of antioxidant 1010, and 6.43 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80° C. for 40 min to obtain a spinning solution, wherein the mass ratio of HMPE resin powder to white oil was 1:13.3; the mass percentage of antioxidant 1010 to HMPE resin powder was 0.5%; the mass percentage of antioxidant 1010 to HMPE resin powder in the first step was 0.5%. The mass percentage of the obtained compound anti-adhesion agent powder is 30% of the total mass of the HMPE resin powder and the compound anti-adhesion agent powder obtained in the first step. The spinning solution is fed into a twin-screw extruder (diameter 60 mm, aspect ratio 68), the plasticizing temperature is 285°C, and the extrusion temperature of the spinning box is 260°C; the diameter of the spinneret hole is 0.80 mm; the solvent is removed by extraction, the extractant is dichloromethane, the mixture is dried and stretched super-multiple, the stretching temperature is 140°C, and the total stretching multiple is about 50 times, to obtain 13 kg of the fiber that can be used for marine ranching.

[0059] The prepared fiber that can be used in marine ranching has a breaking strength of 27.8 g / D, a breaking elongation of 4.56%, and an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 99.8%.

[0060] Example 4

[0061] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0062] The first step is to prepare the anti-adhesion agent powder

[0063] 25kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 6084A, the melt index is 3.7g / 10min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 15%. The polyhexamethylene biguanide hydrochloride grafted polyethylene was purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.), 0.25kg of nano copper (model: MG-Cu-50, particle size: 50nm, Shanghai Maoguo Nano Technology Co., Ltd.), 0.25kg of nano silver (model: LH-Ag -01, particle size: 20nm, purchased from Shanghai Lianghan Nano Technology Development Co., Ltd.) pre-mixed, the mass of nano-copper accounted for 1% of the total mass of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent, nano-copper, and nano-silver, and the mass of nano-silver accounted for 1% of the total mass of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent, nano-copper, and nano-silver. It was extruded and granulated at a temperature of 190°C by a co-rotating twin-screw (with a diameter of 36mm and an aspect ratio of 40), and pulverized at high speed by a pulverizer through a 100-mesh sieve to obtain 20kg of a composite anti-adhesion agent powder.

[0064] The second step is the preparation of fibers that can be used in marine ranching.

[0065] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-700, molecular weight of HMPE resin is 7 million), 215.8 kg of white oil, 0.075 kg of antioxidant 1010, and 1.67 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80° C. for 15 min to obtain a spinning solution, wherein the mass ratio of HMPE resin powder to white oil was 1:14.4; the mass percentage of antioxidant 1010 to HMPE resin powder was 0.5%; the mass percentage of antioxidant 1010 to HMPE resin powder was 0.5%. The mass percentage of the composite anti-adhesion agent powder obtained in the first step to the total mass of the HMPE resin powder and the composite anti-adhesion agent powder obtained in the first step is 10%, the spinning solution is fed into a twin-screw extruder (diameter 60 mm, aspect ratio 68), the plasticizing temperature is 285°C, the extrusion temperature of the spinning box is 260°C; the diameter of the spinneret hole is 0.80 mm; the solvent is extracted and removed, the extractant is dichloromethane, the fiber is dried and stretched, the stretching temperature is 140°C, the total stretching multiple is about 54 times, and 12 kg of the fiber that can be used for marine ranching is obtained.

[0066] The prepared fiber that can be used in marine ranching has a breaking strength of 38.5 g / D, a breaking elongation of 3.67%, and an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 99%.

[0067] Example 5

[0068] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0069] The first step is to prepare the anti-adhesion agent powder

[0070] 25kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 6084A, the melt index is 3.7g / 10min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 15%. The polyhexamethylene biguanide hydrochloride grafted polyethylene was purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.), 0.25kg of nano copper (model: MG-Cu-50, particle size: 50nm, Shanghai Maoguo Nano Technology Co., Ltd.), 0.25kg of nano silver (model: LH-Ag -01, particle size: 20nm, purchased from Shanghai Lianghan Nano Technology Development Co., Ltd.) pre-mixed, the mass of nano-copper accounted for 1% of the total mass of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent, nano-copper, and nano-silver, and the mass of nano-silver accounted for 1% of the total mass of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent, nano-copper, and nano-silver. It was extruded and granulated at a temperature of 190°C by a co-rotating twin-screw (with a diameter of 36mm and an aspect ratio of 40), and pulverized at high speed by a pulverizer through a 100-mesh sieve to obtain 20kg of a composite anti-adhesion agent powder.

[0071] The second step is the preparation of fibers that can be used in marine ranching.

[0072] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-700, molecular weight of HMPE resin is 7 million), 215.8 kg of white oil, 0.075 kg of antioxidant 1010, and 3.75 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80° C. for 30 min to obtain a spinning solution, wherein the mass ratio of HMPE resin powder to white oil was 1:14.4; the mass percentage of antioxidant 1010 to HMPE resin powder was 0.5%; the mass percentage of antioxidant 1010 to HMPE resin powder was 0.5%. The mass percentage of the composite anti-adhesion agent powder obtained in the first step to the total mass of the HMPE resin powder and the composite anti-adhesion agent powder obtained in the first step is 20%, the spinning solution is fed into a twin-screw extruder (diameter 60 mm, aspect ratio 68), the plasticizing temperature is 285°C, the extrusion temperature of the spinning box is 260°C; the diameter of the spinneret hole is 0.80 mm; the solvent is extracted and removed, the extractant is dichloromethane, the fiber is dried and stretched, the stretching temperature is 140°C, the total stretching multiple is about 54 times, and 13 kg of the fiber that can be used for marine ranching is obtained.

[0073] The prepared fiber that can be used in marine ranching has a breaking strength of 36.6 g / D, a breaking elongation of 3.89%, and an anti-attachment rate / anti-fouling rate against Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 99%.

[0074] Example 6

[0075] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0076] The first step is to prepare the anti-adhesion agent powder

[0077] 25kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the brand of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 6084A, the melt index is 3.7g / 10min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 20%. The polyhexamethylene biguanide hydrochloride grafted polyethylene was purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.) and 6.25kg of polyethylene nano-zinc anti-adhesion masterbatch (purchased from Weihai Hongwei Plastic Co., Ltd.) (the content of nano-zinc in the polyethylene nano-zinc anti-adhesion masterbatch is 5%) were crushed at high speed by a crusher. The mass of the polyethylene nano-zinc anti-adhesion masterbatch accounted for 20% of the total mass of the polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent and the polyethylene nano-zinc anti-adhesion masterbatch. After passing through a 60-mesh sieve, 23kg of the composite anti-adhesion agent powder was obtained.

[0078] The second step is the preparation of fibers that can be used in marine ranching.

[0079] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-600, molecular weight of HMPE resin is 6 million), 200 kg of white oil, 0.075 kg of antioxidant 1010, and 3.75 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80° C. for 15 min to obtain a spinning solution, wherein the mass ratio of HMPE resin powder to white oil was 1:13.3; the mass percentage of antioxidant 1010 to HMPE resin powder was 0.5%; the mass percentage of antioxidant 1010 to HMPE resin powder in the first step was 0.5%. The mass percentage of the obtained compound anti-adhesion agent powder accounts for 20% of the total mass of the HMPE resin powder and the compound anti-adhesion agent powder obtained in the first step. The spinning solution is fed into a twin-screw extruder (diameter 60 mm, aspect ratio 68), the plasticizing temperature is 285°C, and the extrusion temperature of the spinning box is 260°C; the aperture of the spinneret is 0.80 mm; the solvent is extracted and removed, the extractant is xylene, the mixture is dried and stretched at an ultra-high multiple, the stretching temperature is 135°C, and the total stretching multiple is about 45 times, to obtain 14 kg of the fiber that can be used for marine ranching.

[0080] The prepared fiber that can be used in marine ranching has a breaking strength of 25.6 g / D, a breaking elongation of 5.02%, and an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 99.8%.

[0081] Example 7

[0082] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0083] The first step is to prepare the anti-adhesion agent powder

[0084] 25 kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 2200J, the melt index is 3.7 g / 10 min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 20%. The polyhexamethylene biguanide hydrochloride grafted polyethylene is purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.) and 6.25 kg of polyethylene nano-copper anti-adhesion masterbatch (purchased from Weihai Hongwei Plastic Co., Ltd.) (the content of nano-copper in the polyethylene nano-copper anti-adhesion masterbatch is 5%) are crushed at high speed by a crusher. The mass of the polyethylene nano-copper anti-adhesion masterbatch accounts for 20% of the total mass of the polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent and the polyethylene nano-copper anti-adhesion masterbatch. After passing through a 60-mesh sieve, 25 kg of compound anti-adhesion agent powder is obtained.

[0085] The second step is the preparation of fibers that can be used in marine ranching.

[0086] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-600, molecular weight of HMPE resin is 6 million), 200 kg of white oil, 0.075 kg of antioxidant 1010, and 3.75 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80° C. for 15 min to obtain a spinning solution, wherein the mass ratio of HMPE resin powder to decalin was 1:13.3; the mass percentage of antioxidant 1010 to the mass percentage of HMPE resin powder ... 0.5%, the mass percentage of the mass of the compound anti-adhesion agent powder obtained in the first step accounts for 20% of the total mass of the HMPE resin powder and the compound anti-adhesion agent powder obtained in the first step, the spinning solution is fed into a twin-screw extruder (diameter 60mm, aspect ratio 68), the plasticizing temperature is 280℃, the extrusion temperature of the spinning box is 260℃; the aperture of the spinneret is 0.80mm; drying and super-stretching, the stretching temperature is 140℃, the total stretching multiple is about 48 times, and 20kg of the fiber that can be used for marine ranching is obtained.

[0087] The prepared fiber that can be used in marine ranching has a breaking strength of 26.34 g / D, a breaking elongation of 3.12%, and an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 99%.

[0088] Example 8

[0089] A method for preparing fiber that can be used in marine ranching comprises the following steps:

[0090] The first step is to prepare the anti-adhesion agent powder

[0091] 25kg of quaternary ammonium salt grafted polyethylene anti-adhesion agent (the brand of polyethylene in the quaternary ammonium salt grafted polyethylene is 2200J, the melt index is 3.7g / 10min, and the grafting rate of quaternary ammonium salt is 8%. The quaternary ammonium salt grafted polyethylene is purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.) and 25kg of polyethylene nano-silver anti-adhesion masterbatch (purchased from Weihai Hongwei Plastic Co., Ltd.) (the content of nano-silver in the polyethylene nano-silver anti-adhesion masterbatch is 1%) are pulverized at high speed by a pulverizer. The mass of the polyethylene nano-silver anti-adhesion masterbatch accounts for 50% of the total mass of the quaternary ammonium salt grafted polyethylene anti-adhesion agent and the polyethylene nano-silver anti-adhesion masterbatch. After passing through a 60-mesh sieve, 46kg of the composite anti-adhesion agent powder is obtained.

[0092] The second step is the preparation of fibers that can be used in marine ranching.

[0093] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-300, molecular weight of HMPE resin is 3 million), 135 kg of decalin, 0.075 kg of antioxidant 1010, and 2.65 kg of the compound anti-adhesion agent powder obtained in the first step were mixed, and emulsified at a temperature of 80° C. for 15 min to obtain a spinning solution, wherein the mass ratio of HMPE resin powder to decalin is 1:9; the mass percentage of antioxidant 1010 to the mass percentage of HMPE resin powder is 0. .5%, the mass percentage of the mass of the compound anti-adhesion agent powder obtained in the first step accounts for 15% of the total mass of the HMPE resin powder and the compound anti-adhesion agent powder obtained in the first step, the spinning solution is fed into a twin-screw extruder (diameter 60mm, aspect ratio 68), the plasticizing temperature is 275℃, the extrusion temperature of the spinning box is 260℃; the aperture of the spinneret is 0.80mm; drying and super-stretching, the stretching temperature is 130℃, the total stretching multiple is about 45 times, and 19kg of the fiber that can be used for marine ranching is obtained.

[0094] The prepared fiber that can be used in marine ranching has a breaking strength of 24.08 g / D, a breaking elongation of 5.12%, and an anti-attachment rate / anti-fouling rate for Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 99%.

[0095] Comparative Example 1

[0096] HMPE fiber preparation:

[0097] 15kg HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-600, the molecular weight of HMPE resin is 6 million), 200kg white oil, and 0.075kg antioxidant 1010 are mixed and emulsified at a temperature of 80°C for 15 minutes to obtain a spinning solution, the mass ratio of HMPE resin powder to white oil is 1:13.3; the mass percentage of antioxidant 1010 to the mass percentage of HMPE resin powder is 0.5%, and the spinning solution is fed into a twin-screw extruder (diameter 60mm, aspect ratio 68), the plasticizing temperature is 285°C, the extrusion temperature of the spinning manifold is 260°C; the pore size of the spinneret is 0.80mm; the solvent is extracted to remove the solvent, the extractant is dichloromethane, dried, super-stretched, the stretching temperature is 140°C, and the total stretching multiple is about 50 times, to obtain 12kg of the fiber that can be used for marine ranching.

[0098] The breaking strength of the prepared HMPE fiber is 40.8 g / D, and the breaking elongation is 3.94%.

[0099] Comparative Example 2

[0100] The preparation method of anti-adhesion HMPE fiber comprises the following steps:

[0101] The first step is to prepare the anti-adhesion agent powder.

[0102] 25 kg of polyhexamethylene biguanide hydrochloride grafted polyethylene anti-adhesion agent (the grade of polyethylene in the polyhexamethylene biguanide hydrochloride grafted polyethylene is 2200J, the melt index is 3.7 g / 10 min, and the grafting rate of polyhexamethylene biguanide hydrochloride is 20%. The polyhexamethylene biguanide hydrochloride grafted polyethylene was purchased from Guilin Xinxianli Antibacterial Materials Co., Ltd.) was crushed at high speed by a crusher and passed through a 40-mesh sieve to obtain 23 kg of anti-adhesion agent powder.

[0103] Step 2: Preparation of anti-adhesion HMPE fibers

[0104] 15 kg of HMPE resin powder (purchased from Shanghai Lianle Chemical Technology Co., Ltd., brand LL-X-600, the molecular weight of HMPE resin is 6 million), 220 kg of white oil, 0.075 kg of antioxidant 1010 and 1.67 kg of the anti-adhesion agent powder prepared in the first step were mixed, and emulsified at a temperature of 80°C for 15 minutes to obtain a spinning solution, the mass ratio of HMPE resin to white oil was 1:14.7; the mass percentage of antioxidant 1010 to HMPE resin was 0.5%; the mass percentage of anti-adhesion agent powder to the total mass of anti-adhesion agent powder and HMPE resin was 10%. The spinning solution was fed into a twin-screw extruder (diameter 60 mm, aspect ratio 68), the plasticizing temperature was 285°C, and the extrusion temperature of the spinning box was 260°C; the diameter of the spinneret hole was 0.80 mm; the solvent was removed by extraction, the extractant was dichloromethane, and the fiber was dried and stretched at an ultra-high multiple, the stretching temperature was 140°C, and the total stretching multiple was about 50 times, to obtain anti-adhesion HMPE fiber.

[0105] The prepared HMPE fiber has a breaking strength of 36.28 g / D, a breaking elongation of 4.32%, and an anti-attachment rate to Escherichia coli, Staphylococcus aureus, and Candida albicans of more than 94%.

[0106] Example effect verification:

[0107] According to the standard for anti-adhesion knitwear (FZ / T 73023-2006), the anti-adhesion effect / anti-fouling effect of the products prepared in the examples and comparative examples was tested, and the test data are shown in Table 1:

[0108] Table 1 Anti-adhesion effect / anti-fouling effect data

[0109]

[0110]

[0111] According to the results of Table 1, in Examples 1 to 8, an organic polymer anti-adhesion agent and an inorganic anti-adhesion agent are prepared together to form a composite anti-adhesion agent powder, which is added to HMPE resin powder for spinning to prepare fibers that can be used in marine ranches, and the anti-adhesion rate for Escherichia coli, Staphylococcus aureus, and Candida albicans is above 98%. In Comparative Example 1, since there is no anti-adhesion agent, there is no anti-adhesion rate for Escherichia coli, Staphylococcus aureus, and Candida albicans. In Comparative Example 2, since only an organic polymer anti-adhesion agent is present, the anti-adhesion rate for Escherichia coli, Staphylococcus aureus, and Candida albicans is relatively low. Therefore, the present invention solves the problem of low anti-adhesion efficiency of HMPE fibers, and has significant effects of significant anti-adhesion effect or anti-fouling effect and long service life.

[0112] The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment, it is not used to limit the present invention. Any technician familiar with this patent can make some changes or modify the technical contents suggested above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the solution of the present invention.

Claims

1. A fiber that can be used in marine ranching, characterized in that: The compound anti-adhesion agent is prepared from a high molecular weight polyethylene resin, a solvent, an antioxidant, and a compound anti-adhesion agent. The compound anti-adhesion agent is prepared from an organic polymer anti-adhesion agent and an inorganic anti-adhesion agent. The mass ratio of the high molecular weight polyethylene resin to the solvent is 1:2-30, the mass percentage of the antioxidant to the mass percentage of the high molecular weight polyethylene resin is 0.1%-1.5%, the mass percentage of the compound anti-adhesion agent to the total mass of the high molecular weight polyethylene resin and the compound anti-adhesion agent is 0.1%-50%, and the mass percentage of the inorganic anti-adhesion agent to the total mass of the organic polymer anti-adhesion agent and the inorganic anti-adhesion agent is 1-50%; The organic polymer anti-adhesion agent is selected from polyhexamethylene biguanide hydrochloride grafted polyethylene and quaternary ammonium salt grafted polyethylene; The inorganic anti-adhesion agent is selected from nano copper, nano silver, polyethylene nano zinc anti-adhesion masterbatch, polyethylene nano copper anti-adhesion masterbatch, and polyethylene nano silver anti-adhesion masterbatch.

2. The fiber that can be used for marine ranching according to claim 1, characterized in that: The particle size of the nano copper is selected from 1 to 100 nm; The particle size of the nano silver is selected from 1 to 100 nm.

3. The fiber that can be used for marine ranching according to claim 1, characterized in that: The content of nano zinc in the polyethylene nano zinc anti-adhesion masterbatch is 1 to 10%; The content of nano copper in the polyethylene nano copper anti-adhesion masterbatch is 1-10%; The content of nano silver in the polyethylene nano silver anti-adhesion masterbatch is 0.1-2%.

4. The fiber that can be used for marine ranching according to claim 1, characterized in that: The molecular weight of the high molecular weight polyethylene resin is 1 to 8 million.

5. The fiber that can be used for marine ranching according to claim 1, characterized in that: The solvent is selected from at least one of white oil and decalin.

6. The fiber that can be used for marine ranching according to claim 1, characterized in that: The antioxidant is selected from at least one of phenolic antioxidants and amine antioxidants.

7. A method for preparing fiber that can be used for marine ranching according to any one of claims 1 to 6, characterized in that: The following steps are involved: A high molecular weight polyethylene resin, a solvent, an antioxidant, and a compound anti-adhesion agent are mixed and emulsified to obtain a spinning solution, and the spinning solution is fed into a twin-screw extruder, the plasticizing temperature is 260-340°C, and the extrusion temperature of the spinning box is 200-320°C; the diameter of the spinneret hole is 0.5-1mm; drying and super-stretching; or, removing the solvent, drying, and super-stretching; to obtain the fiber that can be used in marine ranching.

8. The method for preparing fiber that can be used for marine ranching according to claim 7, characterized in that: The emulsification temperature is 70-90°C and the time is 15-40 minutes; The preparation method of the composite anti-adhesion agent comprises the following steps: Premixing an organic polymer anti-adhesion agent and an inorganic anti-adhesion agent, extruding and granulating, high-speed crushing, and passing through a 20-100 mesh screen to obtain a compound anti-adhesion agent; Alternatively, the organic polymer anti-adhesion agent and the inorganic anti-adhesion agent are crushed at high speed and passed through a 20-100 mesh sieve to obtain a compound anti-adhesion agent.

9. The method for preparing fiber that can be used for marine ranching according to claim 8, characterized in that: The extrusion granulation is carried out by extrusion granulation through a co-rotating twin screw at a temperature of 180 to 210°C; The method for removing the solvent is selected from extraction or direct volatilization of the solvent, and the extractant during extraction is selected from at least one of toluene, xylene, dichloromethane, and gasoline; The stretching temperature is 100° C. to 160° C., and the total stretching multiple is 30 to 90 times.

10. Use of the fiber applicable to marine ranching according to any one of claims 1 to 6 in the preparation of marine ranching materials.

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