阅读说明：本技术 一种具有防海洋污损特性的聚乙烯网线单丝的制备方法 (Preparation method of polyethylene mesh wire monofilament with marine fouling prevention characteristic ) 是由 张海龙 于 2019-08-19 设计创作，主要内容包括：本发明涉及材料科学领域,针对现有技术的涂层会剥落和维护成本高的问题,公开了一种具有防海洋污损特性的聚乙烯网线单丝的制备方法。每100质量份的单丝网线中包含以下物质：2.3-3.8份吡啶硫酮铜、2.2-3.5份吡啶溴代腈、2.8-3.2份改性纳米ZnO粉末、0.8-1.2份丙烯酸锌树脂,剩余质量份为高密度聚乙烯颗粒与聚丙烯粉的混合物。五个制备步骤主要包括：烘干、混匀材料、拉丝、定型及除溶剂。本发明直接将防污剂添加于网线单丝中,使网衣具有较好的防污性能；单丝具有一定的微纳米结构表面、耐磨性好；避免后续繁琐的防污涂料施工以及其对环境的污染；减少使用期间网线的维护工作,单丝制备工艺简单,节约加工成本。(The invention relates to the field of material science, and discloses a preparation method of a polyethylene mesh wire monofilament with marine fouling prevention property aiming at the problems that a coating in the prior art is peeled off and the maintenance cost is high. Every 100 parts by mass of the monofilament net thread comprises the following substances: 2.3-3.8 parts of copper pyrithione, 2.2-3.5 parts of pyridine bromonitrile, 2.8-3.2 parts of modified nano ZnO powder, 0.8-1.2 parts of zinc acrylate resin, and the balance of the mass parts of a mixture of high-density polyethylene particles and polypropylene powder. The five preparation steps mainly comprise: drying, uniformly mixing materials, drawing, shaping and removing a solvent. The invention directly adds the antifouling agent into the monofilament of the net wire, so that the net has better antifouling performance; the monofilament has a certain micro-nano structure surface and good wear resistance; avoiding subsequent complex antifouling paint construction and pollution to the environment; the maintenance work of the net wire during the use is reduced, the monofilament preparation process is simple, and the processing cost is saved.)

1. A preparation method of polyethylene mesh wire monofilament with marine fouling prevention characteristic is characterized in that every 100 parts by mass of the monofilament mesh wire comprise the following substances: 2.3-3.8 parts of copper pyrithione, 2.2-3.5 parts of pyridine bromonitrile, 2.8-3.2 parts of modified nano ZnO powder, 0.8-1.2 parts of zinc acrylate resin, and the balance of the mass parts of a mixture of high-density polyethylene particles and polypropylene powder.

2. The method for preparing the polyethylene mesh wire monofilament with the marine fouling prevention property as claimed in claim 1, is characterized by comprising the following steps:

(1) and drying: drying the mixture of the modified nano ZnO, the high-density polyethylene particles and the polypropylene powder;

(2) and uniformly mixing materials: uniformly mixing and stirring zinc acrylate resin, pyridine bromonitrile, copper pyrithione and modified nano ZnO powder, and continuously stirring for 40-50min to obtain a mixed material;

(3) drawing: drawing the mixed material, wherein the drawing and extruding process needs three stages of heating to draw out monofilaments;

(4) and shaping: cooling and shaping the monofilament drawn in the step (3);

(5) and removing the solvent: and (4) leading the shaped monofilament to enter a heating zone through first traction, and then carrying out second traction and rolling to obtain a finished product.

3. The preparation method of the polyethylene mesh wire monofilament with the marine fouling prevention property as claimed in claim 1, wherein the modification step of the modified nano ZnO powder is as follows:

a. mixing nano ZnO powder with the particle size of 20-50nm and a coupling agent in a xylene solution according to the mass ratio of 5.0-20: 0.5-1.0, and heating and stirring;

b. cooling to room temperature, filtering, adding ether to precipitate filtrate, and drying to obtain modified nanometer ZnO powder with particle diameter of 20-50 nm.

4. The method for preparing polyethylene netting twine monofilament with marine fouling resistance as claimed in claim 1, wherein the mixture of high density polyethylene particles and polypropylene powder, wherein the high density polyethylene particles are two types of type HDPE/T60-800 and HD5000S, and the ratio of HDPE/T60-800: HD 5000S: the ratio of polypropylene powder is 3.8-4.2:1.8-2.2: 0.8-1.2.

5. The method for preparing polyethylene mesh wire monofilament with marine fouling prevention property as claimed in claim 2, wherein the diameter of the monofilament in the step (3) is 0.2 ~ 0.7.7 mm.

6. The method for preparing polyethylene mesh wire monofilament with marine fouling prevention property as claimed in claim 2, wherein the pultrusion speed in the step (3) is 15-20 mm/s.

7. The method as claimed in claim 2, wherein the heating temperature in the step (3) is 115-125 ℃, 155-165 ℃ in the second stage and 195-205 ℃.

8. The method for preparing the polyethylene mesh wire monofilament with the marine fouling prevention property according to the claim 2, wherein the cooling and setting temperature in the step (4) is 10-20 ℃, and the cooling and setting time is 4-6 min.

9. The method for preparing polyethylene mesh wire monofilament with marine fouling prevention property as claimed in claim 2, wherein the heating in step (5) is hot water heating at 90-100 ℃ for 4-6 min.

10. The method for preparing polyethylene mesh wire monofilament with marine fouling prevention property as claimed in claim 3, wherein the heating temperature in step a is 60 ~ 90 ℃, the heating time is 2.5-3.5h, and the stirring speed is 1000-.

Technical Field

The invention belongs to the field of material science, and particularly relates to a preparation method of a polyethylene mesh wire monofilament with marine fouling prevention property.

Background

The aquaculture net cage is placed in seawater for a long time, and a good breeding place is provided for a large number of bacterial colonies in the seawater due to the fact that the net material is non-toxic and large in surface area; and simultaneously, the floating and swimming marine organism larva and spore provides an attaching base and a habitat. When the larvae and spores of the fouling organisms approach the surface of the net cage with the attached bacterial colony, the larvae and spores can actively attach and secrete mucus, and the surface of the net cage is attached by a large amount of fouling organisms along with a series of morphological changes, organic matter predation and growth and reproduction. The attachment of a large amount of fouling organisms can not only obstruct the smooth water flow and the exchange of water, reduce the dissolved oxygen content and the supply of food, but also prevent residual bait and metabolites from discharging out of the tank, thus causing the deterioration of water quality and oxygen deficiency in the tank and influencing the growth of fishes. The removal of the attachments of the netting can bring about a plurality of problems of increasing labor input, disturbing normal growth of fishes, damaging netting gears and the like no matter the netting gears are cleaned by manpower or mechanical mode.

The prior conventional antifouling technology is to coat antifouling paint on the netting twine, the patent number is CN201711356160.X, the patent name is 'fishing net antifouling paint and a preparation method thereof', by using the waterborne polyurethane resin and the vinyl resin as the matrix resin, the pollution of the matrix resin is avoided, the self performance of the coating is improved through the complementation between the two resins, partial epoxidation is carried out under the action of glacial acetic acid and the like, chitosan is utilized for modification, the antibacterial property of the resin is improved, crosslinking under the action of a silane coupling agent, using argil as a carrier, adsorbing tannin and the like by using argil, reducing the adsorption and parasitism of marine microorganisms on a fishing net by using the compounding action of tannin and mixed enzyme, increasing the killing of the microorganisms by using an additive solution, and algae are eliminated, and the heavy metal in the water is adsorbed due to the adsorption effect of the argil.

The method has the disadvantages that the coating is heavy in the task of coating the network cable, the coating is not uniform, the discharge of VOC (volatile organic compounds) is excessive due to a large amount of organic solvent in the coating, the coating is peeled off, the environment is seriously polluted, and the like.

Disclosure of Invention

The invention aims to solve the problems that a coating in the prior art can be peeled off and the maintenance cost is high, and provides a preparation method of a polyethylene mesh wire monofilament with marine fouling prevention property.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of polyethylene mesh wire monofilament with marine fouling prevention characteristic comprises the following substances in every 100 parts by mass of the monofilament mesh wire: 2.3-3.8 parts of copper pyrithione, 2.2-3.5 parts of pyridine bromonitrile, 2.8-3.2 parts of modified nano ZnO powder, 0.8-1.2 parts of zinc acrylate resin, and the balance of the mass parts of a mixture of high-density polyethylene particles and polypropylene powder.

Copper pyrithione (CPT for short) is a broad-spectrum, low-toxicity and environment-friendly bacteriostatic agent for fungi and bacteria, and prevents the adhesion of crustaceans, seaweed and aquatic organisms; especially has positive effect on inhibiting the attachment and the propagation of algae; .

Bromopyridine nitrile (tralopyril) has inhibitory effect on the growth of marine algae and fungi, and can destroy the metabolism of bacteria to make them lose biological activity, and has guiding poisoning effect on carpopodium animals and planktonic crustaceans such as cyclops in the sea;

the nano ZnO powder is also a novel antibacterial agent and has long-acting bactericidal effect on strains such as escherichia coli, staphylococcus aureus and the like; most mucosal organisms attached to the surface of an object in the sea are gram-negative bacteria, and the nano ZnO has a strong antibacterial effect on the gram-negative bacteria. The protein on the cell membrane of the bacteria is easy to combine with the liberated Zn ions and reacts with sulfydryl (-SH), carboxyl and hydroxyl in the structure of the bacteria to destroy the structure of the bacteria, meanwhile, part of the zinc ions enter the cells to denature the protein and destroy the division and proliferation capacity of the bacteria to achieve the aim of resisting bacteria, and after the bacteria die, the zinc ions can be liberated to continuously kill other bacteria. The modified nano ZnO is used for avoiding the agglomeration of nano particles in the implementation, and simultaneously enhancing the dispersion of the nano particles and the combination of the nano particles and a resin system;

the zinc acrylate resin is functional carrier resin with introduced bactericidal and antifouling agent monomer and has certain antifouling performance.

The molecular chain of the high-density polyethylene granular material has no branched chain, so that the molecular chain is regularly arranged, has higher density, acid and alkali resistance, organic solvent resistance and excellent electrical insulation, and can still keep certain toughness, surface hardness, tensile strength, rigidity and other mechanical strength at low temperature. The components are matched with each other, and under the synergistic action, the network cable monofilament with good antifouling effect and no environmental pollution can be prepared.

Preferably, the method comprises the following steps:

(1) and drying: drying the mixture of the modified nano ZnO, the high-density polyethylene particles and the polypropylene powder;

(2) and uniformly mixing materials: uniformly mixing and stirring zinc acrylate resin, pyridine bromonitrile, copper pyrithione and modified nano ZnO powder, and continuously stirring for 40-50min to obtain a mixed material;

(3) drawing: drawing the mixed material, wherein the drawing and extruding process needs three stages of heating to draw out monofilaments;

(4) and shaping: cooling and shaping the monofilament drawn in the step (3);

(5) and removing the solvent: and (4) leading the shaped monofilament to enter a heating zone through first traction, and then carrying out second traction and rolling to obtain a finished product.

Preferably, the modifying step of the modified nano ZnO powder is as follows:

a. mixing nano ZnO powder with the particle size of 20-50nm and a coupling agent in a xylene solution according to the mass ratio of 5.0-20: 0.5-1.0, and heating and stirring;

b. cooling to room temperature, filtering, adding ether to precipitate filtrate, and drying to obtain modified nanometer ZnO powder with particle diameter of 20-50 nm.

The coupling agent can increase the surface activity of the nano ZnO powder and increase some small molecular groups such as hydroxyl, hydrogen ions and the like, so that the nano ZnO powder can be better combined with other components in a formula, and in addition, the modified nano ZnO powder also has antifouling capacity. The heating energy provides power for the close combination of the coupling agent and the nano ZnO powder to promote the reaction, and the heating, the heat preservation and the stirring at a certain stirring speed are carried out to fully carry out the reaction so as to obtain the modified nano ZnO powder with better surface activity.

Preferably, the mixture of the high-density polyethylene particles and the polypropylene powder is prepared by mixing the high-density polyethylene particles and the polypropylene powder, wherein the high-density polyethylene particles are two types of types HDPE/T60-800 and HD5000S, and the proportions of HDPE/T60-800 in each case are as follows: HD 5000S: the ratio of polypropylene powder is 3.8-4.2:1.8-2.2: 0.8-1.2.

Preferably, the monofilament in the step (3) has a diameter of 0.2 ~ 0.7.7 mm.

The monofilament has an overlarge diameter and a larger surface area, when the monofilament is stressed, the probability of generating cracks on the surface of the monofilament is higher, and powder particles exist in the monofilament and are crack initiation areas; when the diameter of the monofilament is too small, the bearing capacity is insufficient, and the monofilament is easy to break, so that the diameter of the monofilament needs to be limited within a reasonable range.

Preferably, the pultrusion speed of the step (3) is 15-20 mm/s.

The drawing and extruding speed is too high, so that the drawn monofilaments have uneven diameters and are easy to break, and all components on the monofilaments cannot be fully and uniformly soaked, so that the quality of the monofilaments is influenced; too slow a pultrusion rate can reduce wire drawing efficiency.

Preferably, the heating temperature in the step (3) is 115-.

The heating in three stages is carried out, because the cross-linking curing temperature of each component is different, so that each formula component in the monofilament fully generates cross-linking reaction to form the monofilament with a fixed shape, and in addition, the organic solvent in the monofilament component is completely volatilized, and the pollution to the marine environment is avoided.

Preferably, the cooling and shaping temperature in the step (4) is 10-20 ℃, and the cooling and shaping time is 4-6 min.

After the wire drawing process is finished, in order to prevent partial components from being pyrolyzed again due to high temperature and further influencing the shape of the monofilament, the extruded monofilament needs to be cooled and shaped.

Preferably, the heating in step (5) is carried out by heating with hot water at 90-100 deg.C for 4-6 min.

The hydrophilic organic solvent on the prepared monofilament is dissolved in water, and heating is carried out to fully dissolve the hydrophilic organic solvent, so that the organic solvent is prevented from being dissolved in seawater to pollute the environment when the environmental temperature rises in the process of cultivation and use.

Preferably, the heating temperature in the step a is 60 ~ 90 ℃, the heating time is 2.5-3.5h, and the stirring speed is 1000-.

The heating energy provides power for the close combination of the coupling agent and the nano ZnO powder to promote the reaction, and the heating, the heat preservation and the stirring at a certain stirring speed are carried out to fully carry out the reaction so as to obtain the modified nano ZnO powder with better surface activity.

Therefore, the invention has the following beneficial effects:

(1) the antifouling agent is directly added into the monofilament of the net wire, so that the net has better antifouling performance;

(2) the monofilament has a certain micro-nano structure surface and has excellent mechanical properties such as high strength and good wear resistance;

(3) avoiding subsequent complex antifouling paint construction and pollution to the environment;

(4) the maintenance work of the net wire during the use is reduced, the monofilament preparation process is simple, and the processing cost is saved.

Detailed Description

The invention is further described with reference to specific embodiments.