阅读说明：本技术 一种防污损抗疲劳的多股单丝混捻网线及其制备方法 (Anti-fouling and anti-fatigue multi-strand monofilament mixed-twisted net wire and preparation method thereof ) 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,针对网线涂层会剥落和网衣抗疲劳性能差的问题,公开了一种防污损抗疲劳的多股单丝混捻网线及其制备方法。包括尼龙单丝,包括尼龙单丝和防污损聚乙烯单丝,所述防污损聚乙烯单丝包覆所述尼龙单丝混合加捻,单丝之间连接有改性环氧树脂,聚乙烯单丝的直径为0.2-0.5mm,尼龙单丝的直径为0.2-1.2 mm。混捻网线的制备步骤包括：活化、浸渍单丝、混合加捻及加热固化四个步骤。本发明通过制备防污网线和引入力学性能好的尼龙单丝,将防污剂复合至网线中,所得单丝网线具有防污功能,无需后续的防污涂料的施工,显著提升防污损能力,减少环境污染,能较大提升混捻网线和网衣的抗污损、抗拉伸和抗疲劳能力。(The invention relates to the field of material science, and discloses an antifouling and antifatigue multi-strand monofilament mixed-twisted netting wire and a preparation method thereof, aiming at the problems that a netting wire coating can be peeled off and the netting fatigue resistance performance is poor. The composite material comprises nylon monofilaments and antifouling polyethylene monofilaments, wherein the antifouling polyethylene monofilaments are coated on the nylon monofilaments and are mixed and twisted, modified epoxy resin is connected among the monofilaments, the diameter of each polyethylene monofilament is 0.2-0.5mm, and the diameter of each nylon monofilament is 0.2-1.2 mm. The preparation method of the mixed twisted net wire comprises the following steps: activating, dipping monofilament, mixing and twisting, and heating and curing. According to the invention, the antifouling net wire is prepared, the nylon monofilament with good mechanical property is introduced, and the antifouling agent is compounded into the net wire, so that the obtained monofilament net wire has an antifouling function, the subsequent construction of antifouling paint is not needed, the antifouling capacity is obviously improved, the environmental pollution is reduced, and the antifouling capacity, the tensile resistance and the fatigue resistance of the mixed-twisted net wire and the netting can be greatly improved.)

1. The anti-fouling and anti-fatigue multi-strand monofilament mixed-twisted net wire comprises nylon monofilaments and is characterized by comprising modified nylon monofilaments and anti-fouling polyethylene monofilaments, wherein the modified nylon monofilaments are coated by the anti-fouling polyethylene monofilaments and are twisted in a mixed mode, modified epoxy resin is connected among the monofilaments, the diameter of each polyethylene monofilament is 0.2-0.5mm, and the diameter of nylon is 0.2-1.2 mm.

2. The method for preparing a multi-ply, anti-fouling and anti-fatigue, single-wire co-twisted yarn as claimed in claim 1, wherein the co-twisted yarn is prepared by the steps of:

1) and activating: putting nylon monofilament into deionized water at 60-70 ℃ for ultrasonic treatment, and then putting the nylon monofilament into dilute nitric acid solution;

2) dipping monofilaments: dipping the activated nylon monofilament in the modified epoxy resin for 50-60 min;

3) and mixing and twisting: twisting the dipped nylon monofilament and the antifouling polyethylene monofilament;

4) and heating and curing: and 3) heating and curing the twisted net wire.

3. An antifouling and fatigue-resistant multi-ply twisted wire according to claim 1 or 2, wherein the antifouling polyethylene monofilament comprises the following per 100 parts by mass: 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 mixture of high-density polyethylene particles and polypropylene powder.

4. An anti-fouling and anti-fatigue multi-strand twisted wire mesh according to claim 3, wherein the anti-fouling polyethylene monofilament is prepared by 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: the mixed material is pultruded, wherein the process of pultrusion needs three stages of heating, and the monofilament is pulled out, wherein the first stage is 115-125 ℃, the second stage is 155-165 ℃, and the third stage is 195-205 ℃;

(4) and shaping: cooling and shaping the monofilament drawn in the step (3) for 4-6 min at 10-20 ℃;

(5) and removing the solvent: and (3) leading the shaped monofilament into a heating zone through first traction, heating the monofilament for 4-6 min by hot water at the temperature of 90-100 ℃, and then carrying out second traction and rolling to obtain a finished product.

5. The method for preparing the antifouling and fatigue-resistant multi-strand monofilament mixed-twisted net wire according to claim 4, wherein the modifying step of the modified nano ZnO powder is as follows:

a. mixing nano ZnO powder and a coupling agent in a xylene solution according to a mass ratio of 5.0-20: 0.5-1.0, heating and stirring at 60 ~ 90 ℃ for 2.5-3.5h at a stirring speed of 1000-1200 r/min;

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.

6. The method for preparing the polyethylene mesh wire monofilament with the marine fouling prevention property according to the claim 2, wherein the modified epoxy resin in the step 2) is prepared by the following steps: firstly raising the temperature of toluene-2, 4-diisocyanate to 45-50 ℃, and dropwise adding 1H,1H, 7H-dodecafluoroheptanol, wherein the mass ratio of the toluene-2, 4-diisocyanate to the 1H,1H, 7H-dodecafluoroheptanol is 1: 1.2-1.4, heating to 60-70 ℃ after dripping, preserving heat for 1.8-2.2h, adding excessive 10-15% of bisphenol A epoxy resin, heating to 85-90 ℃ and reacting for 2-2.5h to obtain the modified epoxy resin.

7. The method as claimed in claim 2, wherein the step 4) of heating and curing comprises two stages, the first stage heating temperature is 100-.

8. The method for preparing polyethylene mesh wire monofilament with marine fouling prevention property according to claim 2, wherein the ultrasonic time in the step 1) is 0.8-1.2 h.

9. 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.

10. The method for preparing polyethylene netting twine monofilament with marine fouling resistance as claimed in claim 3, wherein the high density polyethylene particles and polypropylene powder are mixed, 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.

Technical Field

The invention belongs to the field of material science, and particularly relates to an antifouling and anti-fatigue multi-strand monofilament mixed-twisted net wire and a preparation method thereof.

Background

When the aquaculture net cage is placed in seawater for a long time, the bacterial population can be attached to the surface of the aquaculture net cage, and when larvae and spores of fouling organisms approach the surface of a net cage net coat to which the bacterial population is attached, mucus can be attached and secreted and grow along with a series of metamorphosis, so that the net coat material is attached and fouled. The attachment of a large amount of fouling organisms can not only obstruct the smooth water flow and the exchange of water, cause the deterioration of water quality and oxygen deficiency in the box, influence the growth of fishes, even prevent residual baits and metabolites from being discharged out of the box, cause the dysplasia and even death of cultured marine products, and seriously influence the yield and quality of the marine product culture. In addition, during the cultivation process, the netting or the net wires can be frequently impacted by sea waves, and the netting or the net wires can be dragged or vibrated during net drawing and retracting or ocean current washing and swinging. Therefore, the net wires and the net clothes need to have extremely strong antifouling and fatigue resistance in the long-term deep sea culture process.

The conventional antifouling technology at present is to coat an antifouling paint on a netting mesh wire, the patent number is CN201711356160.X, the patent name is 'fishing net antifouling paint and a preparation method thereof', the pollution of matrix resin is avoided by taking waterborne polyurethane resin and vinyl resin as matrix resin, the performance of the paint is improved by the complementation between the two resins, the paint is partially epoxidized under the action of glacial acetic acid and the like, chitosan is used for modifying to increase the antibacterial performance of the resin, crosslinking is carried out under the action of a silane coupling agent, clay is used as a carrier, tannin and the like are adsorbed by the clay, and the compounding effect of tannin and mixed enzyme is used. The patent number is CN201520054160.4, the patent name is 'an aquaculture device', which comprises a net; each tray body is provided with a first fixing piece and is fixedly connected with the netting through the first fixing piece, a cage body formed by the plurality of tray bodies and the netting is of a foldable structure, and the space of the cage body is divided into a plurality of layers of culture sections by the plurality of tray bodies; and the openable structure is arranged on the netting, and the opening formed by the openable structure is used for taking and placing the cultured objects in each layer of culture section.

The disadvantages are that the task of coating the netting wire is heavy, the coating is not uniform, a large amount of organic solvent in the coating is released and the coating is peeled off, the environment is seriously polluted, and the netting is easy to fatigue and damage under the conditions of long-term seawater immersion, long-term fouling and sea wave impact.

Disclosure of Invention

The invention aims to solve the problems that the coating of the netting twine in the prior art can be peeled off and the netting fatigue resistance performance is poor, and provides an antifouling and fatigue-resistant multi-strand monofilament mixed-twisted netting twine and a preparation method thereof.

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

the anti-fouling and anti-fatigue multi-strand monofilament mixed-twisted net wire comprises nylon monofilaments and anti-fouling polyethylene monofilaments, wherein the anti-fouling polyethylene monofilaments are coated on the nylon monofilaments and are twisted in a mixed mode, modified epoxy resin is connected among the monofilaments, the diameter of each polyethylene monofilament is 0.2-0.5mm, and the diameter of each nylon monofilament is 0.2-1.2 mm.

The antifouling polyethylene monofilament has better antifouling performance, reduces the adhesion of bacterial groups and fouling organisms, and has better corrosion resistance and ageing resistance; the nylon monofilament has high mechanical strength, good toughness, higher tensile strength and compressive strength and outstanding fatigue resistance, and can still maintain the original mechanical strength after being repeatedly bent and folded for many times, so the antifouling polyethylene monofilament is coated on the nylon monofilament to be mixed and twisted; the modified epoxy resin is introduced into the connecting part, so that the bonding force between the antifouling polyethylene monofilament and the nylon monofilament can be improved, the antifouling polyethylene monofilament is tightly coated around the nylon monofilament, seawater is prevented from being soaked into the nylon monofilament inside, the nylon monofilament is prevented from being damaged and corroded, the monofilaments cannot be separated when being soaked in seawater and beaten by sea waves, and the whole body has better mechanical property; the monofilament has an overlarge diameter and a larger volume, 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, which 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 defined in a reasonable range; therefore, a high comprehensive performance network cable with good antifouling effect and strong fatigue resistance can be obtained.

Preferably, the preparation steps of the mixed twisted net wire are as follows:

1) and activating: putting nylon monofilament into deionized water at 60-70 ℃ for ultrasonic treatment, and then putting the nylon monofilament into dilute nitric acid solution;

2) dipping monofilaments: dipping the activated nylon monofilament in the modified epoxy resin for 50-60 min;

3) and mixing and twisting: twisting the dipped nylon monofilament and the antifouling polyethylene monofilament;

4) and heating and curing: and 3) heating and curing the twisted net wire.

Step 1) nylon monofilament activation aims at improving the surface roughness of carbon fibers, so that the activated nylon monofilament has a large specific surface area and contains a large number of active functional groups such as hydroxyl groups and the like, and good adhesion conditions are provided for adhesion and deposition of modified epoxy resin; the dilute nitric acid solution is added to remove impurities mixed in the production process of the nylon monofilament.

And 2) soaking the nylon monofilament in the modified epoxy resin for 50-60min to ensure that the periphery of the nylon monofilament is attached by the modified epoxy resin, and active functional groups on contact surfaces are fully reacted to establish chemical bond connection.

And 4) heating and curing to enable the modified epoxy resin to generate a crosslinking reaction, and tightly connecting the antifouling polyethylene monofilament and the antifouling nylon monofilament together.

Preferably, the antifouling polyethylene monofilament comprises the following substances per 100 parts by mass: 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 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 an inhibiting effect on the growth of marine algae and fungi, can destroy the metabolism of bacteria to lose the biological activity, and has a special guiding 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 Zn ion which is easy to be dissociated from the protein on the bacterial cell membrane is combined and reacts with the sulfydryl (-SH), carboxyl and hydroxyl in the structure to destroy the structure, meanwhile, partial zinc ion enters the cell to denature the protein and destroy the division and proliferation capacity of the bacteria to achieve the aim of antibiosis, and after the bacteria die, the zinc ion can be dissociated 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 a functional carrier resin introduced with monomers with bactericidal action and antifouling agents, and also has certain antifouling property.

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.

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 preparation method of the antifouling polyethylene monofilament comprises the following steps:

(1) and drying: drying the modified nano ZnO and the high-density polyethylene particles;

(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: the mixed material is pultruded, wherein the process of pultrusion needs three stages of heating, and the monofilament is pulled out, wherein the first stage is 115-125 ℃, the second stage is 155-165 ℃, and the third stage is 195-205 ℃;

(4) and shaping: cooling and shaping the monofilament drawn in the step (3) for 4-6 min at 10-20 ℃;

(5) and removing the solvent: and (3) leading the shaped monofilament into a heating zone through first traction, heating the monofilament for 4-6 min by hot water at the temperature of 90-100 ℃, and then carrying out second traction and rolling to obtain a finished product.

And (3) heating in three stages, wherein the cross-linking and curing temperatures of the components are different, so that each formula component in the monofilament is subjected to a cross-linking reaction fully to form the monofilament with a fixed shape, and in addition, an organic solvent in the monofilament component is volatilized completely, so that the pollution to the marine environment is avoided.

And (4) after the wire drawing process is finished, in order to prevent partial components from being pyrolyzed again due to high temperature and further influence the shape of the monofilament, cooling and shaping the pultruded monofilament.

And (5) dissolving the hydrophilic organic solvent on the prepared monofilaments in water, and heating for fully dissolving the hydrophilic organic solvent to avoid the pollution to the environment caused by the organic solvent dissolved in seawater when the environmental temperature rises in the process of cultivation and use.

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

a. mixing nano ZnO powder and a coupling agent in a xylene solution according to a mass ratio of 5.0-20: 0.5-1.0, heating and stirring at 60 ~ 90 ℃ for 2.5-3.5h at a stirring speed of 1000-1200 r/min;

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 modified epoxy resin in the step 2) is prepared by the following steps: firstly raising the temperature of toluene-2, 4-diisocyanate to 45-50 ℃, and dropwise adding 1H,1H, 7H-dodecafluoroheptanol, wherein the mass ratio of the toluene-2, 4-diisocyanate to the 1H,1H, 7H-dodecafluoroheptanol is 1: 1.2-1.4, heating to 60-70 ℃ after dripping, preserving heat for 1.8-2.2h, adding excessive 10-15% (the amount of epoxy resin required by calculation according to the hydroxyl value of the epoxy resin) of bisphenol A epoxy resin, heating to 85-90 ℃ and reacting for 2-2.5h to obtain the modified epoxy resin.

The saturated water absorption of epoxy resin is generally 1% to 2%, and in order to improve the water resistance of epoxy resin, the water absorption of resin must be reduced. Because fluorine atoms have high electronegativity and short chemical bonds, the fluorine-containing surfactant and the polymer have high surface activity, and fluorine carbon chains in molecules of the fluorine-containing surfactant and the polymer are hydrophobic groups, the surface tension of the material can be remarkably reduced. In addition, because the surface free energy of fluorine atoms is low and tends to be enriched to the surface of the material in the matrix, a small amount of fluorine-containing surfactant or polymer can obviously reduce the surface performance of the material, and the fluorine-containing groups are greatly enriched on the surface of epoxy resin-air, so that the hydrophobic property of the surface of epoxy resin-air is increased. The synthesized isocyanate-terminated fluorine-containing compound is grafted to bisphenol A epoxy resin to form epoxy resin with side chains containing fluorine, so that the surface performance of the epoxy resin is improved while the excellent bonding force of the epoxy resin is maintained, the advantages of the epoxy resin and fluorocarbon resin are integrated, and the epoxy resin has the characteristics of good wetting property, hydrophobicity, friction resistance, fatigue resistance and the like.

Preferably, the heating and curing in the step 4) comprises two stages, wherein the heating temperature in the first stage is 100-.

In order to enable the modified epoxy resin to fully react, the first stage enables the modified epoxy resin to be subjected to crosslinking reaction and primary curing, the second stage enables the modified epoxy resin to be further cured, and gas micromolecules in a solvent are volatilized, so that the defect that the cured modified epoxy resin has defects due to the fact that the gas micromolecules are remained in the modified epoxy resin in the curing process is avoided, a crack initiation source is provided for crack expansion, and the anti-fatigue property of the network cable is reduced.

Preferably, the time of the ultrasound in the step 1) is 0.8 to 1.2 hours.

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

For the pultrusion speed, the too high pultrusion speed can cause the diameter of the drawn monofilament to be uneven and easy to break, and each component on the monofilament can not be fully and uniformly soaked, thereby affecting the quality of the monofilament; too slow a pultrusion rate can reduce wire drawing efficiency.

Preferably, the high-density polyethylene particles and the polypropylene powder are mixed, 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.

Therefore, the invention has the following beneficial effects:

(1) the antifouling agent is directly added into the net wire monofilament, so that the net has better antifouling performance, has a certain micro-nano structure surface and excellent mechanical properties such as high strength and good wear resistance;

(2) the subsequent complicated antifouling paint construction and the pollution to the environment are avoided, the maintenance work of the network cable during the use is reduced, the monofilament preparation process is simple, and the processing cost is saved;

(3) the monofilament mixed-twisted net wire has the advantages of strong impact resistance, fatigue resistance, tensile strength, seawater soaking resistance and corrosion resistance.

Detailed Description

The invention is further described with reference to specific embodiments.