CN110129921B - Fishing polyformaldehyde monofilament as well as preparation method and application thereof - Google Patents
Fishing polyformaldehyde monofilament as well as preparation method and application thereof Download PDFInfo
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- CN110129921B CN110129921B CN201910236293.6A CN201910236293A CN110129921B CN 110129921 B CN110129921 B CN 110129921B CN 201910236293 A CN201910236293 A CN 201910236293A CN 110129921 B CN110129921 B CN 110129921B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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Abstract
The invention discloses a fishing polyformaldehyde monofilament which is prepared from the following components in parts by weight: 75-90 parts of polyformaldehyde, 0.5-3 parts of graphene, 7.5-17 parts of thermoplastic polyurethane, 0.5-3 parts of antioxidant, 0.5-1 part of formaldehyde absorbent, 0.5-1 part of formic acid absorbent and 0.5-1 part of lubricant. The fishing polyformaldehyde monofilament provided by the invention is prepared by blending graphene and thermoplastic polyurethane, then performing reinforcing, toughening and modification on polyformaldehyde, and performing melt spinning, three-stage hot stretching and heat setting processes, and has the advantages of simple operation process and low production cost. The reinforced and toughened polyformaldehyde monofilament for fishing prepared by the invention can be used for polyformaldehyde rope nets, ocean trawling nets, breeding nets, polyformaldehyde ropes and the like.
Description
Technical Field
The invention belongs to the technical field of fishing materials, and particularly relates to a fishing polyformaldehyde monofilament as well as a preparation method and application thereof.
Background
Early fisheries were benefited by the use of natural fibers, which had many deficiencies, insufficient strength for some netting gear applications, and insufficient wear resistance and weather resistance for some environmental applications. With the development of science and technology and the appearance of synthetic fibers, the defects of natural fibers are made up, the requirements of large-scale production, modernization and specialization of deep-water operation of modern fishery production are met, the fishery synthetic fibers have more technological progress than the fishery natural fibers, and new fishery synthetic fiber materials such as polyarylate fibers, biodegradable fibers, ultrahigh molecular weight polyethylene fibers, high-strength fishery polyethylene monofilaments and the like are provided. With the continuous development of the state to the marine aquaculture fishery, the basic function of fishery materials is more and more prominent, and the modified fishery materials have important significance for improving the utilization rate of marine fishery resources.
Polyformaldehyde is an unbranched linear polymer with high density and high crystallinity, has excellent comprehensive performance, and belongs to engineering plastics. The fiber prepared from the fiber has the advantages of high strength, good dimensional stability, chemical corrosion resistance, wear resistance and the like, and is superior to the traditional polyolefin fiber. At present, the preparation method of the polyformaldehyde fiber mainly comprises two methods, namely melt spinning and wet spinning, wherein the melt spinning is the main method for producing the polyformaldehyde fiber, and the production cost and the efficiency are low. In order to prepare high-performance polyformaldehyde fibers and enable the polyformaldehyde fibers to have enough tensile breaking strength, high-power hot drawing must be carried out on the polyformaldehyde fibers in the production process, a polyformaldehyde fiber sample with high modulus and high strength can be obtained, but the polyformaldehyde fibers can present larger brittleness after being subjected to super-power drawing, and have the defects of notch sensitivity and low impact strength. The thermoplastic polyurethane has excellent properties of good elasticity, low temperature resistance, good oil resistance, chemical resistance and environmental resistance. The thermoplastic polyurethane is beneficial to reducing the high brittleness of the polyformaldehyde fibers and improving the performance of the polyformaldehyde fibers.
Graphene has good physical and chemical properties and a unique two-dimensional layered planar structure with a large specific surface area, so that the graphene has good development prospects in various fields, is one of the materials with the highest known strength, and has good toughness.
In view of the above, there is a need to develop a polyoxymethylene monofilament fishing material having good toughness.
Disclosure of Invention
The first purpose of the invention is to provide a fishing polyformaldehyde monofilament.
The second purpose of the invention is to provide a preparation method of the fishing polyformaldehyde monofilament.
The third purpose of the invention is to provide the application of the fishing polyformaldehyde monofilament in preparing polyformaldehyde rope nets, ocean trawling nets, breeding nets and polyformaldehyde ropes.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a fishing polyformaldehyde monofilament, which is prepared from the following components in parts by weight: 75-90 parts of polyformaldehyde, 0.5-3 parts of graphene, 7.5-17 parts of thermoplastic polyurethane, 0.5-3 parts of antioxidant, 0.5-1 part of formaldehyde absorbent, 0.5-1 part of formic acid absorbent and 0.5-1 part of lubricant.
Preferably, the polyoxymethylene can be selected from the following parts by weight: 75. 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89 and 90 parts. The following parts by weight of graphene can be selected: 0.5, 1, 1.5, 2, 2.5 and 3 parts. The thermoplastic polyurethane can be selected from the following components in parts by weight: 7.5, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17 parts. The antioxidant can be selected from the following components in parts by weight: 0.5, 1, 1.5, 2, 2.5 and 3 parts. The formaldehyde absorbent can be selected from the following components in parts by weight: 0.5, 0.6, 0.7, 0.8, 0.9, 1. The formic acid absorbent can be selected from the following components in parts by weight: 0.5, 0.6, 0.7, 0.8, 0.9, 1. The lubricant can be selected from the following components in parts by weight: 0.5, 0.6, 0.7, 0.8, 0.9, 1.
The number average molecular weight of the polyformaldehyde is 25W-30W, and specifically N60520922 polyformaldehyde of Chongqing Yunyan Huanshi Tianyun New Material Co., Ltd, MC90 polyformaldehyde of Shenhuan Ningxia coal industry group methanol division Co., Ltd, 300PNC polyformaldehyde of U.S. DuPont, and LW90FSK polyformaldehyde of Nippon Baysian Plastic Co., Ltd.
The graphene is a single-layer graphene with the surface subjected to oleophylic modification, the purity is more than 99.0%, and specifically, the graphene is FH-661 graphene manufactured by Hunan Feng materials development Limited, XF002-1 graphene manufactured by Nanjing Xianfeng nanometer materials science and technology Limited and HGP-2 graphene manufactured by Qingdao ultra-carbon new materials science and technology Limited are selected.
The thermoplastic polyurethane is polyether type thermoplastic polyurethane, the brittleness temperature is lower than-70 ℃, and the universal type 9380A polyether type thermoplastic polyurethane of Germany Bayer company, the universal type T370A polyether type thermoplastic polyurethane of American Lubrizol company and the universal type 1190A polyether type thermoplastic polyurethane of Germany Basofu limited company are specifically selected.
The antioxidant is antioxidant 1010, specifically antioxidant 1010 of German Pasteur GmbH, the initial melting point is more than or equal to 110 ℃, the volatile matter is less than or equal to 0.5%, and the ash content is less than or equal to 0.1%.
The formaldehyde absorbent is a formaldehyde absorbent 660, and is specifically selected from a formaldehyde absorbent of Shanghai purple-wet chemical auxiliary agent Co.
The formic acid absorbent is long-chain alkyl calcium carboxylate, and is specifically calcium dodecyl benzene sulfonate from Wuhan Dahuawei industry pharmaceutical chemical Co.
The lubricant is a hydrocarbon lubricant, and specifically, RLC 657 polyethylene wax of HONEYWELL (China) GmbH is selected.
The diameter of the fishing polyformaldehyde monofilament is 0.1-4 mm.
The second aspect of the invention provides a preparation method of the fishing polyformaldehyde monofilament, which comprises the following steps:
according to the proportion, pre-mixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of the mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament.
The melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 185-205 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:30-1:50, the aperture of spinneret holes on the spinneret plate is 1.03mm, and the number of the holes is 144.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 4-6.2 times, and the stretching temperature is 65-100 ℃; the secondary stretching multiple is 1.2-1.65 times, and the stretching temperature is 100-150 ℃; the third-stage stretching multiple is 1.01-1.05 times, and the stretching temperature is 110-160 ℃; the total stretching ratio is 4.85-10.54 times.
The temperature of the heat setting process is 120-160 ℃.
The invention also provides a method for preparing the polyformaldehyde monofilament, and the fishing polyformaldehyde monofilament is used for preparing polyformaldehyde rope nets, ocean trawling nets, breeding nets and polyformaldehyde ropes.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the fishing polyformaldehyde monofilament component provided by the invention comprises raw material auxiliaries such as polyformaldehyde, thermoplastic polyurethane, graphene, an antioxidant, a formaldehyde absorbent, a formic acid absorbent, a polyethylene wax lubricant and the like with a specific dosage, and is kneaded at a high speed at a specific time, a specific rotating speed and a specific temperature to obtain a special polyformaldehyde modified composite material, so that the raw material composition, spinning flowability and spinnability of the polyformaldehyde monofilament for rope manufacturing are developed, and the smooth and smooth spinning production is ensured; the invention carries out countless development test argumentations under the conditions of different production costs, drafting multiples and raw material compositions, obtains the final technical scheme of the invention, and ensures that the spinnability and the comprehensive performance of the polyformaldehyde monofilament for rope manufacturing are good, and no filament breakage phenomenon exists in batch production.
The invention adopts the thermoplastic polyurethane elastomer to reduce the crystallinity and high brittleness of the polyformaldehyde monofilament, and improve the toughness and knotting strength of the polyformaldehyde monofilament; the modified nano graphene is adopted, so that the crystallization and orientation structure of a polyformaldehyde macromolecule chain can be adjusted, and meanwhile, the modified nano graphene and C-O bonds on the polyformaldehyde macromolecule form a three-dimensional network structure, so that the strength and toughness of polyformaldehyde monofilaments are enhanced; the invention adopts the antioxidant 1010, ensures that the polyformaldehyde is not degraded in the processing process, improves the oxidation resistance and the ultraviolet aging resistance of the product, and improves the service cycle of the product; the formaldehyde absorbent 660 and the formic acid absorbent calcium dodecyl benzene sulfonate are adopted, so that the degradation in the polyformaldehyde processing process is reduced, and the product productivity is improved; the invention adopts the RLC 657 polyethylene wax lubricant, reduces the friction damage in the polyformaldehyde processing process, is beneficial to the smooth spinning process and reduces the filament breakage imagination.
According to the preparation method of the fishing polyformaldehyde monofilament, provided by the invention, the polyformaldehyde is subjected to reinforcing, toughening and modifying after the graphene and the thermoplastic polyurethane are blended, and the fishing polyformaldehyde monofilament prepared through melt spinning, three-stage hot stretching and heat setting processes has the advantages of simple operation process and low production cost. The reinforced and toughened polyformaldehyde monofilament for fishing prepared by the invention can be used for polyformaldehyde rope nets, ocean trawling nets, breeding nets, polyformaldehyde ropes and the like.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 75 parts of N60520922 polyformaldehyde, 3 parts of FH-661 graphene, 17 parts of 9380A polyether type thermoplastic polyurethane, 3 parts of antioxidant 1010, 0.5 part of formaldehyde absorbent 660, 0.5 part of formic acid absorbent calcium dodecyl benzene sulfonate and 1 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 185 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:30, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 4 times, and the stretching temperature is 65 ℃; the secondary stretching multiple is 1.2 times, and the stretching temperature is 100 ℃; the third-stage stretching multiple is 1.01 times, and the stretching temperature is 110 ℃;
the temperature of the heat setting process is 120 ℃, and the total stretching multiple is 4.85 times.
The diameter of the fishing polyformaldehyde monofilament is 0.1 mm.
Example 2
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 80 parts of MC90 polyformaldehyde, 2 parts of XF002-1 graphene, 15 parts of T370A polyether type thermoplastic polyurethane, 1 part of antioxidant 1010, 0.5 part of formaldehyde absorbent 660, 0.5 part of formic acid absorbent calcium dodecyl benzene sulfonate and 1 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 190 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:40, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 4 times, and the stretching temperature is 70 ℃; the secondary stretching multiple is 1.5 times, and the stretching temperature is 110 ℃; the third-stage stretching multiple is 1.05 times, and the stretching temperature is 120 ℃;
the temperature of the heat setting process is 130 ℃, and the total stretching multiple is 6.3 times.
The diameter of the fishing polyformaldehyde monofilament is 0.2 mm.
Example 3
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 85 parts of 300PNC polyformaldehyde, 1 part of HGP-2 graphene, 11 parts of 1190A polyether type thermoplastic polyurethane, 0.5 part of antioxidant 1010, 1 part of formaldehyde absorbent 660, 1 part of formic acid absorbent calcium dodecyl benzene sulfonate and 0.5 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 195 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:50, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 5 times, and the stretching temperature is 80 ℃; the secondary stretching multiple is 1.6 times, and the stretching temperature is 130 ℃; the third-stage stretching multiple is 1.01 times, and the stretching temperature is 130 ℃;
the temperature of the heat setting process is 140 ℃, and the total stretching multiple is 9.09 times.
The diameter of the fishing polyformaldehyde monofilament is 4.0 mm.
Example 4
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 90 parts of N60520922 polyformaldehyde, 0.5 part of XF002-1 graphene, 7.5 parts of 9380A polyether type thermoplastic polyurethane, 0.5 part of antioxidant 1010, 0.5 part of formaldehyde absorbent 660, 0.5 part of calcium dodecyl benzene sulfonate as formic acid absorbent and 0.5 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 200 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:30, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 90 ℃; the secondary stretching multiple is 1.5 times, and the stretching temperature is 140 ℃; the third-stage stretching multiple is 1.05 times, and the stretching temperature is 140 ℃;
the temperature of the heat setting process is 150 ℃, and the total stretching multiple is 9.77 times.
The diameter of the fishing polyformaldehyde monofilament is 1.0 mm.
Example 5
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 85 parts of LW90FSK polyformaldehyde, 0.5 part of HGP-2 graphene, 10.5 parts of T370A polyether type thermoplastic polyurethane, 1 part of antioxidant 1010, 1 part of formaldehyde absorbent 660, 1 part of calcium dodecyl benzene sulfonate as a formic acid absorbent and 1 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 205 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:50, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 1.65 times, and the stretching temperature is 150 ℃; the third-stage stretching multiple is 1.03 times, and the stretching temperature is 150 ℃;
the temperature of the heat setting process is 160 ℃, and the total stretching multiple is 10.54 times.
The diameter of the fishing polyformaldehyde monofilament is 2 mm.
Comparative example 1
Other conditions were as in example 5, except that: graphene is not added.
Comparative example 2
Other conditions were as in example 5, except that: thermoplastic polyurethane was not added.
Comparative example 3
Other conditions were as in example 5, except that: the head temperature of the twin-screw extruder was 215 ℃.
Comparative example 4
Other conditions were as in example 5, except that: no hydrocarbon lubricant was added.
Comparative example 5
Other conditions were as in example 5, except that: no antioxidant was added.
The mechanical property test method refers to aquatic product industry standard SC/T5005-2014 polyethylene monofilament for fishing, and the detection data are shown in Table 1:
TABLE 1 examination of the examples and comparative examples
| Breaking strength (cN/dtex) | Knot strength (cN/dtex) | |
| Example 1 | 4.8 | 2.5 |
| Example 2 | 5.3 | 2.8 |
| Example 3 | 5.8 | 3.3 |
| Example 4 | 6.0 | 3.5 |
| Example 5 | 6.2 | 3.8 |
| Comparative example 1 | 5.0 | 2.6 |
| Comparative example 2 | 5.8 | 2.5 |
| Comparative example 3 | 5.0 | 2.2 |
| Comparative example 4 | 5.5 | 2.8 |
| Comparative example 5 | 4.5 | 2.3 |
Most conditions of comparative examples 1, 2, 3, 4 and 5 are the same as those of example 5 with the best knot strength, but the comparative example 1 is not added with graphene and cannot play a role in reinforcing and toughening polyformaldehyde, so that the fracture strength and the knot strength of the final monofilament are influenced; comparative example 2 is not added with thermoplastic polyurethane, so that the intervention on the macromolecular crystal form in the polyformaldehyde monofilament cannot be caused, and the knot strength of the final monofilament is greatly reduced; comparative example 3 the spinning temperature is 215 ℃, the temperature is higher, which causes thermal degradation of polyformaldehyde to a certain degree, thereby directly influencing the fracture strength and the nodule strength; comparative example 4 no hydrocarbon lubricant is added, which causes filament breakage in the spinning production process, and simultaneously the flowing property of the spinning melt after being discharged from a spinneret orifice is reduced, which causes that the monofilament breaking strength and the nodule strength are not ideal enough; comparative example 5 no antioxidant was added, which resulted in oxidative decomposition at high temperature during polyoxymethylene spinning, resulting in a more significant decrease in breaking strength and knot strength.
Example 6
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 80 parts of MC90 polyformaldehyde, 0.5 part of FH-661 graphene, 15.5 parts of 1190A polyether type thermoplastic polyurethane, 1 part of antioxidant 1010, 1 part of formaldehyde absorbent 660, 1 part of formic acid absorbent calcium dodecyl benzene sulfonate and 1 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 200 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:50, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 1.65 times, and the stretching temperature is 150 ℃; the third-stage stretching multiple is 1.03 times, and the stretching temperature is 150 ℃;
the temperature of the heat setting process is 160 ℃, and the total stretching multiple is 10.54 times.
The diameter of the fishing polyformaldehyde monofilament is 4 mm.
Example 7
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 88 parts of LW90FSK polyformaldehyde, 0.5 part of XF002-1 graphene, 8.5 parts of 9380A polyether type thermoplastic polyurethane, 1 part of antioxidant 1010, 1 part of formaldehyde absorbent 660, 0.5 part of calcium dodecyl benzene sulfonate as a formic acid absorbent, and 0.5 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 205 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:50, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 1.65 times, and the stretching temperature is 150 ℃; the third-stage stretching multiple is 1.03 times, and the stretching temperature is 150 ℃;
the temperature of the heat setting process is 160 ℃, and the total stretching multiple is 10.54 times.
The diameter of the fishing polyformaldehyde monofilament is 2 mm.
Example 8
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 87 parts of 300PNC polyformaldehyde, 2.5 parts of HGP-2 graphene, 7.5 parts of T370A polyether type thermoplastic polyurethane, 0.5 part of antioxidant 1010, 0.5 part of formaldehyde absorbent 660, 1 part of calcium dodecyl benzene sulfonate serving as formic acid absorbent and 1 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 200 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:30, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 1.65 times, and the stretching temperature is 150 ℃; the third-stage stretching multiple is 1.03 times, and the stretching temperature is 150 ℃;
the temperature of the heat setting process is 160 ℃, and the total stretching multiple is 10.54 times.
The diameter of the fishing polyformaldehyde monofilament is 0.5 mm.
Example 9
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 78 parts of N60520922 polyformaldehyde, 2.5 parts of XF002-1 graphene, 15.5 parts of 9380A polyether type thermoplastic polyurethane, 1 part of antioxidant 1010, 1 part of formaldehyde absorbent 660, 1 part of calcium dodecyl benzene sulfonate as a formic acid absorbent and 1 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 205 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:30, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 1.65 times, and the stretching temperature is 150 ℃; the third-stage stretching multiple is 1.03 times, and the stretching temperature is 150 ℃;
the temperature of the heat setting process is 160 ℃, and the total stretching multiple is 10.54 times.
The diameter of the fishing polyformaldehyde monofilament is 0.1 mm.
Example 10
A fishing polyformaldehyde monofilament is prepared from the following components in parts by weight: 80 parts of N60520922 polyformaldehyde, 3 parts of XF002-1 graphene, 15 parts of 9380A polyether type thermoplastic polyurethane, 0.5 part of antioxidant 1010, 0.5 part of formaldehyde absorbent 660, 0.5 part of calcium dodecyl benzene sulfonate as a formic acid absorbent, and 0.5 part of RLC 657 polyethylene wax lubricant.
The preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
premixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of a mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 205 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:30, the aperture of a spinneret hole on the spinneret plate is 1.03mm, and the number of holes is 144 holes.
The three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 1.65 times, and the stretching temperature is 150 ℃; the third-stage stretching multiple is 1.03 times, and the stretching temperature is 150 ℃;
the temperature of the heat setting process is 160 ℃, and the total stretching multiple is 10.54 times.
The diameter of the fishing polyformaldehyde monofilament is 0.2 mm.
According to the preparation method of the fishing polyformaldehyde monofilament, provided by the invention, the polyformaldehyde is subjected to reinforcing, toughening and modifying after the graphene and the thermoplastic polyurethane are blended, and the fishing polyformaldehyde monofilament prepared through melt spinning, three-stage hot stretching and heat setting processes has the advantages of simple operation process and low production cost. The reinforced and toughened polyformaldehyde monofilament for fishing prepared by the invention can be used for polyformaldehyde rope nets, ocean trawling nets, breeding nets, polyformaldehyde ropes and the like.
Comparative example 6
Patent CN107022806 discloses polyoxymethylene monofilaments: the composite material comprises the following components in percentage by mass: 85% of polyformaldehyde, 13% of nano calcium carbonate, 1% of phosphite antioxidant and 1% of hydrocarbon lubricant. The preparation method comprises the following steps:
(1) mixing the polyformaldehyde slices and the nano calcium carbonate in a weight ratio of 1:1, and then granulating by using a double-screw extruder to prepare polyformaldehyde/nano calcium carbonate master batches with the nano calcium carbonate content of 50%, wherein the retention time of materials in the double-screw extruder is 3-5 minutes, and the temperature is 140-160 ℃;
(2) 26 percent of master batch slice, 72 percent of polyformaldehyde slice, 1 percent of phosphite antioxidant and 1 percent of hydrocarbon lubricant are mixed according to a proportion and then are subjected to melt spinning and secondary high-power drawing processes to prepare the polyformaldehyde monofilament for fishing. The melt spinning and secondary high-power drawing process comprises the following steps: the spinning temperature is 205 ℃, the total stretching multiple is 8 times, the first-stage stretching multiple is 4.0 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 2.0 times, and the stretching temperature is 150 ℃.
The data of the performance test of example 5 and comparative example 6 of the present application are shown in table 2:
TABLE 2
| Breaking strength (cN/dtex) | Knot strength (cN/dtex) | |
| Example 5 | 6.2 | 3.8 |
| Comparative example 6 | 6.0 | 3.5 |
As can be seen from the data in Table 2, the breaking strength and the knot strength of the polyoxymethylene fibers obtained by modifying polyoxymethylene with nanocalcium carbonate in comparative example 6 were 6.0cN/dtex and 3.5cN/dtex, respectively, while the breaking strength and the knot strength of the polyoxymethylene fibers obtained in example 5 were 6.2cN/dtex and 3.8cN/dtex, respectively, which are higher than those in comparative example 6. When the fishing polyformaldehyde fiber is used for manufacturing fishing nets, the performance index of the knot strength is the most important. Because the fishing net is often knotted more than is necessary when being made. Due to the addition of the thermoplastic polyurethane, the toughness of polyformaldehyde is improved, so that the node strength of polyformaldehyde fibers is improved, the node strength of the polyformaldehyde fibers in the embodiment 5 is improved by about 8.6% compared with that of the polyformaldehyde fibers in the comparison 6, the mesh fracture strength after the fishing net is manufactured is ensured to a great extent, and the method has important significance for practical production and application.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A fishing polyformaldehyde monofilament is characterized in that: the composition is prepared from the following components in parts by weight: 85 parts of polyformaldehyde, 0.5 part of graphene, 10.5 parts of thermoplastic polyurethane, 1 part of antioxidant, 1 part of formaldehyde absorbent, 1 part of formic acid absorbent and 1 part of lubricant;
the preparation method of the fishing polyformaldehyde monofilament comprises the following steps:
according to the proportion, pre-mixing polyformaldehyde, graphene, thermoplastic polyurethane, an antioxidant, a formaldehyde absorbent, a formic acid absorbent and a lubricant, then pouring into a high-speed kneader, kneading at a high speed for 30-60min under the condition that the rotating speed is 750-800 r/min, and discharging after the temperature of the mixture in the high-speed kneader is raised to 80 ℃ to obtain a polyformaldehyde modified composite material;
the polyformaldehyde modified composite material is subjected to melt spinning, three-stage hot stretching and heat setting processes by a double-screw extruder to prepare the fishing polyformaldehyde monofilament;
the melt spinning process comprises the following steps: the head temperature of the double-screw extruder is 205 ℃, the length-diameter ratio of a spinneret plate of the double-screw extruder is 1:50, the aperture of spinneret holes on the spinneret plate is 1.03mm, and the number of the holes is 144;
the three-stage hot stretching process comprises the following steps: the primary stretching multiple is 6.2 times, and the stretching temperature is 100 ℃; the secondary stretching multiple is 1.65 times, and the stretching temperature is 150 ℃; the third-stage stretching multiple is 1.03 times, and the stretching temperature is 150 ℃; the total stretching multiple is 10.54 times;
the temperature of the heat setting process was 160 ℃.
2. A fishery polyoxymethylene monofilament according to claim 1, wherein: the number average molecular weight of the polyformaldehyde is 25W-30W.
3. A fishery polyoxymethylene monofilament according to claim 1, wherein: the graphene is a single-layer graphene with the surface subjected to oleophylic modification, and the purity is more than 99.0%.
4. A fishery polyoxymethylene monofilament according to claim 1, wherein: the thermoplastic polyurethane is polyether thermoplastic polyurethane, and the brittleness temperature is lower than-70 ℃.
5. A fishery polyoxymethylene monofilament according to claim 1, wherein: the initial melting point of the antioxidant is more than or equal to 110 ℃, the volatile matter is less than or equal to 0.5 percent, and the ash content is less than or equal to 0.1 percent.
6. A fishery polyoxymethylene monofilament according to claim 1, wherein: the formic acid absorbent is long-chain alkyl calcium carboxylate.
7. A fishery polyoxymethylene monofilament according to claim 1, wherein: the lubricant is a hydrocarbon lubricant;
the diameter of the fishing polyformaldehyde monofilament is 2 mm.
8. Use of a fishing polyoxymethylene monofilament according to any one of claims 1 to 7 for the production of polyoxymethylene rope nets, ocean trawls, aquaculture nets, polyoxymethylene ropes.
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