High-wear-resistance chinlon industrial yarn for marine cable and preparation method of high-wear-resistance chinlon industrial yarn

Abstract

The invention relates to the technical field of chinlon spinning, and particularly discloses a high-wear-resistance chinlon industrial yarn for a marine cable and a preparation method of the high-wear-resistance chinlon industrial yarn. The invention relates to a high-wear-resistance chinlon industrial yarn for a marine cable. The raw materials of the high-wear-resistance chinlon industrial yarn comprise 85-95 parts of modified chinlon 6 slices; 3 to 10 parts of nano ceramic particles; 3-5 parts of polytetrafluoroethylene; 3-5 parts of molybdenum disulfide nanosheets; 10 to 15 parts of a hyperbranched polyurethane microcapsule; 1-3 parts of a dispersant; 1-3 parts of a compatilizer; the modified chinlon 6 slice is obtained by performing swelling treatment on a chinlon 6 slice in a solution containing a maleic anhydride grafted ethylene-octylene copolymer and then drying; the wall material of the hyperbranched polyurethane microcapsule is a hyperbranched polyurethane prepolymer, and the core material of the hyperbranched polyurethane microcapsule comprises a fluorine-containing acrylate monomer and benzophenone. The nylon industrial yarn provided by the invention has excellent wear resistance and mechanical properties, and can meet the performance requirements of marine cables.

Description

Technical Field

[0001] The present application relates to the technical field of nylon spinning, and more specifically, to a nylon industrial yarn for highly wear-resistant marine cables and a preparation method thereof. Background Art

[0002] The ocean is an important resource treasure house and transportation channel for mankind, and marine operations are becoming increasingly frequent. Marine cables play a key role in various marine operations. Whether it is ship mooring, marine engineering construction, or fishing, they are inseparable from the support of marine cables. Nylon industrial yarn has become an ideal material for manufacturing marine cables due to its excellent strength, wear resistance, seawater corrosion resistance and good flexibility. Its high strength characteristics can ensure that the marine cable does not break when subjected to huge tension, effectively ensuring the safety of operations; and good wear resistance and seawater corrosion resistance enable the cable to be used stably for a long time in complex and harsh marine environments, reducing the frequency of replacement and saving costs. Therefore, the performance of nylon industrial yarn directly determines the quality and service life of the marine cable.

[0003] In the related art, a patent application document with publication number CN107938016A discloses a marine cable yarn, whose formula includes 100 parts of nylon 6 slices, 0.05-0.1 parts of anti-aging agent, 0.08-0.12 parts of ultraviolet absorber, 1.0-1.4 parts of nylon 6 high-speed spinning oil, and 1.3-1.7 parts of seawater corrosion resistant oil. When preparing the marine cable yarn, on the basis of nylon 6 industrial filament, the yarn bundle is oiled, and 3-4 nozzles are used for oiling. The oil is Galston 12351 seawater corrosion resistant oil; the oil flowing down the nozzle returns to the reflux tank and is recycled by the circulation pump; after the oiling is completed, it is wound and formed. From the feedback of actual applications, the nylon industrial yarn prepared by this technical solution can meet certain usage requirements in some cable application scenarios with conventional strength requirements. However, when applied to the field of marine cables, this nylon industrial yarn exposes obvious defects. Although the nylon industrial yarn prepared by the above-mentioned prior art has improved in strength and uniformity, it is still insufficient in wear resistance. Due to the frequent friction between the cable and the hull, dock facilities, etc. during marine operations, surface wear will occur in a short time, seriously affecting the service life and safety of the cable. It can be seen that how to further improve the wear resistance of nylon industrial yarn so that it can better adapt to the complex marine environment has become a technical problem that needs to be solved urgently. Summary of the invention

[0004] In order to enhance the wear resistance of nylon industrial yarn, the present application provides a highly wear-resistant nylon industrial yarn for marine cables and a preparation method thereof.

[0005] The present application provides a highly wear-resistant nylon industrial yarn for marine cables using the following technical solutions: A highly wear-resistant nylon industrial yarn for marine cables, comprising the following raw materials in parts by weight: Modified nylon 6 slices 85-95 parts; 3-10 parts of nano ceramic particles; 3-5 parts of polytetrafluoroethylene; 3-5 parts of molybdenum disulfide nanosheets; 10-15 parts of hyperbranched polyurethane microcapsules; 1-3 parts of dispersant; 1-3 parts of compatibilizer; The modified nylon 6 slice is obtained by swelling the nylon 6 slice in a solution containing maleic anhydride grafted ethylene-octene copolymer and then drying; The wall material of the hyperbranched polyurethane microcapsule is a hyperbranched polyurethane prepolymer, and the core material comprises a fluorine-containing acrylate monomer and benzophenone.

[0006] By swelling in a solution containing maleic anhydride grafted ethylene-octene copolymer (POE-g-MAH), the long chain structure of POE-g-MAH can be inserted between the molecular chains of nylon 6, increasing the molecular chain spacing, reducing the intermolecular force, and improving the activity of the chain segments. At the same time, the maleic anhydride group can react chemically with the amino and other active groups on the nylon 6 molecular chain to form a chemical bond connection and enhance the interaction between the molecular chains. This not only improves the processing performance of nylon 6, but also improves its compatibility with other components, laying the foundation for subsequent uniform mixing, thereby improving the performance stability and mechanical properties of the overall material, and playing a key matrix support role in improving wear resistance. Nano-ceramic particles have high hardness, high wear resistance and good chemical stability. The particle size is in the range of 50-150nm and can be evenly dispersed in the nylon industrial yarn matrix. During the friction process, the nano-ceramic particles can withstand part of the friction force and play a role similar to a "hard skeleton" to prevent excessive wear of the fiber matrix. It is physically embedded and chemically bonded with the nylon 6 matrix (such as combining with the active sites generated by the reaction in the modified nylon 6 slices), which enhances the overall rigidity and wear resistance of the material and effectively resists the damage to the fiber surface caused by various friction factors in the marine environment.

[0007] Polytetrafluoroethylene has an extremely low surface friction coefficient and can form a lubricating layer inside and on the surface of the fiber. When the fiber is rubbed, polytetrafluoroethylene can slide between the fibers, reducing the friction resistance between the various parts inside the fiber, while reducing the friction coefficient with external objects on the fiber surface, effectively reducing wear. Molybdenum disulfide nanosheets have a layered structure with weak interlayer forces, which can slip during the friction process and play a good solid lubrication role. Therefore, they can work synergistically with polytetrafluoroethylene to further reduce the friction coefficient inside and on the surface of the fiber. At the same time, the two-dimensional structure of molybdenum disulfide nanosheets enables it to form a tight and orderly interface with nano-ceramic particles, nylon 6 matrix, etc. Its unique lamellar morphology can be evenly dispersed in the matrix, interpenetrating and synergizing with nano-ceramic particles, enhancing the overall mechanical properties of the material and improving its resistance to wear. Especially under high-load friction conditions, it can effectively disperse stress and prevent severe wear on the fiber surface.

[0008] Hyperbranched polyurethane prepolymer, the wall material of hyperbranched polyurethane microcapsules, has a highly branched structure. A large number of active groups on the surface can form a good interface interaction with nylon 6 chips and other additives, enhance the binding force between the components inside the fiber, and enable the components to better cooperate to resist the external force when the material is subjected to external friction, avoiding the aggravation of wear due to relative sliding or falling off. After the microcapsules are broken due to wear, the released fluorinated acrylate monomers can undergo polymerization reaction under the action of benzophenone to form a fluorinated polymer film with low surface energy and good lubrication properties, fill the tiny scratches and defects caused by wear, restore the integrity of the fiber surface, and reduce further wear. Benzophenone generates free radicals under ultraviolet irradiation, which can trigger the polymerization reaction of fluorinated acrylate monomers, which is conducive to accelerating the repair process. At the same time, these free radicals have certain antibacterial activity, and their antibacterial properties can inhibit the erosion of nylon yarn by microorganisms in the marine environment, thereby effectively improving the wear resistance and durability of nylon industrial yarn.

[0009] Optionally, the modified nylon 6 slice is prepared by the following method: The nylon 6 slices are swelled in a solution containing maleic anhydride grafted ethylene-octene copolymer at a swelling temperature of 60-80°C for 2-4 hours. The nylon 6 slices are then taken out and dried at 180-200°C for 2-3 hours.

[0010] Optionally, the solvent of the solution is toluene or xylene, and the mass concentration of the maleic anhydride grafted ethylene-octene copolymer in the solution is 3%-8%.

[0011] By adopting the above technical solution, POE-g-MAH can be well dissolved in toluene or xylene solution, and the molecular chain has a certain mobility, which can be effectively inserted into the molecular chain of nylon 6. The swelling time is controlled at 2-4h, which can not only ensure that POE-g-MAH fully diffuses into the interior of nylon 6 slices, but also avoid excessive damage to the molecular chain due to too long a time. The mass concentration of POE-g-MAH in this range can effectively modify nylon 6 while avoiding excessive concentration that increases the viscosity of the system and affects the processing performance.

[0012] Optionally, the mass ratio of the nylon 6 slices to the solution is 1:(5-7).

[0013] By adopting the above technical scheme, the appropriate mass ratio ensures the sufficiency and uniformity of the swelling treatment, so that the modification effect is optimal, providing a good matrix material for the subsequent preparation of high-performance nylon industrial yarn, which is of great significance to improving the comprehensive performance of the material, especially the wear resistance.

[0014] Optionally, the hyperbranched polyurethane microcapsules are prepared by the following method: A. Mix pentaerythritol, toluene diisocyanate and a catalyst, and react at 60-80° C. for 2-4 hours to obtain a hyperbranched polyurethane prepolymer; B. After mixing the fluorinated acrylate monomer, benzophenone and hyperbranched polyurethane prepolymer, acetone is added to dissolve them to form an oil phase, and then an emulsifier and water are added to the oil phase, and stirred at a speed of 1000-2000 r / min for 30-60 min to obtain an emulsion; C. Add diethanolamine to the emulsion, and then react at 50-70° C. for 3-5 hours. After the reaction is completed, remove impurities in the system by vacuum distillation, and then separate the microcapsules by centrifugal separation. Then, wash and dry the microcapsules to obtain hyperbranched polyurethane microcapsules.

[0015] Optionally, in step A, the mass ratio of pentaerythritol, toluene diisocyanate and catalyst is 1:(3-5):(0.01-0.03).

[0016] Optionally, the catalyst in step A is dibutyltin dilaurate.

[0017] Optionally, in step B, the mass ratio of the fluorinated acrylate monomer, benzophenone and hyperbranched polyurethane prepolymer is 1:(0.1-0.3):(3-5).

[0018] Optionally, the fluorine-containing acrylate monomer in step B is preferably ethyl trifluoromethylacrylate.

[0019] By adopting the above technical scheme, pentaerythritol, toluene diisocyanate and catalyst (dibutyltin dilaurate) are reacted at 60-80°C for 2-4h in step A. This condition is conducive to the synthesis of hyperbranched polyurethane prepolymers with suitable molecular weight and branched structure. Its highly branched structure and surface active groups lay the foundation for subsequent good combination with other components. In step B, fluorinated acrylate monomers, benzophenone and hyperbranched polyurethane prepolymers are mixed in a specific proportion to ensure that the components in the microcapsule core material can work synergistically. Ethyl trifluoromethylacrylate, as a preferred fluorinated acrylate monomer, has good self-healing properties and chemical stability. By controlling the stirring speed and time during the emulsification process, a stable emulsion is formed to ensure the uniformity of the particle size and structural stability of the microcapsules. In step C, diethanolamine is added to react at 50-70°C for 3-5h, so that the hyperbranched polyurethane can be further polymerized to form a stable wall material to wrap the core material. Subsequent steps such as reduced pressure distillation, centrifugal separation, washing and drying remove impurities and obtain pure hyperbranched polyurethane microcapsules. Their stable structure and performance provide a strong guarantee for enhancing the wear resistance of nylon industrial yarn.

[0020] The present application also provides a method for preparing a highly wear-resistant nylon industrial yarn for marine cables, which adopts the following technical solution: A method for preparing highly wear-resistant nylon industrial yarn for marine cables comprises the following steps: S1, adding modified nylon 6 slices, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to a proportion, and mixing at a speed of 800-1200 r / min for 15-25 minutes to obtain a premix; S2, adding the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder, melt blending at a temperature of 240-260° C., controlling the screw speed at 300-400 r / min, extruding and granulating to obtain a spinning masterbatch; S3. The spinning masterbatch is put into a spinning machine, and spinning is performed at a spinning temperature of 250-270° C. The spinning speed is set to 3000-4000 m / min. After cooling, stretching, and winding processes, a highly wear-resistant nylon industrial yarn for marine cables is finally obtained.

[0021] The preparation method ensures uniform dispersion and good combination of each component through step-by-step mixing and specific process parameter control. In S1, the modified nylon 6 slices, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant are initially and evenly mixed at a speed of 800-1200r / min in a high-speed mixer for 15-25 minutes, creating favorable conditions for subsequent melt blending. In S2, melt blending is performed at 240-260°C and the screw speed is 300-400r / min. This temperature and speed can not only ensure that each component is fully melted, but also enable them to be further evenly dispersed and interact with each other under the action of shear force. At this time, the hyperbranched polyurethane microcapsules can also form a stable composite structure with other components. In S3, spinning is carried out at a spinning temperature of 250-270℃ and a spinning speed of 3000-4000m / min. After cooling, stretching at a specific stretching multiple (4.5-5.5 times) and winding processes, the fiber forms an orderly molecular orientation and microstructure during the molding process, further enhancing the mechanical properties and wear resistance of the fiber, and finally producing nylon industrial yarn that meets the high wear resistance requirements of marine cables.

[0022] In summary, this application has the following beneficial effects: 1. The modified nylon 6 slices in this application not only increase the molecular chain spacing, reduce the intermolecular force, improve the activity of the chain segments, and improve the processing performance through the modification treatment, but also form chemical bonds through the chemical reaction between the maleic anhydride group and the amino group and other active groups on the nylon 6 molecular chain, thereby enhancing the interaction between the molecular chains and improving the compatibility with other components. This provides a stable and solid matrix for the overall material, allowing other wear-resistant components to play a better role, fundamentally improving the wear resistance of nylon industrial yarn. The highly branched structure of the hyperbranched polyurethane prepolymer wall material of the hyperbranched polyurethane microcapsule contains a large number of isocyanate groups, hydroxyl groups and other unsaturated bonds on its surface. These active groups can form a good interface interaction with the nylon 6 slices and other additives, enhancing the binding force between the components inside the fiber, effectively avoiding the relative sliding or shedding of components caused by external friction, and reducing wear. After the microcapsules are broken due to wear, the released fluorinated acrylate monomers can undergo polymerization under the action of benzophenone to form a fluorinated polymer film with low surface energy and good lubrication properties, filling the tiny scratches and defects caused by wear, restoring the integrity of the fiber surface, and reducing further wear. Benzophenone can not only trigger the polymerization reaction of fluorinated acrylate monomers and accelerate the repair process, but also inhibit the erosion of microorganisms in the marine environment on nylon yarns with its antibacterial properties, further improving the wear resistance and durability of nylon industrial yarns.

[0023] 2. The nano-ceramic particles in this application play an important role in improving the wear resistance of nylon industrial yarn. This application uses nano-ceramic particles with a particle size in the range of 50-150nm, which can be evenly dispersed in the nylon industrial yarn matrix. Nano-ceramic particles have high hardness, high wear resistance and good chemical stability. During the friction process, they can withstand part of the friction force, just like building a "hard skeleton" inside the fiber, effectively preventing excessive wear of the fiber matrix. There are many ways for nano-ceramic particles to interact with the nylon 6 matrix. On the one hand, through physical inlay, the nano-ceramic particles are tightly embedded in the nylon 6 matrix, increasing the overall rigidity of the material; on the other hand, the nano-ceramic particles can chemically bond with the active sites generated by the reaction in the modified nylon 6 slices, further enhancing the bonding force with the matrix. This close combination allows the nano-ceramic particles to remain firmly inside the fiber when subjected to external friction forces, and continue to play a role in resisting wear.

[0024] 3. The synergistic effect of polytetrafluoroethylene and molybdenum disulfide nanosheets in this application greatly promotes the improvement of the wear resistance of nylon industrial yarn. Polytetrafluoroethylene has an extremely low surface friction coefficient and can form a lubricating layer inside and on the surface of the fiber. When the fiber is rubbed, polytetrafluoroethylene can slide freely between the fibers, effectively reducing the friction resistance between the internal parts of the fiber and reducing the fiber damage caused by internal friction. At the same time, on the fiber surface, polytetrafluoroethylene reduces the friction coefficient with external objects, so that the degree of wear of nylon industrial yarn is greatly reduced when it contacts and rubs with various objects in the marine environment. Molybdenum disulfide nanosheets have a unique layered structure, weak interlayer force, and can slip during friction, thereby playing a good solid lubrication role. It cooperates with polytetrafluoroethylene to further reduce the friction coefficient inside and on the surface of the fiber. In addition, the two-dimensional structure of molybdenum disulfide nanosheets enables it to form a good interface with nano-ceramic particles, nylon 6 matrix, etc. This good interface bonding enhances the overall mechanical properties of the material. Under high-load friction conditions, molybdenum disulfide nanosheets can effectively disperse stress and prevent severe wear on the fiber surface. In the actual use of marine cables, polytetrafluoroethylene and molybdenum disulfide nanosheets work together to reduce the wear of nylon industrial yarn in various friction scenarios, significantly improve its wear resistance, and provide strong guarantees for the long-term and stable use of marine cables. DETAILED DESCRIPTION

[0025] The present application is further described in detail below with reference to the embodiments.

[0026] The main sources of raw materials in the examples of this application are as follows: Nylon 6 chips were standard YH800 materials purchased from Xinsuyang Plastics Trading Company in Yuyao City.

[0027] Maleic anhydride grafted ethylene-octene copolymers were prepared by the following method: First, the ethylene-octene copolymer is dried in a vacuum drying oven at 80°C for 4 hours; then, 5% of the mass of the ethylene-octene copolymer is weighed with maleic anhydride, 0.2% of diisopropylbenzene peroxide, and 0.5% of antioxidant 1010, and the dried ethylene-octene copolymer, maleic anhydride, diisopropylbenzene peroxide and antioxidant 1010 are added to a high-speed mixer, and mixed at a speed of 1000r / min at room temperature for 15 minutes; then, the mixed material is added to a twin-screw extruder, and the extruder head temperature is set to 200°C, the screw speed is 200r / min, and the material is retained for 5 minutes for melt grafting reaction; the reacted material is cut into particles of about 2mm by a pelletizer, and then placed in a vacuum drying oven at 80°C for 6 hours to obtain a maleic anhydride grafted ethylene-octene copolymer.

[0028] Preparation example of modified nylon 6 chips Preparation Example 1 The modified nylon 6 slices are prepared by the following method: 100 kg of nylon 6 slices were immersed in 500 kg of toluene containing maleic anhydride grafted ethylene-octene copolymer for swelling treatment. The mass concentration of maleic anhydride grafted ethylene-octene copolymer in toluene was 3%. The swelling temperature was 60°C and the swelling time was 2 hours. After that, the nylon 6 slices were taken out and dried at 180°C for 2 hours.

[0029] Preparation Example 2 The modified nylon 6 slices are prepared by the following method: 100 kg of nylon 6 slices were immersed in 600 kg of toluene containing maleic anhydride grafted ethylene-octene copolymer for swelling treatment. The mass concentration of maleic anhydride grafted ethylene-octene copolymer in toluene was 5%. The swelling temperature was 70°C and the swelling time was 3 hours. After that, the nylon 6 slices were taken out and dried at 190°C for 2.5 hours.

[0030] Preparation Example 3 The modified nylon 6 slices are prepared by the following method: 100 kg of nylon 6 slices were immersed in 700 kg of toluene containing maleic anhydride grafted ethylene-octene copolymer for swelling treatment. The mass concentration of maleic anhydride grafted ethylene-octene copolymer in toluene was 8%. The swelling temperature was 80°C and the swelling time was 4 hours. After that, the nylon 6 slices were taken out and dried at 200°C for 3 hours.

[0031] Preparation example of hyperbranched polyurethane microcapsules Preparation Example 4 Hyperbranched polyurethane microcapsules are prepared by the following method: A. 10 kg of pentaerythritol, 30 kg of toluene diisocyanate and 0.1 kg of dibutyltin dilaurate were mixed and reacted at 60° C. for 2 h to obtain a hyperbranched polyurethane prepolymer; B. After mixing 10 kg of ethyl trifluoromethylacrylate, 1 kg of benzophenone and 30 kg of hyperbranched polyurethane prepolymer, 50 kg of acetone was added to dissolve them to form an oil phase, and then 2 kg of emulsifier and 50 kg of water were added to the oil phase, and stirred at a speed of 1000 r / min for 30 min to obtain an emulsion; C. Add 5 kg of diethanolamine to the emulsion, and then react at 50° C. for 3 hours. After the reaction is completed, remove impurities in the system by vacuum distillation, and then separate the microcapsules by centrifugal separation. Then, wash and dry the microcapsules to obtain hyperbranched polyurethane microcapsules.

[0032] Preparation Example 5 Hyperbranched polyurethane microcapsules are prepared by the following method: A. 10 kg of pentaerythritol, 40 kg of toluene diisocyanate and 0.2 kg of dibutyltin dilaurate were mixed and reacted at 70° C. for 3 h to obtain a hyperbranched polyurethane prepolymer; B. After mixing 10 kg of ethyl trifluoromethylacrylate, 2 kg of benzophenone and 40 kg of hyperbranched polyurethane prepolymer, 50 kg of acetone was added to dissolve them to form an oil phase, and then 2 kg of emulsifier and 50 kg of water were added to the oil phase, and stirred at a speed of 1500 r / min for 50 min to obtain an emulsion; C. Add 5 kg of diethanolamine to the emulsion, and then react at 60° C. for 4 hours. After the reaction is completed, remove impurities in the system by vacuum distillation, and then separate the microcapsules by centrifugal separation. Then, wash and dry the microcapsules to obtain hyperbranched polyurethane microcapsules.

[0033] Preparation Example 6 Hyperbranched polyurethane microcapsules are prepared by the following method: A. 10 kg of pentaerythritol, 50 kg of toluene diisocyanate and 0.3 kg of dibutyltin dilaurate were mixed and reacted at 80° C. for 4 h to obtain a hyperbranched polyurethane prepolymer; B. After mixing 10 kg of ethyl trifluoromethylacrylate, 3 kg of benzophenone and 50 kg of hyperbranched polyurethane prepolymer, 60 kg of acetone was added to dissolve them to form an oil phase, and then 2.5 kg of emulsifier and 50 kg of water were added to the oil phase, and stirred at a speed of 2000 r / min for 60 min to obtain an emulsion; C. Add 5.5 kg of diethanolamine to the emulsion, and then react at 70° C. for 5 hours. After the reaction is completed, remove impurities in the system by vacuum distillation, and then separate the microcapsules by centrifugal separation. Then, wash and dry the microcapsules to obtain hyperbranched polyurethane microcapsules.

[0034] Preparation Example 7 The hyperbranched polyurethane microcapsules are different from those of Preparation Example 4 in that no benzophenone is added in step B of this Preparation Example.

[0035] Preparation Example 8 The hyperbranched polyurethane microcapsules are different from those in Preparation Example 4 in that an equal amount of ethyl methacrylate is used in step B instead of ethyl trifluoromethacrylate.

[0036] Example Example 1 A nylon industrial yarn for highly wear-resistant marine cables, the raw material components and dosages of which are shown in Table 1, wherein the modified nylon 6 slices are the modified nylon 6 slices prepared in Preparation Example 1; the nano-ceramic particles are silicon nitride with a particle size of 150 nm and titanium carbide compounded in a mass ratio of 2:1; the hyperbranched polyurethane microcapsules are the hyperbranched polyurethane microcapsules prepared in Preparation Example 4, the dispersant is zinc stearate; and the compatibilizer is γ-aminopropyltriethoxysilane.

[0037] A highly wear-resistant nylon industrial yarn for marine cables, the preparation method of which is as follows: S1, adding modified nylon 6 slices, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to a proportion, and mixing at a speed of 800 r / min for 25 minutes to obtain a premix; S2. Add the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder, perform melt blending at a temperature of 240° C., control the screw speed at 300 r / min, extrude and granulate to obtain spinning masterbatch. S3. The spinning masterbatch is put into a spinning machine, and spinning is carried out at a spinning temperature of 250° C. The spinning speed is set to 1000 m / min. After cooling, stretching, stretching multiples of 4.5 times, and winding processes, high wear-resistant nylon industrial yarn for marine cables is finally obtained.

[0038] Example 2 A nylon industrial yarn for highly wear-resistant marine cables, the raw material components and dosages of which are shown in Table 1, wherein the modified nylon 6 slices are the modified nylon 6 slices prepared in Preparation Example 2; the nano-ceramic particles are silicon nitride with a particle size of 150 nm and titanium carbide compounded in a mass ratio of 2:1; the hyperbranched polyurethane microcapsules are the hyperbranched polyurethane microcapsules prepared in Preparation Example 4, the dispersant is zinc stearate; and the compatibilizer is γ-aminopropyltriethoxysilane.

[0039] A highly wear-resistant nylon industrial yarn for marine cables, the preparation method of which is as follows: S1, adding modified nylon 6 slices, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to a proportion, and mixing at a speed of 1000 r / min for 20 minutes to obtain a premix; S2. Add the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder, perform melt blending at a temperature of 250° C., control the screw speed at 350 r / min, extrude and granulate to obtain spinning masterbatch. S3. The spinning masterbatch is put into a spinning machine, and spinning is carried out at a spinning temperature of 260° C. The spinning speed is set to 1300 m / min. After cooling, stretching, stretching multiple of 5.0 times, and winding process, high wear-resistant nylon industrial yarn for marine cables is finally obtained.

[0040] Example 3 A nylon industrial yarn for highly wear-resistant marine cables, the raw material components and usage are shown in Table 1, wherein the modified nylon 6 slices are the modified nylon 6 slices prepared in Preparation Example 3; the nano-ceramic particles are silicon nitride with a particle size of 150 nm and titanium carbide compounded in a mass ratio of 2:1; the hyperbranched polyurethane microcapsules are the hyperbranched polyurethane microcapsules prepared in Preparation Example 4, the dispersant is zinc stearate; and the compatibilizer is γ-aminopropyltriethoxysilane.

[0041] A highly wear-resistant nylon industrial yarn for marine cables, the preparation method of which is as follows: S1, adding modified nylon 6 slices, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to a proportion, and mixing at a speed of 1200 r / min for 15 minutes to obtain a premix; S2. Add the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder, perform melt blending at a temperature of 260° C., control the screw speed at 400 r / min, extrude and granulate to obtain spinning masterbatch. S3. The spinning masterbatch is put into a spinning machine, and spinning is carried out at a spinning temperature of 270° C. The spinning speed is set to 1500 m / min. After cooling, stretching, stretching multiples of 5.5 times, and winding processes, high wear-resistant nylon industrial yarn for marine cables is finally obtained.

[0042] Table 1 Raw material components and dosage in Examples 1-3 (kg)

[0043] Example 4 A highly wear-resistant nylon industrial yarn for marine cables, which is different from Example 1 in that the hyperbranched polyurethane microcapsules in this example are the hyperbranched polyurethane microcapsules prepared in Preparation Example 5.

[0044] Example 5 A highly wear-resistant nylon industrial yarn for marine cables, which is different from Example 1 in that the hyperbranched polyurethane microcapsules in this example are the hyperbranched polyurethane microcapsules prepared in Preparation Example 6.

[0045] Example 6 A highly wear-resistant nylon industrial yarn for marine cables, which is different from Example 1 in that the dispersant in this example is polyethylene wax.

[0046] Comparative Example Comparative Example 1 A highly wear-resistant nylon industrial yarn for marine cables, which is different from Example 1 in that an equal amount of unmodified nylon 6 slices are used in this comparative example instead of modified nylon 6 slices.

[0047] Comparative Example 2 A highly wear-resistant nylon industrial yarn for marine cables, which is different from Example 1 in that the hyperbranched polyurethane microcapsules in this comparative example are the hyperbranched polyurethane microcapsules prepared in Preparation Example 7.

[0048] Comparative Example 3 A highly wear-resistant nylon industrial yarn for marine cables, which is different from Example 1 in that the hyperbranched polyurethane microcapsules in this comparative example are the hyperbranched polyurethane microcapsules prepared in Preparation Example 8.

[0049] Comparative Example 4 A highly wear-resistant nylon industrial yarn for marine cables, which differs from Example 1 in that an equal amount of modified nylon 6 slices are used instead of nano-ceramic particles in this comparative example.

[0050] Performance testing Test 1 Wear resistance test With reference to FZ / T01058-1999, the filament samples were tested for wear resistance using a reciprocating wear tester. The tension weight used was 35g, the water sandpaper was 400, and it was rotated continuously at a speed of 75m / min. The number of frictions when it broke was recorded to evaluate its wear resistance. The test results are shown in Table 2.

[0051] Test 2: Fracture strength test From the nylon industrial yarn prepared in the embodiment and the comparative example, a sample with a length of 250 mm was cut, and the two ends of the sample were respectively fixed on the upper and lower clamps of the universal material testing machine to ensure that the sample was installed vertically and without distortion, and the clamp spacing was set to 200 mm. The stretching speed was set to 200 mm / min, and the universal material testing machine was started to stretch the sample at a uniform speed until the sample broke. During the stretching process, the testing machine automatically recorded the maximum force value when the sample broke, and the elongation at break was measured and calculated after the sample broke. The test results are shown in Table 2.

[0052] Table 2 Test results of Examples 1-6 and Comparative Examples 1-4

[0053] The wear resistance data of Examples 1-5 are 128,000 times, 126,000 times, 125,000 times, 126,000 times, and 124,000 times, respectively, which are at a relatively high level and relatively stable as a whole. This is mainly due to the synergistic effect between the raw materials. The modified nylon 6 slices are subjected to swelling treatment, which not only improves the processing performance, but also improves the compatibility with other components, providing a stable matrix for the material. Nano-ceramic particles rely on high hardness and chemical stability to bear part of the force during friction and prevent excessive wear of the fiber matrix. Polytetrafluoroethylene and molybdenum disulfide nanosheets synergistically form a lubricating layer to reduce the friction coefficient. Hyperbranched polyurethane microcapsules release fluorinated acrylate monomers to repair the fiber surface when worn. These factors work together to make the nylon industrial yarns of Examples 1-5 have good wear resistance. The breaking strength of Examples 1-5 fluctuates between 22.7-23.3cN / dtex. The modified nylon 6 chips enhance the interaction between molecular chains, the nano-ceramic particles are tightly combined with the matrix to enhance rigidity, and the wall material of the hyperbranched polyurethane microcapsule has good interface interactions with other components, all of which help to improve the breaking strength of nylon industrial yarn.

[0054] The wear resistance of Example 6 is 108,000 times, which is lower than that of Examples 1-5. The main reason is that the dispersant is changed from zinc stearate to polyethylene wax. Zinc stearate can better reduce the surface tension of nano-ceramic particles, etc., so that they are evenly dispersed in the system and give full play to the wear resistance; while the dispersion effect of polyethylene wax is poor, resulting in uneven dispersion of each component, which reduces the overall wear resistance of the material. The fracture strength of Example 6 is 20.3cN / dtex, which is lower than that of Examples 1-5. The change of the dispersant affects the uniformity of the dispersion of each component, destroys the uniformity and continuity of the internal structure of the material, aggravates the stress concentration phenomenon when subjected to force, reduces the material's ability to resist fracture, and thus leads to a decrease in fracture strength.

[0055] Comparative Example 1 uses unmodified nylon 6 chips, which lacks the molecular chain optimization and compatibility improvement brought by modification, and cannot provide a good matrix for other wear-resistant components, resulting in a wear resistance of only 38,000 times. The molecular chain interaction of unmodified nylon 6 chips in Comparative Example 1 is weak, and the breaking strength is only 8.6 cN / dtex. This proves the importance of modified nylon 6 chips in improving wear resistance and breaking strength.

[0056] In Comparative Example 2, no benzophenone was added to the microcapsules, and in Comparative Example 3, ethyl methacrylate was used instead of ethyl trifluoromethacrylate, both of which destroyed the self-repairing function of the microcapsules, making it difficult to effectively repair the fiber surface after wear, and the wear resistance dropped to 53,000 times and 46,000 times respectively. In Comparative Example 4, an equal amount of modified nylon 6 slices were used instead of nano-ceramic particles, which lacked the "hard skeleton" effect of nano-ceramic particles, and the wear resistance was 96,000 times, which was significantly lower than that of the embodiment.

[0057] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A highly wear-resistant nylon industrial yarn for marine cables, characterized in that: The invention comprises the following raw materials in parts by weight: Modified nylon 6 slices 85-95 parts; 3-10 parts of nano ceramic particles; 3-5 parts of polytetrafluoroethylene; 3-5 parts of molybdenum disulfide nanosheets; 10-15 parts of hyperbranched polyurethane microcapsules; 1-3 parts of dispersant; 1-3 parts of compatibilizer; The modified nylon 6 slice is obtained by swelling the nylon 6 slice in a solution containing maleic anhydride grafted ethylene-octene copolymer and then drying; The wall material of the hyperbranched polyurethane microcapsule is a hyperbranched polyurethane prepolymer, and the core material comprises a fluorine-containing acrylate monomer and benzophenone.

2. The highly wear-resistant nylon industrial yarn for marine cables according to claim 1, characterized in that: The modified nylon 6 slice is prepared by the following method: The nylon 6 slices are swelled in a solution containing maleic anhydride grafted ethylene-octene copolymer at a swelling temperature of 60-80°C for 2-4 hours. The nylon 6 slices are then taken out and dried at 180-200°C for 2-3 hours.

3. The highly wear-resistant nylon industrial yarn for marine cables according to claim 2, characterized in that: The solvent of the solution is toluene or xylene, and the mass concentration of the maleic anhydride grafted ethylene-octene copolymer in the solution is 3%-8%.

4. The highly wear-resistant nylon industrial yarn for marine cables according to claim 2, characterized in that: The mass ratio of the nylon 6 slices to the solution is 1:(5-7).

5. The highly wear-resistant nylon industrial yarn for marine cables according to claim 1, characterized in that: The hyperbranched polyurethane microcapsules are prepared by the following method: A. Mix pentaerythritol, toluene diisocyanate and a catalyst, and react at 60-80° C. for 2-4 hours to obtain a hyperbranched polyurethane prepolymer; B. After mixing the fluorinated acrylate monomer, benzophenone and hyperbranched polyurethane prepolymer, acetone is added to dissolve them to form an oil phase, and then an emulsifier and water are added to the oil phase, and stirred at a speed of 1000-2000 r / min for 30-60 min to obtain an emulsion; C. Add diethanolamine to the emulsion, and then react at 50-70° C. for 3-5 hours. After the reaction is completed, remove impurities in the system by vacuum distillation, and then separate the microcapsules by centrifugal separation. Then, wash and dry the microcapsules to obtain hyperbranched polyurethane microcapsules.

6. The highly wear-resistant nylon industrial yarn for marine cables according to claim 5, characterized in that: In step A, the mass ratio of pentaerythritol, toluene diisocyanate and catalyst is 1:(3-5):(0.01-0.03).

7. The highly wear-resistant nylon industrial yarn for marine cables according to claim 5, characterized in that: The catalyst in step A is dibutyltin dilaurate.

8. The highly wear-resistant nylon industrial yarn for marine cables according to claim 5, characterized in that: In step B, the mass ratio of the fluorinated acrylate monomer, benzophenone and hyperbranched polyurethane prepolymer is 1:(0.1-0.3):(3-5).

9. The highly wear-resistant nylon industrial yarn for marine cables according to claim 5, characterized in that: The fluorine-containing acrylate monomer in step B is preferably ethyl trifluoromethacrylate.

10. A method for preparing the highly wear-resistant nylon industrial yarn for marine cables according to any one of claims 1 to 9, characterized in that: The steps include: S1, adding modified nylon 6 slices, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to a proportion, and mixing at a speed of 800-1200 r / min for 15-25 minutes to obtain a premix; S2, adding the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder, melt blending at a temperature of 240-260° C., controlling the screw speed at 300-400 r / min, extruding and granulating to obtain a spinning masterbatch; S3. The spinning masterbatch is put into a spinning machine, and spinning is performed at a spinning temperature of 250-270° C. The spinning speed is set to 1000-1500 m / min. After cooling, stretching, and winding processes, a highly wear-resistant nylon industrial yarn for marine cables is finally obtained.

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