A Nylon Industrial Yarn for High-Wear-Resistant Marine Cable and Its Preparation Method

Abstract

This application relates to the technical field of nylon spinning, and specifically discloses a nylon industrial yarn for high-wear-resistant marine cables and a preparation method thereof. A nylon industrial yarn for high-wear-resistant marine cables, the raw materials of which include: 85-95 parts of modified nylon 6 chips; 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 chips are obtained by swelling nylon 6 chips in a solution containing maleic anhydride-grafted ethylene-octene copolymer and then drying; the wall material of the hyperbranched polyurethane microcapsules is a hyperbranched polyurethane prepolymer, and the core material includes a fluorinated acrylate monomer and benzophenone. The nylon industrial yarn of this application 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, it relates to a nylon industrial yarn for high-abrasion-resistant marine ropes 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. In various marine operations, marine ropes play a crucial role. Whether it is ship mooring, marine engineering construction, or fishing and other scenarios, marine ropes are indispensable. Nylon industrial yarn has become an ideal material for manufacturing marine ropes due to its excellent strength, abrasion resistance, seawater corrosion resistance, and good flexibility. Its high-strength characteristic can ensure that the marine rope does not break under huge tensile forces, effectively guaranteeing operation safety; while good abrasion resistance and seawater corrosion resistance enable the rope to be stably used for a long time in a complex and harsh marine environment, reducing the replacement frequency and saving costs. Therefore, the performance of nylon industrial yarn directly determines the quality and service life of marine ropes.

[0003] In related technologies, for example, the patent application document with the publication number CN107938016A discloses a yarn for marine ropes, whose formula includes 100 parts of nylon 6 chips, 0.05 - 0.1 part of anti-aging agent, 0.08 - 0.12 part of ultraviolet absorber, 1.0 - 1.4 parts of nylon 6 high-speed spinning oil agent, and 1.3 - 1.7 parts of seawater corrosion-resistant oil agent. When preparing this yarn for marine ropes, on the basis of nylon 6 industrial filament, oiling is carried out on the filament bundle, and 3 - 4 nozzle oilings are adopted. The oil agent is Galsdon 12351 seawater corrosion-resistant oil agent; the oil agent flowing down through the nozzle returns to the reflux tank and is recycled by a circulating pump; after oiling, winding and forming are carried out. From the feedback of actual application, the nylon industrial yarn prepared by this technical solution can meet certain use requirements in some rope application scenarios with conventional strength requirements.

[0004] However, when applied to the field of marine ropes, this nylon industrial yarn exposes obvious defects. The nylon industrial yarn prepared by the above-mentioned existing technology, although having certain improvements in strength and uniformity, is still insufficient in abrasion resistance. During marine operations, the rope frequently rubs against the hull, dock facilities, etc., and surface wear will occur in a short time, seriously affecting the service life and safety of the rope. Thus, how to further improve the abrasion resistance of nylon industrial yarn so that it can better adapt to the complex marine environment has become an urgent technical problem to be solved. Summary of the Invention

[0005] In order to enhance the abrasion resistance of nylon industrial yarn, the present application provides a nylon industrial yarn for high-abrasion-resistant marine ropes and a preparation method thereof.

[0006] The nylon industrial yarn for high-abrasion-resistant marine ropes provided by this application adopts the following technical solution:

[0007] A nylon industrial yarn for high-abrasion-resistant marine ropes, comprising raw materials in the following weight parts:

[0008] 85-95 parts of modified nylon 6 chips;

[0009] 3-10 parts of nano-ceramic particles;

[0010] 3-5 parts of polytetrafluoroethylene;

[0011] 3-5 parts of molybdenum disulfide nanosheets;

[0012] 10-15 parts of hyperbranched polyurethane microcapsules;

[0013] 1-3 parts of dispersant;

[0014] 1-3 parts of compatibilizer;

[0015] The modified nylon 6 chips are obtained by swelling nylon 6 chips in a solution containing maleic anhydride-grafted ethylene-octene copolymer and then drying.

[0016] The wall material of the hyperbranched polyurethane microcapsules is hyperbranched polyurethane prepolymer, and the core material includes fluorinated acrylate monomer and benzophenone.

[0017] By swelling treatment 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 nylon 6 molecular chains, increasing the molecular chain spacing, reducing the intermolecular force, and improving the mobility of the chain segments. At the same time, the maleic anhydride group can chemically react with active groups such as amino groups on the nylon 6 molecular chain to form chemical bond connections, enhancing the interaction between molecular chains. This not only improves the processing performance of nylon 6 but also enhances its compatibility with other components, laying a foundation for subsequent uniform mixing, and further enhancing the performance stability and mechanical properties of the overall material, playing a key matrix support role in improving wear resistance. Nano-ceramic particles have high hardness, high wear resistance, and good chemical stability. With a particle size in the range of 50-150 nm, they can be evenly dispersed in the nylon industrial yarn matrix. During the friction process, the nano-ceramic particles can bear part of the frictional force, playing a role similar to a "rigid skeleton" to prevent excessive wear of the fiber matrix. It is physically embedded and chemically bonded with the nylon 6 matrix (such as binding to the active sites generated in the reaction of the modified nylon 6 chips), enhancing the overall rigidity and wear resistance of the material, and effectively resisting the damage of various frictional factors in the marine environment to the fiber surface.

[0018] 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 subjected to friction, polytetrafluoroethylene can slide between the fibers, reducing the frictional resistance between different parts inside the fiber. At the same time, it can reduce the friction coefficient with external objects on the fiber surface, effectively reducing wear. Molybdenum disulfide nanosheets have a layered structure with relatively weak interlayer forces and can undergo slip during the friction process, playing a good role in solid lubrication. Therefore, it can cooperate 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 them to form a tight and orderly interfacial bond with nano-ceramic particles, nylon 6 matrix, etc. Their unique sheet-like morphology can be evenly dispersed in the matrix, interpenetrate and cooperate with nano-ceramic particles, enhancing the overall mechanical properties of the material and improving the resistance to wear. Especially under high-load friction conditions, it can effectively disperse stress and prevent severe wear on the fiber surface.

[0019] The wall material of the hyperbranched polyurethane microcapsule, the hyperbranched polyurethane prepolymer, has a highly branched structure. A large number of active groups on the surface can form good interfacial interactions with nylon 6 chips and other additives, enhancing the binding force between components inside the fiber. When the material is subjected to external friction, each component can better cooperate to resist the external force, avoiding increased wear caused by relative sliding or detachment. After the microcapsules rupture due to wear, the released fluorinated acrylate monomer can undergo a polymerization reaction under the action of benzophenone to form a fluorinated polymer film with low surface energy and good lubrication performance, filling the micro-scratches and defects generated by wear, restoring the integrity of the fiber surface, and reducing further wear. Benzophenone generates free radicals under ultraviolet irradiation, which can initiate the polymerization reaction of the fluorinated acrylate monomer, facilitating the acceleration of the repair process. At the same time, these free radicals have certain antibacterial activity, and their antibacterial properties can inhibit the erosion of nylon filaments by microorganisms in the marine environment, thus effectively improving the wear resistance and durability of nylon industrial yarns.

[0020] Optionally, the modified nylon 6 chips are prepared by the following method:

[0021] The nylon 6 chips are subjected to a swelling treatment in a solution containing maleic anhydride-grafted ethylene-octene copolymer. The swelling temperature is 60 - 80 °C, and the swelling time is 2 - 4 h. Then, the nylon 6 chips are taken out and dried at 180 - 200 °C for 2 - 3 hours.

[0022] Optionally, the solvent of the solution is toluene or xylene, and the mass concentration of maleic anhydride-grafted ethylene-octene copolymer in the solution is 3% - 8%.

[0023] By adopting the above technical solution, POE-g-MAH can be well dissolved in toluene or xylene solution, and its molecular chain has a certain mobility, which can effectively insert into the molecular chain of nylon 6. The swelling time is controlled within 2 - 4 h, which can not only ensure that POE-g-MAH fully diffuses into the nylon 6 chips, but also avoid excessive damage to the molecular chain caused by too long time. When the mass concentration of POE-g-MAH is within this range, it can effectively modify nylon 6 while avoiding an excessive increase in the viscosity of the system, which affects the processing performance.

[0024] Optionally, the mass ratio of the nylon 6 chips to the solution is 1:(5 - 7).

[0025] By adopting the above technical solution, the appropriate mass ratio ensures the sufficiency and uniformity of the swelling treatment, making the modification effect reach the best, providing a good matrix material for the subsequent preparation of high-performance nylon industrial yarn, and is of great significance for improving the comprehensive performance of the material, especially the wear resistance.

[0026] Optionally, the hyperbranched polyurethane microcapsules are prepared by the following method:

[0027] A. Mix pentaerythritol, toluene diisocyanate and a catalyst, and react at 60 - 80 °C for 2 - 4 h to obtain a hyperbranched polyurethane prepolymer;

[0028] B. Mix the fluorinated acrylate monomer, benzophenone and the hyperbranched polyurethane prepolymer, add acetone to dissolve them to form an oil phase, then add an emulsifier and water to the oil phase, and stir at a speed of 1000 - 2000 r / min for 30 - 60 min to obtain an emulsion;

[0029] C. Add diethanolamine to the emulsion, then react at 50 - 70 °C for 3 - 5 h. After the reaction is completed, remove the impurities in the system by vacuum distillation, then separate the microcapsules by centrifugation, and then wash and dry the microcapsules to obtain hyperbranched polyurethane microcapsules.

[0030] Optionally, in step A, the mass ratio of pentaerythritol, toluene diisocyanate and the catalyst is 1:(3 - 5):(0.01 - 0.03).

[0031] Optionally, the catalyst in step A is dibutyltin dilaurate.

[0032] Optionally, in step B, the mass ratio of the fluorinated acrylate monomer, benzophenone and the hyperbranched polyurethane prepolymer is 1:(0.1 - 0.3):(3 - 5).

[0033] Optionally, the fluorinated acrylate monomer in step B is preferably ethyl trifluoromethylacrylate.

[0034] By adopting the above technical solution, in step A, pentaerythritol, toluene diisocyanate and a catalyst (dibutyltin dilaurate) react at 60 - 80 °C for 2 - 4 h. This condition is beneficial to synthesize a hyperbranched polyurethane prepolymer with a suitable molecular weight and branched structure. Its highly branched structure and surface active groups lay a foundation for good combination with other components in the subsequent steps. In step B, a fluorinated acrylate monomer, benzophenone and the hyperbranched polyurethane prepolymer are mixed in a specific proportion, ensuring that each component in the microcapsule core material can play a synergistic role. Ethyl trifluoromethacrylate, as a preferred fluorinated acrylate monomer, has good self-healing performance and chemical stability. By controlling the stirring speed and time during the emulsification process, a stable emulsion is formed, ensuring the particle size uniformity and structural stability of the microcapsules. In step C, diethanolamine is added and reacts at 50 - 70 °C for 3 - 5 h, enabling the further polymerization of the hyperbranched polyurethane to form a stable wall material to encapsulate the core material. Subsequent steps such as vacuum distillation, centrifugal separation, washing and drying remove impurities, obtaining pure hyperbranched polyurethane microcapsules. Their stable structure and performance provide a strong guarantee for enhancing the abrasion resistance of nylon industrial yarns.

[0035] This application also provides a method for preparing nylon industrial yarns for high-abrasion-resistant marine cables, adopting the following technical solution:

[0036] A method for preparing nylon industrial yarns for high-abrasion-resistant marine cables includes the following steps:

[0037] S1. Add modified nylon 6 chips, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and a dispersant into a high-speed mixer according to the ratio, and mix at a rotation speed of 800 - 1200 r / min for 15 - 25 minutes to obtain a premix;

[0038] S2. Add the premix, hyperbranched polyurethane microcapsules and a compatibilizer into a twin-screw extruder, and conduct melt blending at a temperature of 240 - 260 °C. The screw rotation speed is controlled at 300 - 400 r / min, and then pelletize by extrusion to obtain a spinning masterbatch;

[0039] S3. Put the spinning masterbatch into a spinning machine, and conduct spinning at a spinning temperature of 250 - 270 °C. The spinning speed is set at 3000 - 4000 m / min, and through the processes of cooling, stretching and winding, finally prepare nylon industrial yarns for high-abrasion-resistant marine cables.

[0040] This preparation method ensures the uniform dispersion and good combination of each component through step-by-step mixing and control of specific process parameters. In S1, mixing at a speed of 800 - 1200 r / min in a high-speed mixer for 15 - 25 minutes can preliminarily and uniformly mix the modified polyamide 6 chips, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets, and dispersant, creating favorable conditions for subsequent melt blending. In S2, melt blending is carried out at 240 - 260 °C with a screw speed of 300 - 400 r / min. This temperature and speed can not only ensure the full melting of each component but also enable them to be further uniformly dispersed and interact 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 °C and a spinning speed of 3000 - 4000 m / min. Through cooling, stretching at a specific stretching ratio (4.5 - 5.5 times), and winding processes, the fibers form an ordered molecular orientation and microstructure during the forming process, further enhancing the mechanical properties and wear resistance of the fibers, and finally producing polyamide industrial yarns that meet the high wear resistance requirements of marine cables.

[0041] In summary, the present application has the following beneficial effects:

[0042] 1. In the present application, through modification treatment, the modified polyamide 6 chips not only increase the molecular chain spacing, reduce the intermolecular force, improve the mobility of the chain segments, and enhance the processing performance, but also form chemical bond connections through chemical reactions between maleic anhydride groups and active groups such as amino groups on the polyamide 6 molecular chain, strengthening the interaction between molecular chains and improving the compatibility with other components. This provides a stable and solid matrix for the overall material, enabling other wear-resistant components to better play their roles and fundamentally enhancing the wear resistance of the polyamide industrial yarns. The hyperbranched polyurethane microcapsules have a highly branched structure of the wall material hyperbranched polyurethane prepolymer, which makes its surface contain a large number of isocyanate groups, hydroxyl groups, and other unsaturated bonds. These active groups can form good interfacial interactions with the polyamide 6 chips 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 a polymerization reaction under the action of benzophenone to form a fluoropolymer film with low surface energy and good lubrication performance, filling the micro-scratches and defects generated by wear, restoring the integrity of the fiber surface, and reducing further wear. Benzophenone can not only initiate the polymerization reaction of fluorinated acrylate monomers and accelerate the repair process but also inhibit the erosion of microorganisms in the marine environment on the polyamide filaments with its antibacterial properties, further enhancing the wear resistance and durability of the polyamide industrial yarns.

[0043] 2. The nano-ceramic particles in this application play an important role in enhancing the abrasion resistance of polyamide industrial yarns. Nano-ceramic particles with a particle size in the range of 50 - 150 nm are selected in this application, and they can be evenly dispersed in the polyamide industrial yarn matrix. Nano-ceramic particles have high hardness, high abrasion resistance, and good chemical stability. During the friction process, they can bear part of the frictional force, just like building "hard skeletons" inside the fibers, effectively preventing excessive wear of the fiber matrix. There are various interaction modes between the nano-ceramic particles and the polyamide 6 matrix. On the one hand, through physical embedding, the nano-ceramic particles are tightly embedded in the polyamide 6 matrix, increasing the overall rigidity of the material; on the other hand, the nano-ceramic particles can form chemical bonds with the active sites generated during the reaction of the modified polyamide 6 chips, further enhancing the binding force with the matrix. This tight binding enables the nano-ceramic particles to stably exist inside the fibers when subjected to frictional external forces, continuously playing the role of resisting wear.

[0044] 3. In this application, polytetrafluoroethylene and molybdenum disulfide nanosheets act synergistically, greatly promoting the improvement of the abrasion resistance of polyamide industrial yarns. Polytetrafluoroethylene has an extremely low surface friction coefficient and can form a lubricating layer inside and on the surface of the fibers. When the fibers are subjected to friction, polytetrafluoroethylene can freely slide between the fibers, effectively reducing the frictional resistance between various parts inside the fibers and reducing fiber damage caused by internal friction. At the same time, on the fiber surface, polytetrafluoroethylene reduces the friction coefficient with external objects, significantly reducing the degree of wear when the polyamide industrial yarn comes into contact and frictions with various objects in the marine environment. Molybdenum disulfide nanosheets have a unique layered structure with weak interlayer forces and can undergo slip during the friction process, thus playing a good solid lubrication role. It cooperates with polytetrafluoroethylene to further reduce the friction coefficient inside and on the surface of the fibers. In addition, the two-dimensional structure of molybdenum disulfide nanosheets enables them to form good interfacial bonding with nano-ceramic particles, polyamide 6 matrix, etc. This good interfacial 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 polyamide industrial yarns in various friction scenarios, significantly improving their abrasion resistance and providing strong guarantee for the long-term stable use of marine cables. Detailed implementation manners

[0045] The following further elaborates on this application with reference to the embodiments.

[0046] The sources of the main raw materials in the embodiments of this application are as follows:

[0047] The polyamide 6 chips are the YH800 type standard material purchased from Yuyao Xinsuyang Plasticizing Business.

[0048] The maleic anhydride grafted ethylene-octene copolymer is prepared by the following method:

[0049] First, the ethylene-octene copolymer is dried in a vacuum drying oven at 80 °C for 4 h; then, maleic anhydride is weighed at 5% of the mass of the ethylene-octene copolymer, dicumyl peroxide is weighed at 0.2%, and antioxidant 1010 is weighed at 0.5%. The dried ethylene-octene copolymer, maleic anhydride, dicumyl peroxide, and antioxidant 1010 are added to a high-speed mixer and mixed at a speed of 1000 r / min for 15 min at room temperature; subsequently, the mixed material is added to a twin-screw extruder. The head temperature of the extruder is set at 200 °C, the screw speed is 200 r / min, and the material stays for 5 minutes for melt grafting reaction; the reacted material is cut into particles about 2 mm by a pelletizer and then dried in a vacuum drying oven at 80 °C for 6 h to obtain the maleic anhydride grafted ethylene-octene copolymer.

[0050] Preparation example of modified polyamide 6 chips

[0051] Preparation example 1

[0052] The modified polyamide 6 chips are prepared by the following method:

[0053] 100 kg of polyamide 6 chips are 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 is 3%, the swelling temperature is 60 °C, and the swelling time is 2 h. Then, the polyamide 6 chips are taken out and dried at 180 °C for 2 hours.

[0054] Preparation example 2

[0055] The modified polyamide 6 chips are prepared by the following method:

[0056] 100 kg of polyamide 6 chips are 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 is 5%, the swelling temperature is 70 °C, and the swelling time is 3 h. Then, the polyamide 6 chips are taken out and dried at 190 °C for 2.5 hours.

[0057] Preparation example 3

[0058] The modified polyamide 6 chips are prepared by the following method:

[0059] 100 kg of nylon 6 chips 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 h. After that, the nylon 6 chips were taken out and dried at 200 °C for 3 hours.

[0060] Preparation Example of Hyperbranched Polyurethane Microcapsules

[0061] Preparation Example 4

[0062] The hyperbranched polyurethane microcapsules were prepared by the following method:

[0063] 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;

[0064] B. 10 kg of ethyl trifluoromethacrylate, 1 kg of benzophenone and 30 kg of hyperbranched polyurethane prepolymer were mixed, and 50 kg of acetone was added to dissolve them to form an oil phase. Then, 2 kg of emulsifier and 50 kg of water were added to the oil phase, and the mixture was stirred at a speed of 1000 r / min for 30 min to obtain an emulsion;

[0065] C. 5 kg of diethanolamine was added to the emulsion, and then the reaction was carried out at 50 °C for 3 h. After the reaction was completed, impurities in the system were removed by vacuum distillation, and then the microcapsules were separated by centrifugation. Then, the microcapsules were washed and dried to obtain hyperbranched polyurethane microcapsules.

[0066] Preparation Example 5

[0067] The hyperbranched polyurethane microcapsules were prepared by the following method:

[0068] 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;

[0069] B. 10 kg of ethyl trifluoromethacrylate, 2 kg of benzophenone and 40 kg of hyperbranched polyurethane prepolymer were mixed, and 50 kg of acetone was added to dissolve them to form an oil phase. Then, 2 kg of emulsifier and 50 kg of water were added to the oil phase, and the mixture was stirred at a speed of 1500 r / min for 50 min to obtain an emulsion;

[0070] C. 5 kg of diethanolamine was added to the emulsion, and then the reaction was carried out at 60 °C for 4 h. After the reaction was completed, impurities in the system were removed by vacuum distillation, and then the microcapsules were separated by centrifugation. Then, the microcapsules were washed and dried to obtain hyperbranched polyurethane microcapsules.

[0071] Preparation Example 6

[0072] Hyperbranched polyurethane microcapsules were prepared by the following method:

[0073] 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;

[0074] B. 10 kg of ethyl trifluoromethacrylate, 3 kg of benzophenone and 50 kg of the hyperbranched polyurethane prepolymer were mixed, and then 60 kg of acetone was added to dissolve them to form an oil phase. Then, 2.5 kg of emulsifier and 50 kg of water were added to the oil phase, and the mixture was stirred at a speed of 2000 r / min for 60 min to obtain an emulsion;

[0075] C. 5.5 kg of diethanolamine was added to the emulsion, and then the reaction was carried out at 70 °C for 5 h. After the reaction was completed, impurities in the system were removed by vacuum distillation, and then the microcapsules were separated by centrifugation. Then, the microcapsules were washed and dried to obtain hyperbranched polyurethane microcapsules.

[0076] Preparation Example 7

[0077] Hyperbranched polyurethane microcapsules, different from Preparation Example 4 in that: in this preparation example, benzophenone was not added in step B.

[0078] Preparation Example 8

[0079] Hyperbranched polyurethane microcapsules, different from Preparation Example 4 in that: in this preparation example, an equal amount of ethyl methacrylate was used instead of ethyl trifluoromethacrylate in step B.

[0080] Example

[0081] Example 1

[0082] A nylon industrial yarn for high-wear-resistant marine cables, the raw material components and their dosages are shown in Table 1, wherein the modified nylon 6 chips are the modified nylon 6 chips prepared in Preparation Example 1; the nano-ceramic particles are a compound of silicon nitride and titanium carbide with a particle size of 150 nm 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; the compatibilizer is γ-aminopropyltriethoxysilane.

[0083] A method for preparing a nylon industrial yarn for high-wear-resistant marine cables is as follows:

[0084] S1. Add the modified polyamide 6 chips, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to the ratio, and mix for 25 minutes at a rotation speed of 800 r / min to obtain a premix;

[0085] S2. Add the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder together, and conduct melt blending at a temperature of 240 °C, control the screw rotation speed at 300 r / min, extrude and pelletize to obtain a spinning masterbatch.

[0086] S3. Put the spinning masterbatch into a spinning machine, conduct spinning at a spinning temperature of 250 °C, set the spinning speed at 1000 m / min, and after cooling, stretching with a stretching ratio of 4.5 times and winding process, finally obtain the polyamide industrial yarn for highly wear-resistant marine cables.

[0087] Example 2

[0088] A polyamide industrial yarn for highly wear-resistant marine cables, the raw material components and dosages are shown in Table 1, wherein the modified polyamide 6 chips are the modified polyamide 6 chips prepared in Preparation Example 2; the nano-ceramic particles are a compound of silicon nitride and titanium carbide with a particle size of 150 nm according to 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; the compatibilizer is γ-aminopropyltriethoxysilane.

[0089] A method for preparing a polyamide industrial yarn for highly wear-resistant marine cables is as follows:

[0090] S1. Add the modified polyamide 6 chips, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to the ratio, and mix for 20 minutes at a rotation speed of 1000 r / min to obtain a premix;

[0091] S2. Add the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder together, and conduct melt blending at a temperature of 250 °C, control the screw rotation speed at 350 r / min, extrude and pelletize to obtain a spinning masterbatch.

[0092] S3. Put the spinning masterbatch into a spinning machine, conduct spinning at a spinning temperature of 260 °C, set the spinning speed at 1300 m / min, and after cooling, stretching with a stretching ratio of 5.0 times and winding process, finally obtain the polyamide industrial yarn for highly wear-resistant marine cables.

[0093] Example 3

[0094] A polyamide industrial yarn for high-abrasion-resistant marine cable, the raw material components and dosages of which are shown in Table 1, wherein the modified polyamide 6 chips are the modified polyamide 6 chips prepared in Preparation Example 3; the nano-ceramic particles are silicon nitride and titanium carbide with a particle size of 150 nm 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; the compatibilizer is γ-aminopropyltriethoxysilane.

[0095] A polyamide industrial yarn for high-abrasion-resistant marine cable, the preparation method of which is as follows:

[0096] S1. Add the modified polyamide 6 chips, nano-ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant into a high-speed mixer according to the ratio, and mix at a rotation speed of 1200 r / min for 15 minutes to obtain a premix.

[0097] S2. Add the premix, hyperbranched polyurethane microcapsules and compatibilizer into a twin-screw extruder together, and carry out melt blending at a temperature of 260 °C, control the screw rotation speed at 400 r / min, and extrude and pelletize to obtain a spinning masterbatch.

[0098] S3. Put the spinning masterbatch into a spinning machine, carry out spinning at a spinning temperature of 270 °C, set the spinning speed at 1500 m / min, and go through the processes of cooling, stretching with a stretching multiple of 5.5 times, and winding to finally obtain the polyamide industrial yarn for high-abrasion-resistant marine cable.

[0099] Table 1 Raw material components and dosages (kg) in Examples 1-3

[0100]

[0101] Example 4

[0102] A polyamide industrial yarn for high-abrasion-resistant marine cable, 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.

[0103] Example 5

[0104] A polyamide industrial yarn for high-abrasion-resistant marine cable, 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.

[0105] Example 6

[0106] A polyamide industrial yarn for high-abrasion-resistant marine cable, which is different from Example 1 in that the dispersant in this example is polyethylene wax.

[0107] Comparative Example

[0108] Comparative Example 1

[0109] A polyamide industrial yarn for high wear-resistant marine cable, different from Example 1 in that in this comparative example, an equal amount of unmodified polyamide 6 chips are used to replace the modified polyamide 6 chips.

[0110] Comparative Example 2

[0111] A polyamide industrial yarn for high wear-resistant marine cable, different from Example 1 in that in this comparative example, the hyperbranched polyurethane microcapsules used are the hyperbranched polyurethane microcapsules prepared in Preparation Example 7.

[0112] Comparative Example 3

[0113] A polyamide industrial yarn for high wear-resistant marine cable, different from Example 1 in that in this comparative example, the hyperbranched polyurethane microcapsules used are the hyperbranched polyurethane microcapsules prepared in Preparation Example 8.

[0114] Comparative Example 4

[0115] A polyamide industrial yarn for high wear-resistant marine cable, different from Example 1 in that in this comparative example, an equal amount of modified polyamide 6 chips are used to replace the nano-ceramic particles.

[0116] Performance detection test

[0117] Test 1 Abrasion resistance test

[0118] Referring to FZ / T01058-1999, a reciprocating abrasion tester is used to conduct abrasion tests on filament samples. The tension weight used is 35 g, the water sandpaper is No. 400, and it rotates continuously at a speed of 75 m / min. Record the number of friction times at break to evaluate its abrasion resistance. The test results are shown in Table 2.

[0119] Test 2 Tensile strength test

[0120] From the polyamide industrial yarns prepared in the examples and comparative examples, specimens with a length of 250 mm are intercepted. The two ends of the specimens are respectively fixed on the upper and lower clamps of a universal material testing machine to ensure that the specimens are installed vertically and without distortion, and the clamp spacing is set to 200 mm. Set the tensile speed to 200 mm / min, start the universal material testing machine, and conduct uniform stretching on the specimens until the specimens break. During the stretching process, the testing machine automatically records the maximum force value at break of the specimens, and the elongation at break is measured and calculated after the specimens break. The test results are shown in Table 2.

[0121] Table 2 Test results of Examples 1-6 and Comparative Examples 1-4

[0122]

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A nylon industrial yarn for high-wear-resistant marine cable, characterized in that, It comprises raw materials in the following parts by weight: 85 - 95 parts of modified polyamide 6 chips; 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 wall material of the hyperbranched polyurethane microcapsules is hyperbranched polyurethane prepolymer, and the core material includes fluoroacrylate monomer and benzophenone; The modified polyamide 6 chips are prepared by the following method: The polyamide 6 chips are swollen in a solution containing maleic anhydride - grafted ethylene - octene copolymer at a swelling temperature of 60 - 80°C for 2 - 4 h, and then the polyamide 6 chips are taken out and dried at 180 - 200°C for 2 - 3 h; the solvent of the solution is toluene or xylene.

2. The polyamide industrial yarn for high-wear-resistant marine cable according to claim 1, characterized in that: The mass concentration of maleic anhydride - grafted ethylene - octene copolymer in the solution is 3% - 8%.

3. The polyamide industrial yarn for highly wear-resistant marine cable according to claim 1, wherein: The mass ratio of the polyamide 6 chips to the solution is 1:(5 - 7).

4. The polyamide industrial yarn for highly wear-resistant marine cable according to claim 1, characterized in that: The hyperbranched polyurethane microcapsules are prepared by the following method: A. Pentaerythritol, toluene diisocyanate and a catalyst are mixed and reacted at 60 - 80°C for 2 - 4 h to obtain a hyperbranched polyurethane prepolymer; B. The fluoroacrylate monomer, benzophenone and the hyperbranched polyurethane prepolymer are mixed, and then acetone is added to dissolve them to form an oil phase. Then, an emulsifier and water are added to the oil phase, and the mixture is stirred at a speed of 1000 - 2000 r / min for 30 - 60 min to obtain an emulsion; C. Diethanolamine is added to the emulsion, and then the reaction is carried out at 50 - 70°C for 3 - 5 h. After the reaction, impurities in the system are removed by vacuum distillation, and then the microcapsules are separated by centrifugation. Then, the microcapsules are washed and dried to obtain hyperbranched polyurethane microcapsules.

5. The polyamide industrial yarn for highly wear-resistant marine cable according to claim 4, characterized in that: In step A, the mass ratio of pentaerythritol, toluene diisocyanate and the catalyst is 1:(3 - 5):(0.01 - 0.03).

6. The polyamide industrial yarn for highly wear-resistant marine cable according to claim 4, characterized in that: The catalyst in step A is dibutyltin dilaurate.

7. The polyamide industrial yarn for high-wear-resistant marine cable according to claim 4, characterized in that: In step B, the mass ratio of the fluoroacrylate monomer, benzophenone and the hyperbranched polyurethane prepolymer is 1:(0.1 - 0.3):(3 - 5).

8. A polyamide industrial yarn for highly wear-resistant marine ropes according to claim 4, characterized in that: The fluoroacrylate monomer in step B is preferably ethyl trifluoromethylacrylate.

9. A preparation method of nylon industrial yarn for highly wear-resistant marine cable according to any one of claims 1-8, characterized in that, It includes the following steps: S1. The modified polyamide 6 chips, nano - ceramic particles, polytetrafluoroethylene, molybdenum disulfide nanosheets and dispersant are added to a high - speed mixer according to the ratio and mixed at a speed of 800 - 1200 r / min for 15 - 25 min to obtain a premix; S2. The premix, hyperbranched polyurethane microcapsules and compatibilizer are added to a twin - screw extruder and melt - blended at a temperature of 240 - 260°C, and the screw speed is controlled at 300 - 400 r / min, and then pelletized to obtain a spinning masterbatch; S3. Put the spinning masterbatch into a spinning machine and carry out spinning at a spinning temperature of 250 - 270 °C. Set the spinning speed at 1000 - 1500 m / min. After cooling, stretching, and winding processes, finally produce polyamide industrial yarn for highly wear-resistant marine cables.

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