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KR-20260067504-A - Nylon-modified thermoplastic elastomer composition and Polar operating ship cable sheathed therewith, with enhanced durability and self-lubrication

KR20260067504AKR 20260067504 AKR20260067504 AKR 20260067504AKR-20260067504-A

Abstract

The present invention relates to a nylon-modified thermoplastic elastomer composition and a polar navigation ship cable coated therewith with enhanced durability and self-lubrication. More specifically, the invention provides a nylon-modified thermoplastic elastomer composition and a polar navigation ship cable coated therewith with enhanced durability and self-lubrication, which improves self-lubrication, durability, heat resistance, oil resistance, and mechanical properties, enables low hardness, and additionally reduces construction efficiency and costs.

Inventors

  • 정영섭

Assignees

  • (주)인테크놀로지

Dates

Publication Date
20260513
Application Date
20241105

Claims (5)

  1. In a reactor equipped with a stirrer, a temperature controller, and a condenser, while supplying and discharging a purge gas selected from neon, argon, nitrogen, or hydrogen gas at a rate of 1 to 3 L/hour, 10,000 parts by weight of distilled water and succinic acid, oxalic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, suberic acid, sebaic acid, 1,10-decanedicarboxylic acid, and 1,11-undecanedicarboxylic acid 12,000 to 16,000 parts by weight of a diacid selected from (1,11-undecanedicarboxylic acid), 1,12-dodecanedicarboxylic acid, and benzene diacetic acid, norbornane dimethylamine or 1,3-bis(aminomethyl)benzene, 1,4-bis(aminomethyl)benzene, 2,5-bis(aminomethyl)benzene, 1,3-bis(aminomethyl)benzene, 1,4-bis(aminomethyl)benzene, A diamine selected from 2,5-bis-aminomethylcyclohexane [2,5-bis(aminomethyl)benzene], 1,3-bis(aminophenoxy)benzene [1,3-bis(4-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene], and 2,5-bis(aminophenoxy)benzene [2,5-bis(4-aminophenoxy)benzene], 12,000 to 15,500 parts by weight, ethyl hypophosphite or hypophosphorous acid, phenylmethylphosphinic acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, and magnesium 10 to 40 parts by weight of a reaction catalyst selected from magnesium hypophosphite and calcium hypophosphite, and 1 to 15 parts by weight of a regulator selected from lithium hydroxide or metal compounds among sodium hydroxide, potassium hydroxide, lithium acetate, sodium acetate, potassium acetate, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, and sodium carbonate are added and sealed. A polyamide oligomer manufacturing step comprising: raising the reactor temperature to 180–240°C while stirring at a speed of 50–500 RPM and adjusting the internal pressure of the reactor to 15–30 atmospheres to react for 30–240 minutes; after the reaction is finished, stopping the stirring, opening the bottom drain valve to atmospheric pressure to remove the reaction mixture, filtering it, and then drying it using a vacuum drying oven at 130–170°C for 4–24 hours to manufacture a polyamide oligomer; 1,000 parts by weight of a polyolefin resin selected from high-density polyethylene, medium-density polyethylene, linear low-density polyethylene, and low-density polyethylene, or selected from polypropylene and polybutene, and 10,000 to 20,000 parts by weight of an aromatic solvent selected from benzene, toluene, monochlorobenzene, and xylene are introduced into a reactor equipped with a stirrer and a temperature controller, and the polyolefin resin is completely dissolved while stirring at a speed of 50 to 500 RPM and acrylic anhydride or methacrylate A polyolefin grafting step of preparing a polyolefin graftmer by adding 40 to 150 parts by weight of an anhydride monomer selected from methacrylic anhydride and maleic anhydride, and 20 to 150 parts by weight of an organic peroxide selected from benzoyl peroxide, dichlorobenzoyl peroxide, and dicumyl peroxide, performing graft polymerization, then cooling and recrystallizing the reaction mixture and drying at 60 to 100°C for 12 to 48 hours; In a mixer selected from a kneader mixer, a Banbury mixer, or an extruder, 100,000 parts by weight of the polyolefin graftmer prepared in the polyolefin grafting step, 1,000 to 10,000 parts by weight of the polyamide oligomer prepared in the polyamide oligomer preparation step, and phthalimide, N-acetoxy-phthalimide, N-(5-amino-4-cyano-1-pyrazolyl)phthalimide, N-(4-homoadamantyl)phthalimide, N-(N-morpholindithio)phthalimide A nylon modification step of adding 1,000 to 5,000 parts by weight of a reaction accelerator selected from phthalimide compounds and kneading at a temperature of 80 to 200°C for 20 to 120 minutes, and then transferring the resulting dough mass to a single-screw or twin-screw extruder to produce nylon-modified elastomer pellets of size 2 to 5 mm through extrusion molding; In a continuous flow reactor equipped with a stirrer and temperature controller, while continuously supplying and discharging purge gas at a rate of 1–10 L/hour, a polymerization solvent selected from hexane, heptane, octane, nonane, or decane at a rate of 20,000–25,000 g/hour, ethene at a rate of 1,000–4,000 g/hour, or an alkene monomer selected from linear alkenes among butene, pentene, hexene, octene, and nonene at a rate of 100–1,000 g/hour is supplied, along with bis(indenyl)hafnium dichloride or bis(isopropylcyclopentadienyl)hafnium Dichloride [bis(isopropylcyclopentadienyl)hafnium dichloride], bis(2-methyl-4,5,6,7-tetrahydroindenyl)hafnium dichloride [bis(2-methyl-4,5,6,7-tetrahydroindenyl)hafnium dichloride], racemic-ethylenebis(indenyl)hafnium dichloride [rac ethylenebis(indenyl)hafnium dichloride], racemic-[ethylenebis(2-(tert-butyldimethylsiloxy)indenyl)]hafnium dichloride {rac [ethylenebis(2-(tert-butyldimethylsiloxy)indenyl)]hafnium dichloride}, racemic-dimethylsilanediylbis(2-methyl-4-(1-naphthyl)indenyl)hafnium dichloride [rac-dimethylsilanediylbis(2-methyl-4-(1- Polymerization catalyst selected from rac-dimethylsilanediylbis[2-methyl-4-(1-naphthyl)indenyl]hafnium dichloride], racemi-dimethylsilanediylbis[2-methyl-4-(1-naphthyl)indenyl]hafnium dichloride, racemi-dimethylsilanediylbis[2-methyl-4-(1-naphthyl)-4,5,6,7-tetrahydroindenyl]hafnium dichloride, 0.01–0.2 mmol/hour and methylaluminoxane, methylisobutylalumoxane A copolymer manufacturing step comprising: introducing an auxiliary catalyst selected from organoaluminoxanes at a rate of 0.01 to 1.2 mmol/hour to carry out a polymerization reaction for 4 to 24 hours while maintaining a reactor pressure of 1.2 to 2.4 atms and a temperature of 80 to 110℃; after the reaction is completed, adding alcohol to the polymerization solution extracted from the bottom of the continuous reactor to terminate the reaction mixture, treating the reaction mixture by steam stripping to separate the copolymer from the solvent, and then drying the copolymer under reduced pressure at 60 to 100℃ for 12 to 48 hours; In a mixing mixer such as a ribbon, kneader, Henschel, or Banbury, 100,000 parts by weight of polyethylene resin, 100,000 to 180,000 parts by weight of a copolymer prepared in the copolymer manufacturing step, 1,500 to 100,000 parts by weight of an ethylene block copolymer selected from ethylene-propylene block copolymer, ethylene-butene block copolymer, ethylene-hexene block copolymer, and ethylene-octene block copolymer, 50,000 to 130,000 parts by weight of a nylon-modified elastomer prepared in the nylon modification step, and silane or fatty acid 400,000 to 950,000 parts by weight of a metal hydrate flame retardant selected from surface-treated magnesium hydroxide phosphate, aluminum hydroxide, or magnesium hydroxide, and in the polysiloxane copolymer of a poly(dimethylsiloxane)-poly(ethylene oxide) copolymer, a poly(dimethylsiloxane)-poly(propylene oxide) copolymer, a poly(dimethylsiloxane)-poly(butylene oxide) copolymer, or a poly(dimethylsiloxane)-poly(phenylene oxide) copolymer. 14,000 to 36,000 parts by weight of a selected auxiliary flame retardant, 10,000 to 32,000 parts by weight of a silane selected from tetramethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, tetraethoxysilane, and methyltriethoxysilane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]{pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]}, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione[1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione], 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol)[4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol)], 3,000 to 12,000 parts by weight of an antioxidant selected alone or in two or more of 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene; 14,000 to 22,000 parts by weight of a pigment selected alone or in two or more of iron oxide, carbon black, and titanium dioxide; and calcium stearate or magnesium A nylon-modified thermoplastic elastomer composition characterized by being manufactured through a step of manufacturing a nylon-modified thermoplastic elastomer composition in which 800 to 5,400 parts by weight of a lubricant selected from metal stearates among magnesium stearate, sodium stearate, and zinc stearate are sequentially added and melt-mixed for 10 to 60 minutes at a temperature of 80 to 140°C to produce a nylon-modified thermoplastic elastomer composition, a lump dough produced through this step is transferred to a single-screw or twin-screw extruder to produce composition pellets of a size of 2 to 5 mm through extrusion molding, and then dried in an oven at 60 to 80°C and subjected to a pelletizing and sorting step to sort the particle size.
  2. A cross-linked insulating composition manufacturing step for manufacturing cross-linked insulating composition pellets; An insulated wire manufacturing step for manufacturing an insulated wire having an insulating layer formed thereon by subjecting the cross-linked insulating composition pellets manufactured in the above cross-linked insulating composition manufacturing step to an extrusion vulcanization step; A multiply wire manufacturing step for manufacturing a multiply wire by stranding the insulated wires manufactured in the above insulated wire manufacturing step using a multiply wire assembly machine; A joint shielding layer forming step of forming a combined wire having a joint shielding layer formed by passing the combined wire manufactured in the above combined wire manufacturing step and a filler together, and taping the outer circumference with a metal tape or a metal coating film, or braiding with a metal wire, a metal-plated wire, or an alloy wire; A taping step of passing the combined wire with the joint shielding layer formed thereon, manufactured in the joint shielding layer formation step, through the taping column of a cable taping machine and taping it with a binder tape selected from polymer tapes; An inner coating layer forming step in which the nylon-modified thermoplastic elastomer composition obtained in claim 1 is extruded at a speed of 5 to 50 kg/hour in an extruder having a molding die attached to the outer circumference of an insulated wire having a binder tape layer formed in the above taping step to form an inner coating layer; An external reinforcement layer forming step in which a single to two or more types of metal wires, inorganic fiber yarns, or aramid fiber yarns are combined and braided to form a reinforcement layer on the outer circumference of an insulated wire having an internal coating layer formed in the above internal coating layer forming step; A polar navigation ship cable with reinforced durability and self-lubricating properties coated with a nylon-modified thermoplastic elastomer composition, characterized by being manufactured through an external coating layer formation step in which the nylon-modified thermoplastic elastomer composition obtained in claim 1 is extruded at a speed of 5 to 50 kg/hour in an extruder having an extrusion molding die attached to the outer circumference of an insulated wire having a reinforcing layer formed in the above external reinforcing layer formation step to form an external coating layer.
  3. Steps for manufacturing a cross-linked semiconducting composition; A step for manufacturing an insulated wire with a semiconducting layer formed thereon, which manufactures an insulated wire with a semiconducting layer formed thereon through an extrusion vulcanization step; A shielding layer forming step in which a shielding layer is formed by taping the outer circumference of an insulated wire having a semiconducting layer formed in the above-mentioned insulated wire manufacturing step with a semiconducting layer, using a metal tape or a metal coating film, or by braiding it with a metal wire or metal wire; A taping step of passing an insulated wire with multiple combined shielding layers and a filler together through the taping column of a cable taping machine and taping them with binder tape; An inner coating layer forming step in which the nylon-modified thermoplastic elastomer composition obtained in claim 1 is extruded at a speed of 5 to 50 kg/hour in an extruder having a molding die attached to the outer circumference of an insulated wire having a binder tape layer formed in the above taping step to form an inner coating layer; An external reinforcement layer forming step in which a single to two or more types of metal wires, inorganic fiber yarns, or aramid fiber yarns are combined and braided to form a reinforcement layer on the outer circumference of an insulated wire having an internal coating layer formed in the above internal coating layer forming step; A polar navigation ship cable with reinforced durability and self-lubricating properties coated with a nylon-modified thermoplastic elastomer composition, characterized by being manufactured through an external coating layer formation step in which the nylon-modified thermoplastic elastomer composition obtained in claim 1 is extruded at a speed of 5 to 50 kg/hour in an extruder having an extrusion molding die attached to the outer circumference of an insulated wire having a reinforcing layer formed in the above external reinforcing layer formation step to form an external coating layer.
  4. In paragraph 2, The step of manufacturing the above-mentioned cross-linked insulating composition comprises, in a mixing mixer among a kneader, Henschel, or Banbury, 100,000 parts by weight of an ethylene polymer or ethylene copolymer selected from polyethylene, ethylene-propylene copolymer, or ethylene-propylene-diene copolymer; 60,000 to 100,000 parts by weight of a metal hydrate flame retardant surface-treated with silane or fatty acid; 100 to 12,000 parts by weight of a reinforcing agent selected from silica, carbon black, magnesium carbonate, aluminum silicate, magnesium silicate, and diatomaceous earth; and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydrooxyphenyl)propionate][thiodiethylene 50 to 200 parts by weight of an antioxidant, used alone or in a mixture of two or more types selected from [bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodipropionic acid dioctadecyl ester, distearyl thiodipropionate, and sulfur compounds in 3-mercaptopropionic acid, and 100 to 1,200 parts by weight of a metal stearate activator are sequentially added, and a dough is kneaded at a temperature of 80 to 130°C for 5 to 60 minutes. The resulting mixture is then transferred to a single-screw or twin-screw extruder to produce insulating composition pellets with a size of 3 to 5 mm through extrusion molding. The insulating composition pellets and organic peroxide or A method for preparing by adding 1,000 to 20,000 parts by weight of a crosslinking agent selected from irradiation crosslinking agents and mixing at a temperature of 60 to 100°C for 10 to 60 minutes; The above-mentioned insulated wire manufacturing step involves feeding the cross-linked insulation composition pellets produced in the cross-linked insulation composition manufacturing step into a hopper, and then passing a conductor made of a metal wire, metal-plated wire, or metal alloy wire through the head of an extruder equipped with an extrusion die, while vulcanizing the conductor at a speed of 10–40 kg/hour under temperature conditions where Cylinder 1 is 100–120°C, Cylinder 2 is 100–120°C, Cylinder 3 is 105–125°C, the extrusion head is 110–130°C, and the extrusion die is 110–130°C; at this time, the vulcanization method involves passing the conductor through a continuous vulcanization pipe maintained at 80–120°C and 10–20 atmospheres at a speed of 20–50 m/min, or Irradiated with an electron beam of 1~20 Mrad; The above-mentioned joint shielding layer forming step is characterized by forming a combined wire with a joint shielding layer by passing a filler made of a polymer fiber yarn composed of polypropylene or nylon, which serves to maintain the concentricity of the bundled wire and the insulated wire manufactured in the bundled wire manufacturing step of the process flow diagram, together with the wire, and taping the outer periphery with a metal tape or metal coating film, or braiding it with a metal wire, metal-plated wire, or alloy wire. This describes a polar navigation ship cable coated with a nylon-modified thermoplastic elastomer composition that has reinforced durability and self-lubrication.
  5. In paragraph 3, The step of manufacturing the above cross-linked semiconducting composition involves sequentially adding 10,000 parts by weight of an ethylene copolymer, 500 to 2,000 parts by weight of an electro-conductive filler selected from electro-conductive carbon black, carbon nanotubes, graphite, and graphene, 43 to 64 parts by weight of an antioxidant, and 25 to 40 parts by weight of a metal stearate activator into a mixing mixer such as a kneader, Henschel, or Banbury, and mixing the mixture for 10 to 60 minutes at a temperature of 100 to 140°C. The resulting dough is then transferred to a single-screw or twin-screw extruder to produce semiconducting elastomer pellets of size 3 to 5 mm with a surface resistance of 10⁵ to 10⁸ Ω through extrusion molding. A method for producing cross-linked semiconducting composition pellets by adding 10,568 to 12,104 parts by weight of the above semiconducting elastomer pellets and 95 to 150 parts by weight of an organic peroxide to a separate mixing mixer such as a kneader, Henschel, or Banbury, and kneading at a temperature of 60 to 100°C for 10 to 60 minutes; A polar navigation cable reinforced with durability and self-lubricating properties, coated with a nylon-modified thermoplastic elastomer composition, characterized in that the filler in the above taping step maintains the concentricity of the insulated wire, acts as a waterproofing agent, and is made of a non-hygroscopic inorganic fiber yarn or polymer fiber yarn.

Description

Nylon-modified thermoplastic elastomer composition and Polar operating ship cable sheathed therewith, with enhanced durability and self-lubrication The present invention relates to a nylon-modified thermoplastic elastomer composition and a polar navigation ship cable coated therewith with enhanced durability and self-lubricity. More specifically, the invention relates to a nylon-modified thermoplastic elastomer composition and a polar navigation ship cable coated therewith with enhanced durability and self-lubricity, which improves self-lubricity, durability, heat resistance, oil resistance, and mechanical properties, enables low hardness, and additionally reduces construction efficiency and costs. Electric cables enable the transmission of power and electrical signals from one device to another, and there is a growing demand for lightweight, flexible, and high-efficiency electric cables in the shipbuilding industry. In addition, they must not contain halogen elements and must be flame-retardant and self-extinguishing. Electric cables are used to transmit communication signals and electricity to equipment and machinery in polar icebreakers and drilling rigs. They must be able to stably transmit current even under extremely low temperatures of minus 60°C and must not crack even when subjected to external impact or bending. Consequently, the market for cable sheath materials for special vessels is advancing globally due to the expansion of high-value-added special-purpose ship types. Cables used in ships equipped with crude oil and gas production facilities or special polar vessels must be made of materials that are resistant to heat, oil vapors, and ozone generated under the ship's deck while maintaining cold flexibility even in extreme marine environments such as the polar regions. Thermoplastic elastomers are considered one of the most versatile plastics on the market due to their design and manufacturing flexibility. Combining the processing advantages of thermoplastic resins with the performance characteristics of elastomers, thermoplastic elastomers can be processed relatively easily using thermoplastic methods such as extrusion and injection molding. Therefore, vulcanization, a time-intensive rubber processing method, is not required, and in addition, thermoplastic elastomers possess high elastic properties due to the characteristics of their molecular structure, which consists of crystalline and amorphous domains. These may be physical blends or alloys of crystalline and amorphous polymers, or block copolymers in which crystalline and amorphous domain blocks are chemically bonded in a polymer chain. Here, the hard block imparts plastic properties to the final product, including material characteristics such as easy processing, heat resistance, tear and tensile strength, or chemical resistance to the thermoplastic elastomer, while the soft block imparts elastomer or elastic properties such as hardness, flexibility, or extent of permanent deformation. Nylon resin is a crystalline resin with a low coefficient of friction and excellent wear resistance, self-lubrication, and electrical insulation properties, and can be reactively blended or compounded with maleic anhydride-containing copolymers. In particular, when nylon resin is introduced as a hard block of an olefin-type thermoplastic elastomer, improvements in properties such as durability, self-lubrication, and heat resistance are expected. However, regarding the development of thermoplastic olefin materials based on such reactive compounding technology, most foreign countries have secured technological competitiveness and preempted the relevant market. Consequently, the market entry barriers perceived by domestic compounding companies are relatively high, making the development of core technologies in this field urgent within Korea. Accordingly, there is an urgent need to develop an olefin-type thermoplastic elastomer composition for cable insulation sheathing with excellent flexibility, durability, self-lubricity, and flame retardancy, as well as cables for polar-operating vessels utilizing this composition. To improve these characteristics, the prior art and patent literature developed and patented to date are as follows. FIG. 1 is a process flow diagram illustrating a method for implementing a nylon-modified thermoplastic elastomer composition of the present invention. FIG. 2 is a process flow diagram illustrating a method of implementing a polar navigation vessel cable according to the present invention. FIG. 3 is a process flow diagram illustrating a method of implementing a cable for a polar navigation vessel according to another aspect of the present invention. The present invention, which best meets the above objectives and features, will be described in detail below with reference to the drawings illustrating the process flow of an embodiment. If we look at the implementation according to the process flow of Fig. 1, In a reactor equipped wit