KR20230157190A - Cold-resistant and high-flammability polymer composite using siloxane-modified thermoplastic elastomer and thereof sheathed electric cable for vessels operating in ice-covered waters - Google Patents

Abstract

The present invention maximizes the dispersion characteristics of inorganic fillers to provide excellent flexibility and cold resistance without deteriorating flame retardancy even when minimizing the content of flame retardants when mixing thermoplastic cold-resistant and highly flame-resistant polymer composites, as well as electrical, This relates to a cold-resistant, high-flammability polymer composite using siloxane-modified thermoplastic elastomer that can improve mechanical and chemical properties, and a polar shipping cable coated with the same.
Therefore, the present invention adjusts the types of resins, additives, and fillers used in the insulation coating composition of each component and their usage amounts, thereby improving flexibility, cold resistance, oil resistance, flame retardancy, and resistance compared to the insulation coating composition of a conventional polar shipping cable. By improving icing properties, when applied to polar ships, constructability and productivity can be improved in addition to electrical, mechanical, and chemical properties.

Description

Siloxane-modified thermoplastic elastomer, cold-resistant and high-flammability polymer composite using the same, polar operating ship cable coated with the same, and method of manufacturing the same {Cold-resistant and high-flammability polymer composite using siloxane-modified thermoplastic elastomer and its sheathed electric cable for vessels operating in ice-covered waters}

The present invention relates to a siloxane-modified thermoplastic elastomer, a cold-resistant, high-flammability polymer composite using the same, a polar sailing ship cable coated with the same, and a method of manufacturing the same. More specifically, it relates to a method for manufacturing the same by maximizing the dispersion characteristics of the inorganic filler when mixing the thermoplastic elastomer composition. A siloxane-modified thermoplastic elastomer that has excellent flexibility and cold resistance without deteriorating flame retardancy even when the content of flame retardants is minimized, and can improve electrical, mechanical, chemical properties and productivity when applied as an insulating coating for polar ship cables. Cold resistance and high flame resistance using this elastomer. It relates to a polymer composite, a polar navigation ship cable coated therewith, and a method of manufacturing the same.

There is a tendency for crude oil development offshore plant facilities to increasingly move to polar regions due to limitations in drilling areas, and there have been technical attempts to improve this as they have vulnerabilities in cold resistance below -40℃.

Recently, in the polar waters of the North and South Poles, the sea ice area has expanded due to global warming and the sea ice season in which navigation without icebreakers can be carried out has become longer, increasing the possibility of using the Northern Sea Route.

As such, the decrease in Arctic sea ice area is having a significant impact on the global environmental system, but in terms of the shipbuilding and marine industry, the opening of the Northern Sea Route in the summer can lead to demand for new ice-sea ships or polar marine plants, providing new opportunities.

In line with this, demand for container ship transportation is increasing to shorten the route between Asia and Europe. Transportation of underground resources such as oil and liquefied natural gas (LNG) is also being actively carried out.

For example, when using the Arctic route, the sailing distance between Korea (Busan) and Europe (Rotterdam) is shortened by up to 32% and sailing days by up to 10 days compared to the existing route via the Suez Canal, significantly reducing the sailing period and cost. do.

In particular, as the Polar Code went into effect in January 2017, all newly built ships are subject to the Polar Code, and interest in the safety of ships operating in polar regions is also increasing, and cold weather technology ( Winterization is also increasingly considered a very important issue from the perspective of ship design and operation.

Accordingly, the demand for cables that can withstand extreme temperatures is increasing, and the level of technology requirements is also increasing.

The polymer material for flame retardant wires that is mainly used in offshore plant equipment is the crosslinked polyolefin series because it is economical and stable.

Polyvinyl chloride cannot be halogen-free by itself, and chemical cross-linking is not possible with polypropylene. Moreover, companies that can manufacture these polymer materials are specialized in the characteristics of the extrusion equipment currently used by wire companies, so there is a need to select the most widely used polymer materials and develop technology.

Cables are used to transmit communication signals and electricity to devices and equipment in polar icebreakers and drilling facilities. They must stably transmit current even in cryogenic conditions of -70°C and must not crack even when subjected to external shocks or bending.

Therefore, the market for cable sheath materials for special ships is advancing as the types of high-value-added special-purpose ships expand around the world. Cables used on ships equipped with crude oil and gas production facilities or special ships for polar regions maintain cold flexibility even in extreme marine environments such as polar regions and are highly resistant to heat, oil vapor, and ozone generated from the lower part of the ship deck. Material is essential.

In addition, since a fire on board a ship is directly linked to a large-scale accident, the requirements for fire safety are particularly strict for ship materials. In the event of a fire, smoke generation should be minimized, and halogens or corrosive gases that cause significant damage to machines and people should not be generated.

However, in the case of most of these technologies, technological competitiveness is secured overseas and the related markets are occupied first, so the market entry barriers felt by domestic shipyards and equipment companies are relatively high, and there is an urgent need to develop core technologies in related fields domestically.

In addition, since wire manufacturers have been improving productivity by extruding cables at as high a speed as possible, insulation coating materials for cables must satisfy both the above physical properties and extrusion processability.

Accordingly, there is an urgent need for the development of cable insulation coating compositions with excellent flexibility, cold resistance, and flame retardancy, as well as cables for polar navigation ships using the same.

In order to improve these characteristics, the prior art and patent documents that have been developed and patented so far are examined as follows.

Republic of Korea Patent Publication No. 1020150090358 discloses a composition consisting of 150 to 200 parts by weight of an inorganic flame retardant, 5 to 10 parts by weight of a flame retardant auxiliary, 20 to 30 parts by weight of a plasticizer, and 5 to 10 parts by weight of a crosslinking agent per 100 parts by weight of the base resin. By cross-linking the conductor or insulator through a cross-linking method, it can be used up to -60°C, so it can be used even in polar regions. It is manufactured through a peroxide cross-linking method to simplify the manufacturing process and reduce manufacturing costs. Optical cable is provided. Republic of Korea Patent No. 101716231 discloses a method of producing a polyketone solution from carbon monoxide, ethylene and propylene copolymers, polyketone fibers with excellent strength from the polyketone solution, and a polyketone cryogenic insulation material containing the same. Republic of Korea Patent No. 101792609 is a cold-resistant vessel in which the inner sheath and outer sheath are made of low smoke zero halogen (LSHZ) material, and the cable's physical properties and usage characteristics are continuously maintained even in extremely low temperatures below -65℃. A method of manufacturing a marine power cable is disclosed. Republic of Korea Patent Publication No. 1020190141387 has cold resistance of -40℃, while oil resistance and chemical resistance, which are trade-offs, are not reduced, and mechanical properties are excellent, and despite the use of non-halogenated flame retardants, Provided is a non-halogen-based sheath composition that is excellent in flame retardancy and environmental friendliness, and has excellent processability as well as cold resistance and oil resistance, and a cable including a sheath layer formed therefrom. Republic of Korea Patent Publication No. 1020190055932 provides an insulating composition with excellent cold resistance and flexibility and a cable including an insulating layer formed therefrom. According to the above invention, it is possible to easily manufacture an insulating composition that not only has excellent oil resistance, heat resistance, cold resistance, and flexibility, which are difficult to secure at the same time, but is also environmentally friendly and has excellent processability, and a cable including an insulating layer formed therefrom. . Republic of Korea Patent No. 100644490 discloses 100 parts by weight of a base resin containing 5 to 80 parts by weight of chlorosulfonated polyethylene and 30 to 90 parts by weight of ethylene vinyl acetate copolymer with a vinyl acetate content of 28 to 80% by weight; As a flame retardant, 30 to 150 parts by weight of metal hydroxide; 1 to 30 parts by weight of cold-resistant plasticizer; 0.5 to 10 parts by weight of a silane-based coupling agent; 0.5 to 8 parts by weight of cross-linking aid; and 3 to 20 parts by weight of a cross-linking agent. A flame-retardant wire covering material composition comprising the same and a marine cable using the same are provided. The flame-retardant wire covering material composition according to the above invention not only has excellent durability against oil components without deteriorating mechanical properties, and has cold resistance that can withstand even -40°C, but also emits toxic gases in the event of a fire. There is an advantage in providing a wire covering material composition that minimizes this and has excellent flame retardancy and a marine cable using the same. Republic of Korea Patent No. 100745170 is a composite insulating fiber made by mixing para-aramid fiber, silica fiber, and Teflon fiber, a fluorine fiber, and is non-asbestos. It maintains the properties of the fiber over a long period of time at both high and low temperatures, and has fire resistance and Provides a composite fiber using heat- and cold-resistant composite fiber yarns that not only have good insulation properties, but also have excellent non-adhesion, low coefficient of friction, oiliness, electrical properties, and chemical resistance, and a method for manufacturing the same. Republic of Korea Patent No. 101457612 provides a halogen-free polymer resin composition and a polymer resin material manufactured using the composition, particularly cables for ships or drillships. The polymer resin material manufactured using the composition according to the above invention maintains flexibility even at a low temperature of -40°C, has flame retardancy that satisfies the standard characteristics of general marine cables, and has oil resistance that can be used inside marine structures such as oil drilling ships and oil drilling structures. Or, it satisfies the standard characteristics for use in drill ships. Republic of Korea Patent No. 101535079 uses magnesium hydroxide instead of environmentally hazardous substances such as antimony, bromine, and chlorine, which are previously used as flame retardants, so it is environmentally friendly and has excellent flame retardant properties, and uses polypropylene and high-density polyethylene to improve tensile strength and As mechanical strength improves, mechanical properties such as durability and wear resistance improve, and by realizing cross-linking between molecules, it is resistant to scratches and has strong vibration resistance, and can prevent destruction and thermal deformation due to temperature. By realizing cross-linking, it is strong against scratches and has strong vibration resistance, and can prevent destruction and thermal deformation due to temperature, so it is applied to insulating materials required for manufacturing wires, power lines, communication lines, and cables, and can be used in extreme and high-temperature environments. It can be used as automotive wire materials, interior materials for cars such as artificial leather and fillers, and wire materials for ships that require vibration and durability, including PO (Poly Olefin), TPE (Thermo Plastic Elastomer), TPU (Thermoplastic Poly Urethane), and TPR. Provides a TOE flame retardant resin composition that can secure flame retardancy by being used as a flame retardant material in (Thermo Plastic Rubber), TPO (Thermo Plastic Olefin), and TPEE (Thermoplastic Polyether Ester Elastomer), and a manufacturing method thereof. Republic of Korea Patent No. 100874990 relates to a composite resin composition for covering cables that is resistant to solvents contained in paint and has excellent cold resistance, oil resistance, abrasion resistance, and tear resistance characteristics. Specifically, it is compatible with polyvinyl chloride (PVC). Thermoplastic polyurethane elastomer (TPU), which has excellent properties and chemical resistance, is alloyed with polyvinyl chloride (PVC), and more preferably, maleic anhydride-modified ethylene vinyl acetate (EVA-g-MAH) is used as a compatibilizer. By containing a surface-modified inorganic flame retardant or a mixture thereof, it completely improves the phenomenon of rapid decline in elongation retention after aging due to degradation of the polymer molecular chain by paint or solvent, and improves cold resistance, oil resistance, abrasion resistance, and tear resistance. An excellent composite resin composition for covering cables with properties comparable to those of cross-linked rubber is provided. Republic of Korea Patent Publication No. 1020190022909 provides a crosslinkable polymer composition for use as a sheath layer of a cable and a cable comprising a crosslinked layer obtained from the composition. The crosslinkable polymer composition according to the present invention is characterized by comprising ethylene vinyl acetate copolymer and ethylene methyl acrylate copolymer, flame retardant filler and crosslinking agent.

Accordingly, the technical problem to be achieved by the present invention is to solve the above-mentioned needs, and the purpose of the present invention is to provide a cold-resistant, highly flame-resistant polymer composite using a siloxane-modified thermoplastic elastomer and a polar navigation ship cable coated with the same.

The present invention for achieving the above object is to mix α,ω-hydrogensiloxane (α) in a reactor equipped with a stirrer, temperature controller, dropping funnel, and condenser. After administering 1,000 parts by weight of ω-hydrogensiloxane, the reactor temperature was raised to 60-100°C while stirring at a speed of 100-500 RPM, then 0.002-2.0 parts by weight of catalyst was added, and allyl glycidyl ether (allyl) was added. 20 to 200 parts by weight of glycidyl ether) was supplied through a dropping funnel mounted on the reactor for 10 to 60 minutes while maintaining the temperature of the reactor at 60 to 100°C and allowing the reaction to proceed for 60 to 240 minutes. Then, alcohol ( After adding 1,000 parts by weight of alcohol and 100 to 400 parts by weight of amino polyalkylene oxide, the temperature of the reactor was maintained at 60 to 100°C and the reaction proceeded for 60 to 240 minutes while stirring at a speed of 100 to 500 RPM. , a siloxane-modified thermoplastic elastomer manufacturing step of vacuum drying the obtained polymer solution to produce a siloxane-modified thermoplastic elastomer;

A purge gas is continuously supplied and discharged at a rate of 0.5 to 8 L/hour to a flow reactor equipped with a stirrer and a temperature controller, while discharging 20,000~20,000 polymerization solvent. Supplying at a rate of 25,000g/hour, ethene 2,000~4,000g/hour, alkene monomer 1,000~3,000g/hour, polymerization catalyst selected from zirconium compound 0.01~ The polymerization reaction was carried out for 4 to 20 hours while maintaining the reactor pressure at 1.5 to 2 atm and the temperature at 80 to 110°C by adding 0.1 mmol/hour and cocatalyst at a rate of 0.10 to 0.50 mmol/hour, and then performing the above continuous reaction. The reaction was terminated by adding alcohol to the polymerization reaction solution extracted from the bottom of the reactor. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then decompressed at 60 to 100°C for 12 to 48 hours. A polyolefin elastomer manufacturing step of manufacturing a polyolefin elastomer by drying under low temperature;

1,000 parts by weight of aromatic solvent and 100 to 500 parts by weight of polyolefin resin were administered while circulating nitrogen in a reactor equipped with a stirrer, temperature controller, and nitrogen purging equipment. Then, the reactor temperature is raised to 80-150°C and stirred at a speed of 100-500 RPM. When the polyolefin resin is completely dissolved, acrylic anhydride or methacrylic anhydride is added to the reactor. Add 1 to 15 parts by weight of anhydride selected from anhydride, maleic anhydride, etc. and 1 to 15 parts by weight of peroxide compound, cool and recrystallize the mixture reacted for 1 to 3 hours. A compatibilizing agent manufacturing step of manufacturing a compatibilizing agent;

100,000 parts by weight of polyethylene resin in a mixing mixer and 100,000 to 180,000 parts by weight of polyolefin elastomer manufactured in the polyolefin elastomer manufacturing stage, with a glass transition temperature of -65°C or lower and a tensile strength of 3 to 5 MPa. 200,000 to 500,000 parts by weight of ethylene-octene block copolymer, 60,000 to 100,000 parts by weight of compatibilizer prepared in the compatibilizer manufacturing stage, metal oxide surface treated with silane or fatty acid. 400,000 to 800,000 parts by weight of flame retardant, 10,000 to 40,000 parts by weight of siloxane-modified thermoplastic elastomer manufactured in the siloxane-modified thermoplastic elastomer manufacturing stage, 3,000 to 15,000 parts by weight of silane, 12,000 to 35,000 parts by weight of polysiloxane, Antioxidant 5,000~ 9,000 parts by weight, 10,000 to 40,000 parts by weight of pigment, and 1,500 to 4,000 parts by weight of lubricant are sequentially added and melt-mixed at a temperature of 80 to 170°C for 10 to 60 minutes to form a lump of dough using a single-screw or twin-screw extruder. Manufacturing of a cold-resistant, highly flammable polymer composite by transporting it to a 2-5mm-sized composition pellet through extrusion molding, drying it in an oven at 60-80°C, and going through a particle size selection process to produce a cold-resistant, highly flammable polymer composite. Steps and;

In a mixing mixer such as Kneader, Henschel, or Banbury, 100,000 parts by weight of ethylene polymer or ethylene copolymer, 60,000 to 100,000 parts by weight of metal oxide flame retardant surface-treated with silane or fatty acid, and 100 to 12,000 parts by weight of reinforcing agent. parts, 50 to 200 parts by weight of antioxidant, and 100 to 1,200 parts by weight of lubricant are sequentially administered and kneaded for 5 to 60 minutes at a temperature of 80 to 130°C. The lump dough is transferred to a single-screw or twin-screw extruder and extruded into 3 to 5 mm sizes. manufacturing insulating composition pellets; manufacturing insulating composition pellets;

In a separate mixing mixer such as Kneader, Henschel, Banbury, etc., 100,000 parts by weight of the insulating composition pellets and 1,000 parts by weight of a crosslinking agent selected from organic peroxide, irradiation crosslinking agent, silane-crosslinking catalyst, etc. A cross-linked insulation composition manufacturing step of preparing a cross-linked insulation composition by administering ~20,000 parts by weight and kneading at a temperature of 60-100°C for 10-60 minutes;

The cross-linked insulating composition prepared in the cross-linked insulating composition manufacturing step is administered to a hopper, and then passed through a conductor through the head of an extruder equipped with an extrusion die for 10 to 40 hours. The insulated wire is extruded at a rate of ㎏/hour and passed through a continuous vulcanization pipe maintained at 80~120℃ and 10~20 atmospheres at a speed of 20~50m/min, and the insulating layer is formed through the extrusion vulcanization step. An insulated wire manufacturing step of manufacturing;

A bundled strand manufacturing step of manufacturing a bundled stranded wire by stranding the insulated wire manufactured in the insulated wire manufacturing stage with a bundler;

While passing the aggregate strand manufactured in the aggregate strand manufacturing step and the filler together, the outer circumference thereof is taped with metal tape or metal coating film, or braided with metal wire such as metal wire, metal plated wire, or alloy wire. A common shielding layer forming step of forming a joint line in which a common shielding layer is formed;

The stranded wire with the common shielding layer manufactured in the common shielding layer forming step is passed through a taping column of a cable taping machine and is applied with a binder tape selected from polymer tape. A taping step of taping;

In an extruder with a molding die attached to the outer periphery of the insulated wire on which the binder tape layer prepared in the taping step is formed, the cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is processed at 5 to 50 kg/hour. An inner coating layer forming step of forming the inner coating layer by extruding at a speed of;

An external reinforcement layer forming step of forming a reinforcement layer by plying and braiding single or two or more types of metal wire, inorganic fiber yarn, aramid fiber yarn, etc. on the outer periphery of the insulated wire on which the internal coating layer prepared in the inner coating layer forming step is formed;

In an extruder in which an extrusion die is attached to the outer periphery of the insulated wire on which the reinforcing layer manufactured in the external reinforcement layer forming step is formed, the cold-resistant, high-flammability polymer composite manufactured in the cold-resistant, high-flammability polymer composite manufacturing step is 5 to 50 kg/kg. A polar shipping cable coated with a cold-resistant, highly flame-resistant polymer composite using a siloxane-modified thermoplastic elastomer can be easily manufactured through the outer coating layer forming step of extruding at the speed of time and forming the outer coating layer.

In addition, 10,000 parts by weight of ethylene copolymer, 500 to 2,000 parts by weight of electrically conductive filler, 43 to 64 parts by weight of antioxidant, and 25 to 40 parts by weight of metal stearate lubricant are sequentially added to a mixing mixer such as Kneader, Hensel, or Banbury. The lump dough that is put in and kneaded for 10 to 60 minutes at a temperature of 100 to 140℃ is transferred to a single-screw or twin-screw extruder and extruded to produce semiconducting elastomer pellets of 3 to 5 mm in size with a surface resistance of 105 to 108 Ω. A semiconducting elastomer pellet manufacturing step;

Add 10,568 to 12,104 parts by weight of the semiconducting elastomer pellets and 95 to 150 parts by weight of the organic peroxide to a separate mixing mixer such as Kneader, Hensel, Banbury, etc. and knead at a temperature of 60 to 100°C for 10 to 60 minutes to produce a crosslinked semiconductive composition. A cross-linked semiconducting composition manufacturing step for preparing a;

The semiconducting elastomer pellets prepared in the semiconducting elastomer pellet manufacturing step are placed in a first hopper, and the crosslinked insulating composition prepared in the crosslinked insulating composition manufacturing step are placed in a second hopper. The cross-linked semiconducting composition prepared in the step is injected into the third hopper and then passed through the conductor through the head of the extruder equipped with a co-extrusion die at 10 to 40 kg/hour. Peninsula manufactures insulated wires with a semiconducting layer formed through the extrusion vulcanization step by extruding at a speed of 80~120℃ and passing through a continuous vulcanization pipe maintained at 10~20 atm at a speed of 20~50m/min. A step of manufacturing an insulated wire in which all layers are formed;

A shielding layer forming step of forming a shielding layer by taping the outer periphery of the insulated wire on which the semiconducting layer is formed, which is manufactured in the insulated wire manufacturing step, with a metal tape or metal coating film, or braiding it with a metal wire or metal wire;

A taping step of passing an insulated wire with a plurality of combined shielding layers and a filler through the taping column of a cable taping machine with a binder tape;

In an extruder with a molding die attached to the outer periphery of the insulated wire on which the binder tape layer prepared in the taping step is formed, the cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is processed at 5 to 50 kg/hour. An inner coating layer forming step of forming the inner coating layer by extruding at a speed of;

An outer reinforcing layer forming step of forming a reinforcing layer by plying and braiding single to two or more types of metal wire, inorganic fiber yarn, aramid fiber yarn, etc. on the outer peripheral edge of the insulated wire on which the inner coating layer prepared in the inner coating layer forming step is formed; ;

In an extruder in which an extrusion die is attached to the outer periphery of the insulated wire on which the reinforcing layer manufactured in the external reinforcement layer forming step is formed, the cold-resistant, high-flammability polymer composite manufactured in the cold-resistant, high-flammability polymer composite manufacturing step is 5 to 50 kg/kg. Through the outer coating layer forming step of forming the outer coating layer by extruding at the speed of time, a polar shipping cable coated with a cold-resistant, high-flammability polymer composite using a different form of siloxane-modified thermoplastic elastomer can be easily manufactured.

As explained above, the present invention maximizes the dispersion characteristics of the inorganic filler, so that even if the content of the flame retardant is minimized when mixing the thermoplastic elastomer composition, it provides excellent flexibility and cold resistance without deteriorating the flame retardancy, as well as electrical, It has the effect of improving mechanical, chemical properties and productivity.

1 is a process flow diagram illustrating a method of implementing the siloxane-modified thermoplastic elastomer composition of the present invention.
Figure 2 is a process flow diagram illustrating the method of implementing the cable for polar navigation ships of the present invention.
Figure 3 is a process flow diagram illustrating a method of implementing a cable for a polar sailing ship according to another aspect of the present invention.

The present invention, which can meet the above purposes and features in the best form, will be described in detail with reference to Figure 1 by way of an embodiment as follows.

An embodiment according to the process flow diagram of Figure 1.

Siloxane-modified thermoplastic elastomer manufacturing step;

1,000 parts by weight of α,ω-hydrogensiloxane was added to a reactor equipped with a stirrer, temperature controller, dropping funnel, and condenser. Raise the reactor temperature to 60-100°C while stirring at a speed of 100-500 RPM, then add a catalyst selected from hexahydroxy platinic acid or hexachloroplatinic acid. 0.002 to 2.0 parts by weight were administered, and 20 to 200 parts by weight of allyl glycidyl ether was supplied through a dropping funnel mounted on the reactor for 10 to 60 minutes, maintaining the reactor temperature at 60 to 100°C and maintaining the reactor temperature at 60 to 100°C. The reaction proceeds for ~240 minutes. After the reaction is completed, 1,000 parts by weight of alcohol selected from ethanol, propanol, butanol, etc., amino polyethyleneoxide, amino polypropyleneoxide, After administering 100 to 400 parts by weight of amino polyalkylene oxide selected from amino polybutylene oxide, etc., the temperature of the reactor was maintained at 60 to 100°C, and the reaction mixture was stirred at a speed of 100 to 500 RPM for 60 to 60 minutes. The polymer solution obtained by proceeding with the reaction for 240 minutes is vacuum dried to produce a siloxane-modified thermoplastic elastomer.

Polyolefin elastomer manufacturing step;

A purge gas selected from neon, argon, nitrogen, hydrogen, etc. is applied to a flow reactor equipped with a stirrer and temperature controller. Polymerization solvent selected from pentane, hexane, heptane, octane, nonane, decane, etc. while continuously supplying and discharging at a rate of ~8L/hour. solvent 20,000~25,000g/hour, ethene 2,000~4,000g/hour, linear alkenes such as propene, butene, pentene, hexene, octene, etc. alkene) while supplying an alkene monomer selected from bis(indenyl)zirconium dichloride [bis(indenyl)zirconium dichloride], dimethylsilylene bis(4,5,6) at a rate of 1,000 to 3,000 g/hour. , 7-tetrahydroindenyl) zirconium dichloride [dimethylsilylene bis (4,5,6,7- tetrahydroindenyl) zirconium dichloride], bis (1-methyl, 3-n-butyl cycle pentadienyl) zirconium dichloride [bis (1-methyl,3-n-butylcyclpentadienyl)zirconium dichloride], dimethylsilylene bis(indenyl)zirconium dichloride], dimethylsilylene bis(2-methylindenyl)zirconium dichloride Zirconium compounds such as [dimethylsilylene bis(2-methyl indenyl)zirconium dichloride], ethylenebisindenylzirconium dichloride, and bis(2-propylindenyl)zirconium dichloride] A polymerization catalyst selected from 0.01 to 0.1 mmol/hour and a cocatalyst selected from organoaluminoxane such as methylaluminoxane and methylisobutylaluminoxane at 0.10 to 0.50 mmol/hour. The polymerization reaction proceeds for 4 to 20 hours while maintaining the reactor pressure at 1.5 to 2 atm and the temperature at 80 to 110°C. After the reaction was completed, alcohol was added to the polymerization reaction liquid extracted from the bottom of the continuous reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent and then heated at 60 to 100°C. Polyolefin elastomer is prepared by drying under reduced pressure for 12 to 48 hours.

Compatibilizer manufacturing step;

An aromatic solvent selected from benzene, xylene, chlorobenzene, etc. is circulated through a reactor equipped with a stirrer, temperature controller, and nitrogen purging equipment. Add 1,000 parts by weight of solvent and 100 to 500 parts by weight of polyolefin resin selected from polyethylene, polypropylene, or ethylene copolymer, and then set the reactor temperature to 80 to 150°C. The polyolefin resin is completely dissolved while stirring at a speed of 100 to 500 RPM. Once the polyolefin resin is completely dissolved, acrylic anhydride, methacrylic anhydride, or maleic acid is added to the reactor. 1 to 15 parts by weight of anhydride selected from maleic anhydride, etc., and peroxide selected from benzoyl peroxide, dichlorobenzoyl peroxide, and dicumyl peroxide. A compatibilizer is prepared by adding 1 to 15 parts by weight of the oxide compound and reacting for 1 to 3 hours, followed by cooling and recrystallization.

Cold-resistant, highly flame-resistant polymer composite manufacturing step;

High density polyethylene, medium density polyethylene, linear low density polyethylene, and low density polyethylene are mixed in a mixing mixer using a kneader mixer or banbury mixer. 100,000 parts by weight of polyethylene resin selected from polyethylene, etc., and 100,000 to 180,000 parts by weight of polyolefin elastomer manufactured in the polyolefin elastomer manufacturing stage, with a glass transition temperature of -65°C or lower and a tensile strength of 3 to 5 MPa. 200,000 to 500,000 parts by weight of ethylene-octene block copolymer, 60,000 to 100,000 parts by weight of compatibilizer prepared in the compatibilizer manufacturing stage, metal oxide surface treated with silane or fatty acid. 400,000 to 800,000 parts by weight of flame retardant, 10,000 to 40,000 parts by weight of siloxane-modified thermoplastic elastomer manufactured in the siloxane-modified thermoplastic elastomer manufacturing stage, tetramethoxy silane, methyltrimethoxysilane, or propyltrimethoxysilane 3,000 to 15,000 parts by weight of silane selected from propyltrimethoxy silane, tetraethoxy silane, methyltriethoxysilane, etc., polydimethylsiloxane, polydiphenylsiloxane, 12,000 to 35,000 parts by weight of polysiloxane selected from polymethylhydrogensiloxane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate [octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Nate]{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-meta-cresol)[4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol)], 6,6'-di-tert-butyl -4,4'-butylidenedi-meta-cresol [6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol], 3,9-bis {2-[3-(3 -tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane{3,9-Bis{ 2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane}, 1,3,5 -tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene [1,3,5-tris(3,5-di-tert-butyl-4- 5,000 to 9,000 parts by weight of antioxidants selected individually or in combination of two or more from [hydroxyphenylmethyl)-2,4,6-trimethylbenzene], carbon black, titanium dioxide, zinc oxide, and tungsten. 10,000 to 40,000 parts by weight of pigments used singly or in combination of two or more selected from tungsten oxide, cesium dioxide, sodium stearate, zinc stearate, and calcium stearate. 1,500 to 4,000 parts by weight of a metal stearate lubricant selected from stearate, magnesium stearate, etc. are sequentially added and melt-mixed for 10 to 60 minutes at a temperature of 80 to 170°C. It is transferred to a twin-screw extruder or a twin-screw extruder to produce composition pellets of 2 to 5 mm in size through extrusion molding, then dried in an oven at 60 to 80 ° C and subjected to a particle size selection process to produce a cold-resistant, highly flammable polymer composite.

FMS embodiment according to the process flow diagram of Figure 2.

Cross-linked insulating composition manufacturing step;

Add ethylene polymer selected from polyethylene, ethylene-propylene copolymer, or ethylene-propylene-diene copolymer to a mixing mixer such as Kneader, Henschel, or Banbury. 100,000 parts by weight of polymer or ethylene copolymer, 60,000 to 100,000 parts by weight of metal oxide flame retardant surface-treated with silane or fatty acid, silica or carbon black, magnesium carbonate, aluminum silicate, magnesium 100 to 12,000 parts by weight of reinforcing agent selected from silicate, diatomaceous earth, etc., thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][thiodiethylene bis(3-(3) ,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodipropionic acid dioctadecylester, distearyl thiodipropionate, 3-mercapto Sequentially administer 50 to 200 parts by weight of antioxidants used alone or in combination of two or more types of sulfur compounds such as propionic acid (3-mercaptopropionic acid) and 100 to 1,200 parts by weight of metal stearate lubricant, and incubate for 5 minutes at a temperature of 80 to 130°C. The lump of dough kneaded for ~60 minutes is transferred to a single-screw or twin-screw extruder and extruded to produce an insulating composition of 3 to 5 mm in size.

Cross-linked insulating composition manufacturing step;

In a separate mixing mixer such as Kneader, Henschel, Banbury, etc., 100,000 parts by weight of the insulating composition pellets and 1,000 parts by weight of a crosslinking agent selected from organic peroxide, irradiation crosslinking agent, silane-crosslinking catalyst, etc. Add ~20,000 parts by weight and mix for 10 to 60 minutes at a temperature of 60 to 100°C to prepare a crosslinked insulation composition.

Insulated wire manufacturing step;

The cross-linked insulating composition prepared in the cross-linked insulating composition manufacturing step is administered to a hopper, and then a metal wire or metal-plated wire is attached to the head of an extruder equipped with an extrusion die. As it passes through a conductor made of metal plated wire and metal alloy wire, the temperature conditions are 100~120℃ for cylinder 1, 100~120℃ for cylinder 2, and 105~125℃ for cylinder 3. , the extrusion head is 110~130℃, and the extrusion die is extruded at a rate of 10~40kg/hour under temperature conditions of 110~130℃ and maintained at 80~120℃ and 10~20 atm. An insulated wire with an insulating layer is manufactured through an extrusion vulcanization step by passing a continuous vulcanization pipe at a speed of 20 to 50 m/min.

Collective strand manufacturing steps;

The insulated wire manufactured in the above insulated wire manufacturing step is stranded in a bundle to produce a bundled strand.

Joint shielding layer forming step;

While passing the aggregate strand manufactured in the aggregate strand manufacturing step and the filler together, the outer circumference thereof is taped with metal tape or metal coating film, or braided with metal wire such as metal wire, metal plated wire, or alloy wire. This forms a joint line with a common shielding layer.

Taping step;

The stranded wire with the common shielding layer manufactured in the common shielding layer formation step is passed through the taping column of a cable taping machine, and polyester, polyketone, or polyimide ( Tape with a binder tape selected from polyimide, polysulfone tape, etc.

Internal coating layer forming step;

In an extruder in which a molding die is attached to the outer periphery of the insulated wire on which the binder tape layer produced in the taping step is formed, cylinder 1 is 100 to 180 ℃, cylinder 2 is 100 to 180 ℃, cylinder 3 is 120 to 200 ℃, die : The cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is extruded at a rate of 5-50 kg/hour under a temperature condition of 120-200°C to form an inner coating layer.

External reinforcement layer forming step;

Metal wires such as copper wire, metal-plated copper wire, iron wire, and nickel wire, or glass fiber yarn, basalt fiber yarn, elvanite fiber yarn, ceramic fiber yarn, and carbon fiber yarn are placed around the outer periphery of the insulated wire on which the inner coating layer is formed in the inner coating layer forming step. The same inorganic fiber yarn, aramid fiber yarn, etc. are spun and braided singly or two or more to form a reinforcing layer.

External coating layer forming step;

In the extruder with an extrusion die attached to the outer periphery of the insulated wire on which the reinforcing layer manufactured in the external reinforcing layer forming step is formed, cylinder 1 is 100 to 180 ℃, cylinder 2 is 100 to 180 ℃, and cylinder 3 is 120 to 200 ℃, Die: The cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is extruded at a rate of 5-50 kg/hour under temperature conditions of 120 ~ 200 ℃ to form an outer coating layer.

Through the above-mentioned steps, a polar shipping cable coated with a cold-resistant, highly flame-resistant polymer composite using a siloxane-modified thermoplastic elastomer can be easily manufactured.

FMS embodiment according to the process flow diagram of Figure 3.

Semiconductive elastomer pellet manufacturing step;

Add 10,000 parts by weight of ethylene copolymer and electro-conductive carbon black, carbon nanotubes, graphite, or graphene to a mixing mixer such as Kneader, Henschel, or Banbury. 500 to 2,000 parts by weight of an electrically conductive filler, 43 to 64 parts by weight of an antioxidant, and 25 to 40 parts by weight of a metal stearate lubricant are sequentially added and kneaded at a temperature of 100 to 140°C for 10 to 60 minutes. A lump of dough is transferred to a single-screw or twin-screw extruder and extruded to produce semiconducting elastomer pellets of 3 to 5 mm in size with a surface resistance of 10 ^{5 to} 10 ⁸ Ω.

Cross-linked semiconducting composition manufacturing step;

Add 10,568 to 12,104 parts by weight of the semiconducting elastomer pellets and 95 to 150 parts by weight of the organic peroxide to a separate mixing mixer such as Kneader, Hensel, or Banbury, and knead for 10 to 60 minutes at a temperature of 60 to 100°C to obtain crosslinked semiconductivity. Prepare composition pellets.

Insulated wire manufacturing step;

The semiconducting elastomer pellets prepared in the semiconducting elastomer pellet manufacturing step are placed in a first hopper, and the crosslinked insulating composition prepared in the crosslinked insulating composition manufacturing step are placed in a second hopper. The cross-linked semiconducting composition prepared in step is injected into the third hopper, and then a metal wire or metal plated wire is inserted into the head of the extruder equipped with a co-extrusion die. ), passing through a conductor made of metal alloy wire, the temperature conditions are 100~120℃ for cylinder 1, 100~120℃ for cylinder 2, 105~125℃ for cylinder 3, and extrusion head. (extrusion head) 110~130℃, extrusion die extrudes at a rate of 10~40kg/hour under temperature conditions of 110~130℃, and the curing tube ( A semiconducting layer is formed by passing a continuous vulcanization pipe at a speed of 20 to 50 m/min to produce an insulated wire with a semiconducting layer through the extrusion and vulcanization step.

Shielding layer forming step;

A shielding layer is formed by taping the outer periphery of the insulated wire on which the semiconducting layer is formed, manufactured in the insulated wire manufacturing step, with a metal tape or metal coating film, or braiding it with a metal wire or metal wire.

Taping step;

The insulated wire and the filler formed with multiple combined shielding layers are passed together through the taping column of the cable taping machine and taped with a binder tape.

Internal coating layer forming step;

In an extruder in which a molding die is attached to the outer periphery of the insulated wire on which the binder tape layer produced in the taping step is formed, cylinder 1 is 100 to 180 ℃, cylinder 2 is 100 to 180 ℃, cylinder 3 is 120 to 200 ℃, die The cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is extruded at a rate of 5-50 kg/hour under a temperature condition of 120-200°C to form an inner coating layer.

External reinforcement layer forming step;

A reinforcing layer is formed by plying and braiding metal wire, inorganic fiber yarn, aramid fiber yarn, etc. singly or two or more types on the outer circumferential edge of the insulated wire on which the inner coating layer prepared in the inner coating layer forming step is formed.

External coating layer forming step;

In an extruder with a 20 mm extrusion die attached to the outer periphery of the insulated wire with the reinforcing layer manufactured in the external reinforcing layer forming step, cylinder 1 is 100 to 180 ℃, cylinder 2 is 100 to 180 ℃, and cylinder 3 is 120 to 200 ℃. , the cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is extruded at a rate of 5-50 kg/hour under temperature conditions of 120 to 200 ° C. to form an outer coating layer.

Through the above-described steps, it is possible to easily manufacture a polar shipping cable coated with a cold-resistant, high-flammability polymer composite using another form of siloxane-modified thermoplastic elastomer.

The catalyst in the siloxane-modified thermoplastic elastomer manufacturing step initiates copolymerization and is selected from hexahydroplatinic acid or hexachloroplatinic acid and used in an amount of 0.002 to 2.0 parts by weight, but the present invention is not limited thereto.

At this time, if the catalyst is less than 0.002 parts by weight, the yield decreases, and if it is more than 2 parts by weight, economic efficiency decreases.

The amino polyalkylene oxide in the siloxane-modified thermoplastic elastomer manufacturing step forms a silicone copolymer and is selected from amino polyethylene oxide, amino polypropylene oxide, amino polybutylene oxide, etc., and is used in an amount of 100 to 400 parts by weight, but the present invention is limited thereto. no.

At this time, if the amino polyalkylene oxide is less than 100 parts by weight, the yield decreases, and if it is more than 400 parts by weight, the purity rate decreases.

The polymerization catalyst used in the polyolefin elastomer manufacturing step is a catalyst that initiates polymerization and includes bis(indenyl)zirconium dichloride, dimethylsilylene bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, and bis(1). -methyl, 3-n-butylcyclepentadienyl)zirconium dichloride, dimethylsilylene bis(indenyl)zirconium dichloride, dimethylsilylene bis(2-methylindenyl)zirconium dichloride, ethylene bisynedenyl zirconium dichloride Zirconium compounds such as chloride and bis(2-propylindenyl)zirconium dichloride are preferred. In addition, hafnium compounds and palladium compounds can also be used and are supplied at a rate of 0.01 to 0.1 mmol/hour.

At this time, if the supply rate of the polymerization catalyst is less than 0.01 mmol/hour, the yield decreases, and if it is more than 0.1 mmol/hour, catalyst residue increases.

The metal oxide flame retardant surface-treated with silane or fatty acid in the siloxane-modified thermoplastic elastomer manufacturing step is used in an amount of 400,000 to 800,000 parts by weight as the main flame retardant that imparts flame retardancy to the composition.

At this time, the metal oxide flame retardant may be used singly or in combination of two or more such as magnesium hydroxide phosphate, aluminum hydroxide, or magnesium hydroxide, but the present invention is not limited thereto.

At this time, the silane used for surface treatment of metal oxide flame retardants is tetramethoxy silane, methyltrimethoxysilane, propyltrimethoxy silane, tetraethoxy silane, Methyltriethoxysilane and the like are preferred, but the present invention is not limited thereto.

At this time, the fatty acid used for surface treatment of the metal oxide flame retardant is preferably palmitic acid, stearic acid, or lauric acid, but the present invention is not limited thereto.

At this time, if the surface-treated metal oxide flame retardant is less than 400,000 parts by weight, the flame retardancy of the composition deteriorates, and if it is more than 800,000 parts by weight, the mechanical properties deteriorate.

The pigment in the siloxane-modified thermoplastic elastomer manufacturing step gives color to the composition and is selected singly or two or more from titanium dioxide, carbon black, zinc oxide, tungsten oxide, cesium dioxide, etc. and is used in an amount of 10,000 to 40,000 parts by weight, but the present invention is limited thereto. It's not.

At this time, if the pigment is less than 10,000 parts by weight, the light stability of the composition is reduced, and if it is more than 40,000 parts by weight, the compatibility is poor.

In the insulated wire manufacturing step where the semiconducting layer is formed, the conductor is a component that transmits signals or power, and it is preferable to use copper wire, tin-plated copper wire, nickel-plated copper wire, etc. with high electrical conductivity, but the present invention is not limited.

It is preferable to use a single metal wire as the conductor as well as a plurality of metal wires.

The filling material in the taping step maintains the concentricity of the insulated wire, plays a waterproof role, and is preferably a moisture-resistant (non-hygroscopic) inorganic fiber yarn or polymer fiber yarn, but is not limited to the present invention.

The binder tape in the taping step combines the filler and the insulated wire to maintain a concentric circle, and it is preferable to use polyester, polyceptone, polyimide, or polysulfone tape, but it is not limited to the present invention.

The external reinforcement layer forming step and the external reinforcement layer are made of metal wire such as copper wire, metal-plated copper wire, iron wire, and nickel wire, or glass fiber yarn, basalt fiber yarn, and elvan stone fiber to protect the insulation from external shock and prevent rodents from gnawing. It is selected from yarns, ceramic fiber yarns, inorganic fiber yarns such as carbon fiber yarns, and aramid fiber yarns, and is formed by plying and braiding singly or two or more types.

The cold-resistant, high-flammability polymer composite using the siloxane-modified thermoplastic elastomer according to the present invention and the polar shipping cable coated therewith will be examined in more detail, and examples thereof will be described as follows.

The present invention will be described in more detail through examples below.

However, the scope of the present invention is not limited to only the illustrative examples.

Example 1

1,000 g of α,ω-hydrogensiloxane was added to the reactor, then raised to 80°C while stirring at a speed of 100 RPM, then 0.02 g of hexahydroplatinic acid was added, and 100 g of alli glycidyl ether was added through a dropping funnel. While supplying for 30 minutes, the reactor temperature was maintained at 80°C and the reaction proceeded for 120 minutes. After the reaction was completed, 1,000 g of ethanol and 200 g of amino polyethylene oxide were added, the reactor temperature was maintained at 80°C, the reaction was allowed to proceed for 120 minutes while stirring at a speed of 100 RPM, and the obtained polymer solution was vacuum dried to prepare a siloxane-modified thermoplastic elastomer. did.

Hydrogen was supplied and discharged to the continuous reactor at a rate of 5 L/hour, and heptane was supplied at a rate of 22,000 g/hour, ethene 3,000 g/hour, and octene at a rate of 1,000 g/hour, and dimethylsilylene bis(indenyl)zirconium dichloride was added. Polymerization reaction was carried out for 20 hours while maintaining the reactor pressure of 1.7 atm and temperature of 90°C by adding methylaluminoxane at a rate of 0.03 mmol/hour and 0.15 mmol/hour. After the reaction was completed, methanol was added to the polymerization reaction liquid extracted from the bottom of the continuous reactor to terminate the reaction, and the copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for 24 hours to prepare a polyolefin elastomer. .

While circulating nitrogen in the reactor, 1,000 parts by weight of xylene and 200 g of polyethylene resin were added, then the temperature of the reactor was raised to 120°C and the resin was completely dissolved while stirring at a speed of 200 RPM. When the dissolution of the resin was complete, 6 g of maleic anhydride and 6 g of dicumyl peroxide were added and the mixture reacted for 2 hours was cooled and recrystallized to prepare a compatibilizer.

In a kneader mixer, 100,000g of medium-density polyethylene, 150,000g of polyolefin elastomer, 380,000g of ethylene-octene block copolymer with a glass transition temperature of -65℃ and tensile strength of 3MPa, 86,000g of compatibilizer, and magnesium surface-treated with methyltriethoxy silane. Hydrooxide 650,000g, functional silicone copolymer 22,000g, propyltrimethoxysilane 5,000g, polymethylhydrogensiloxane 25,000g, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- 4,200g of hydroxyphenyl)propionate, 3,000g of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 20,000g of carbon black, and 2,800g of zinc stearide sequentially. A lump of dough is melted and mixed at a temperature of 120°C for 20 minutes, then transferred to a single-screw or twin-screw extruder to produce composition pellets of 2 to 5 mm in size through extrusion, then dried in an oven at 60°C and screened for particle size. Through this process, a cold-resistant, highly flame-resistant polymer composite was manufactured.

In a kneader mixer, 100,000 g of linear low-density polyethylene, 80,000 g of magnesium hydroxide surface-treated with methyltriethoxy silane, 1,800 g of diatomaceous earth, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxy). [Phenyl)propionate] 150g, thiodipropionic acid dioctadecyl ester 20g, and zinc stearade 150g were sequentially added and kneaded at 120°C for 20 minutes. Then, the kneaded dough was transferred to a twin-screw extruder for extrusion molding. Insulating composition pellets with a size of 3 to 5 mm were manufactured through this process.

100,000 parts by weight of insulation composition pellets and 4,200 g of dicumyl oxide were added to a separate Henschel mixer and kneaded for 10 minutes at a temperature of 80°C to prepare a crosslinked insulation composition.

10,000 g of ethylene propylene copolymer, 1,400 g of electrically conductive carbon black, 52 g of tris(2,4-ditert-butylphenyl)phosphite, and 30 g of zinc stearate were sequentially added to the kneader mixer and kneaded at 100°C for 20 minutes. The lump dough was transferred to a twin-screw extruder and extruded to produce semiconducting ethylene propylene copolymer pellets of 3 to 5 mm in size and with a surface resistance of 10 ⁶ Ω. Semiconducting ethylene propylene copolymer pellets prepared in a separate Henschel mixer and 120 g of dicumyl peroxide were added and kneaded at 80°C for 20 minutes to prepare crosslinked semiconducting composition pellets.

The semiconducting elastomer pellets prepared in the semiconducting elastomer pellet manufacturing step are placed in a first hopper, and the crosslinked insulating composition prepared in the crosslinked insulating composition manufacturing step are placed in a second hopper. The crosslinked semiconducting composition prepared in step was administered to the third hopper and then passed through a tin-plated wire with a diameter of 23Φmm through the head of an extruder equipped with co-extrusion dies with diameters of 24Φmm, 31Φmm, and 32Φmm, respectively, while cylinder 1 was 105 ℃, cylinder 2 is 110℃, cylinder 3 is 115℃, extrusion head is 115℃, and extrusion die is 120℃. Extrusion is performed at a rate of 22 kg/hour, and the curing tube maintained at 110℃ and 15 atm is stretched for 30 m/min. An insulated wire with a semiconducting layer is manufactured by passing it at a speed of 100 min, then braided with tin-plated wire with a diameter of 0.1 mm to form a shielding layer, and the insulated wire with a shielding layer formed by combining 3 strands with a taping column of a cable taping machine and poly. Pass the propylene yarn filling together and tap it with polyethylene terephthalate polyester tape, and then use a single-screw extruder equipped with a 78mm extrusion die (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175 ℃) A cold-resistant, high-flammability polymer composite is injected into the hopper and extruded to a thickness of 2mm at a speed of 20kg/hour to form an inner coating layer. Braided with a copper cladding wire with a diameter of 0.2mm to form a reinforcing layer, and then an 84mm extrusion die is used. The cold-resistant, highly flammable polymer composite was injected into the hopper of the attached single-screw extruder (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃) and extruded at a speed of 20kg/hour to a thickness of 2.6mm. Manufacturing of the cable was completed by extruding and forming the outer covering layer.

Example 2

1,000 g of α,ω-hydrogensiloxane was added to the reactor, then raised to 80°C while stirring at a speed of 100 RPM, then 0.02 g of hexachloroplatinic acid was added, and 100 g of alli glycidyl ether was added through a dropping funnel. While supplying for 30 minutes, the reactor temperature was maintained at 80°C and the reaction proceeded for 120 minutes. After the reaction was completed, 1,000 g of ethanol and 200 g of amino polypropylene oxide were added, the reactor temperature was maintained at 80°C, and the reaction was allowed to proceed for 120 minutes while stirring at a speed of 100 RPM. Then, the obtained polymer solution was vacuum dried to produce a siloxane-modified thermoplastic elastomer. was manufactured.

Hydrogen was supplied and discharged to the continuous reactor at a rate of 5L/hour, while heptane was supplied at a rate of 22,000g/hour, ethene 3,000g/hour, and octene 1,000g/hour, and dimethylsilylene bis(4,5,6, 7-Tetrahydroindenyl) zirconium dichloride dichloride was added at a rate of 0.03 mmol/hour and methylaluminoxane at a rate of 0.15 mmol/hour, and the polymerization reaction was carried out for 20 hours while maintaining the reactor pressure at 1.7 atm and temperature at 90°C. . After the reaction was completed, methanol was added to the polymerization reaction liquid extracted from the bottom of the continuous reactor to terminate the reaction, and the copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for 24 hours to prepare a polyolefin elastomer. .

While circulating nitrogen in the reactor, 1,000 parts by weight of xylene and 100 g of polypropylene resin were added, then the temperature of the reactor was raised to 120°C and the resin was completely dissolved while stirring at a speed of 200 RPM. When the dissolution of the resin was complete, 6 g of maleic anhydride and 6 g of dicumyl peroxide were added and the mixture reacted for 2 hours was cooled and recrystallized to prepare a compatibilizer.

In a kneader mixer, 100,000g of low-density polyethylene and 150,000g of polyolefin elastomer, 380,000g of ethylene-octene block copolymer with a glass transition temperature of -65℃ and tensile strength of 3MPa, 86,000g of compatibilizer, and magnesium hydro treated with stearic acid surface. 650,000g oxide, 22,000g functional silicone copolymer, 5,000g propyltrimethoxysilane, 25,000g polymethylhydrogensiloxane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydride) Sequentially 4,200g of hydroxyphenyl)propionate, 3,000g of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 20,000g of carbon black, and 2,800g of zinc stearide. A lump of dough is melted and mixed at a temperature of 120°C for 20 minutes, then transferred to a single-screw or twin-screw extruder to produce composition pellets of 2 to 5 mm in size through extrusion, then dried in an oven at 60°C and particle size selection process. Through this process, a cold-resistant, highly flame-resistant polymer composite was manufactured.

In a kneader mixer, 100,000 g of linear low-density polyethylene, 80,000 g of magnesium hydroxide surface-treated with methyltriethoxy silane, 1,800 g of diatomaceous earth, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxy). [Phenyl)propionate] 150g, thiodipropionic acid dioctadecyl ester 20g, and zinc stearade 150g were sequentially added and kneaded at 120°C for 20 minutes. Then, the kneaded dough was transferred to a twin-screw extruder for extrusion molding. Insulating composition pellets with a size of 3 to 5 mm were manufactured through this process.

100,000 parts by weight of insulation composition pellets and 4,200 g of dicumyl oxide were added to a separate Henschel mixer and kneaded for 10 minutes at a temperature of 80°C to prepare a crosslinked insulation composition.

10,000 g of ethylene propylene copolymer, 1,400 g of electrically conductive carbon black, 52 g of tris(2,4-ditert-butylphenyl)phosphite, and 30 g of zinc stearate were sequentially added to the kneader mixer and kneaded at 100°C for 20 minutes. The lump dough was transferred to a twin-screw extruder and extruded to produce semiconducting ethylene propylene copolymer pellets of 3 to 5 mm in size and with a surface resistance of 10 ⁶ Ω. Semiconducting ethylene propylene copolymer pellets prepared in a separate Henschel mixer and 120 g of dicumyl peroxide were added and kneaded at 80°C for 20 minutes to prepare crosslinked semiconducting composition pellets.

The semiconducting elastomer pellets prepared in the semiconducting elastomer pellet manufacturing step are placed in a first hopper, and the crosslinked insulating composition prepared in the crosslinked insulating composition manufacturing step are placed in a second hopper. The crosslinked semiconducting composition prepared in step was administered to the third hopper and then passed through a tin-plated wire with a diameter of 23Φmm through the head of an extruder equipped with co-extrusion dies with diameters of 24Φmm, 31Φmm, and 32Φmm, respectively, while cylinder 1 was 105 ℃, cylinder 2 is 110℃, cylinder 3 is 115℃, extrusion head is 115℃, and extrusion die is 120℃. Extrusion is performed at a rate of 22 kg/hour, and the curing tube maintained at 110℃ and 15 atm is stretched for 30 m/min. After manufacturing the insulated wire with a semiconducting layer formed by passing it at a speed of Pass the propylene yarn filling together and tape it with polyketone tape, then use a single-screw extruder with a 78mm extrusion die attached (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃) hopper. A cold-resistant, high-flammability polymer composite is administered and extruded to a thickness of 2 mm at a rate of 20 kg/hour to form an inner coating layer, and braided with a 0.1 mm diameter copper steel wire to form a reinforcing layer, and an 84 mm extrusion die is attached. The cold-resistant, high-flammability polymer composite is injected into the hopper of a single-screw extruder (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃) and extruded to a thickness of 2.6mm at a speed of 20kg/hour. Manufacturing of the cable was completed by molding the outer covering layer.

Example 3

1,000 g of α,ω-hydrogensiloxane was added to the reactor, then raised to 80°C while stirring at a speed of 100 RPM, then 0.02 g of hexachloroplatinic acid was added, and 100 g of alli glycidyl ether was added through a dropping funnel. While supplying for 30 minutes, the reactor temperature was maintained at 80°C and the reaction proceeded for 120 minutes. After the reaction was completed, 1,000 g of ethanol and 200 g of amino polybutylene oxide were added, the reactor temperature was maintained at 80°C, the reaction was allowed to proceed for 120 minutes while stirring at a speed of 100 RPM, and the obtained polymer solution was vacuum dried to produce a siloxane-modified thermoplastic elastomer. was manufactured.

Hydrogen was supplied and discharged to the continuous reactor at a rate of 5 L/hour, while heptane was supplied at a rate of 22,000 g/hour, ethene 3,000 g/hour, and octene at a rate of 1,000 g/hour, and bis(1-methyl, 3-n-butyl) was supplied to the continuous reactor. Cycpentadienyl)zirconium dichloride was added at a rate of 0.03 mmol/hour and methylaluminoxane at a rate of 0.15 mmol/hour, and polymerization was carried out for 20 hours while maintaining the reactor pressure at 1.7 atm and temperature at 90°C. After the reaction was completed, methanol was added to the polymerization reaction liquid extracted from the bottom of the continuous reactor to terminate the reaction, and the copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for 24 hours to prepare a polyolefin elastomer. .

While circulating nitrogen in the reactor, 1,000 parts by weight of xylene and 100 g of polyethylene resin were added, then the temperature of the reactor was raised to 120°C and the resin was completely dissolved while stirring at a speed of 200 RPM. When the dissolution of the resin was complete, 6 g of maleic anhydride and 6 g of dicumyl peroxide were added and the mixture reacted for 2 hours was cooled and recrystallized to prepare a compatibilizer.

In a kneader mixer, 100,000g of linear low-density polyethylene, 150,000g of polyolefin elastomer, 380,000g of ethylene-octene block copolymer with a glass transition temperature of -65℃ and tensile strength of 3MPa, 86,000g of compatibilizer, and magnesium surface-treated with methyltriethoxy silane. Hydrooxide 650,000g, functional silicone copolymer 22,000g, propyltrimethoxysilane 5,000g, polymethylhydrogensiloxane 25,000g, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- 4,200g of hydroxyphenyl)propionate, 3,000g of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 20,000g of carbon black, and 2,800g of zinc stearide sequentially. A lump of dough is melted and mixed at a temperature of 120°C for 20 minutes, then transferred to a single-screw or twin-screw extruder to produce composition pellets of 2 to 5 mm in size through extrusion, then dried in an oven at 60°C and screened for particle size. Through this process, a cold-resistant, highly flame-resistant polymer composite was manufactured.

In a kneader mixer, 100,000 g of linear low-density polyethylene, 80,000 g of magnesium hydroxide surface-treated with methyltriethoxy silane, 1,800 g of diatomaceous earth, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxy). [Phenyl)propionate] 150g, thiodipropionic acid dioctadecyl ester 20g, and zinc stearade 150g were sequentially added and kneaded at 120°C for 20 minutes. Then, the kneaded dough was transferred to a twin-screw extruder for extrusion molding. Insulating composition pellets with a size of 3 to 5 mm were manufactured through this process.

100,000 parts by weight of insulation composition pellets and 4,200 g of dicumyl oxide were added to a separate Henschel mixer and kneaded for 10 minutes at a temperature of 80°C to prepare a crosslinked insulation composition.

10,000 g of ethylene propylene copolymer, 1,400 g of electrically conductive carbon black, 52 g of tris(2,4-ditert-butylphenyl)phosphite, and 30 g of zinc stearate were sequentially added to the kneader mixer and kneaded at 100°C for 20 minutes. The lump dough was transferred to a twin-screw extruder and extruded to produce semiconducting ethylene propylene copolymer pellets of 3 to 5 mm in size and having a surface resistance of 10 ⁶ Ω. Semiconducting ethylene propylene copolymer pellets prepared in a separate Henschel mixer and 120 g of dicumyl peroxide were added and kneaded at 80°C for 20 minutes to prepare crosslinked semiconducting composition pellets.

The semiconducting elastomer pellets prepared in the semiconducting elastomer pellet manufacturing step are placed in a first hopper, and the crosslinked insulating composition prepared in the crosslinked insulating composition manufacturing step are placed in a second hopper. The crosslinked semiconducting composition prepared in step was administered to the third hopper and then passed through a tin-plated wire with a diameter of 23Φmm through the head of an extruder equipped with co-extrusion dies with diameters of 24Φmm, 31Φmm, and 32Φmm, respectively, while cylinder 1 was 105 ℃, cylinder 2 is 110℃, cylinder 3 is 115℃, extrusion head is 115℃, and extrusion die is 120℃. Extrusion is performed at a rate of 22 kg/hour, and the curing tube maintained at 110℃ and 15 atm is stretched for 30 m/min. After manufacturing an insulated wire with a semiconducting layer formed by passing it at a speed of The insulated wire with the formed shielding layer and the Kevlar yarn filling are passed together, taped with polyimide tape, and then extruded through a single-screw extruder equipped with a 78mm extrusion die (cylinder 1 at 160℃, cylinder 2 at 170℃, and cylinder 3 at 180℃). ℃, die 175℃) Cold-resistant, high-flammability polymer composite is injected into the hopper and extruded to a thickness of 2mm at a speed of 20kg/hour to form the inner covering layer and braided with carbon fiber yarn/Kevlar yarn (50:50 blended yarn) to form a reinforcement layer. Form a single-screw extruder equipped with an 84mm extrusion die (cylinder 1: 160°C, cylinder 2: 170°C, cylinder 3: 180°C, die 175°C). Cold-resistant, highly flammable polymer composite is administered to the hopper and 20 The outer coating layer was formed by extruding to a thickness of 2.6 mm at a rate of kg/hour to complete the production of a highly flame retardant thermoplastic elastomer composition with flexibility, cold resistance, oil resistance, and ice resistance, and a polar shipping cable coated with the same.

Example 4

100,000 parts by weight of cross-linked insulating composition pellets were prepared using the cold-resistant, high-flammability polymer composite and cross-linked insulating composition prepared in Example 1. After dosing into the hopper , a tin-plated wire with a diameter of 1.2Φmm is passed through the head of an extruder equipped with an extrusion die with a diameter of 2.2Φmm, and extrusion is performed at 105℃ for cylinder 1, 110℃ for cylinder 2, and 115℃ for cylinder 3. The head is 115℃, the extrusion die is extruded at a rate of 22kg/hour under a temperature condition of 120℃, and the insulated wire is manufactured by passing it through a vulcanizing tube maintained at 110℃ and 15 atm at a speed of 30m/min. Gathering 2 strands of insulated wire and stranding 7 strands of insulated wire taped with polyethylene terephthalate tape, the assembled strand and polypropylene yarn filler are passed together through the taping column of a cable taping machine and taped with polyethylene terephthalate tape, A common shielding layer is formed by braiding with tin plating with a thickness of 0.2 mm in diameter. The cold-resistant, high-flammability polymer composite is injected into the hopper and the extrusion head of a single-screw extruder equipped with a 15.2mm extrusion die (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃). The inner covering layer is formed by extruding the bundled wire with the cavity shielding layer formed to a thickness of 1.2 mm while supplying at a rate of 20 kg/hour, forming a reinforcing layer by braiding it with a copper clad steel wire with a diameter of 0.3 mm, and then a 17 mm extrusion die is attached. The cold-resistant, high-flammability polymer composite is injected into the hopper of a single-screw extruder (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃) and extruded to a thickness of 0.9mm at a speed of 20kg/hour. Then, the outer covering layer was formed to complete the production of the cable.

Example 5

Using the cold-resistant, high-flammability polymer composite and the cross-linked insulating composition prepared in Example 2, cross-linked insulating composition pellets were injected into a hopper and then injected into the head of an extruder with a 2.2 Φ mm diameter extrusion die attached. While passing through the tin-plated wire, cylinder 1 is extruded at a rate of 22 kg/hour under temperature conditions of 105°C, cylinder 2 at 110°C, cylinder 3 at 115°C, extrusion head at 115°C, and extrusion die at 120°C. An insulated wire is manufactured by passing it through a vulcanization tube maintained at 15 atmospheres at a speed of 30 m/min, then the two strands of the manufactured insulated wire are assembled, and a set is formed by stranding 7 strands of the insulated wire taped with polyethylene terephthalate. The stranded wire and the polypropylene yarn filling are passed together through the taping column of a cable taping machine, taped with polyethylene terephthalate tape, and then braided with tin plating with a diameter of 0.2 mm to form a common shielding layer.

The cold-resistant, high-flammability polymer composite is injected into the hopper and the extrusion head of a single-screw extruder equipped with a 15.2mm extrusion die (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃). The inner covering layer is formed by extruding the bundled wire with the cavity shielding layer formed to a thickness of 1.2 mm while supplying at a rate of 20 kg/hour, forming a reinforcing layer by braiding it with a copper clad steel wire with a diameter of 0.3 mm, and then a 17 mm extrusion die is attached. The cold-resistant, high-flammability polymer composite is injected into the hopper of a single-screw extruder (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃) and extruded to a thickness of 0.9mm at a speed of 20kg/hour. Then, the outer covering layer was formed to complete the production of the cable.

Example 6

Using the cold-resistant, high-flammability polymer composite and cross-linked insulating composition prepared in Example 3, cross-linked insulating composition pellets were injected into a hopper and then placed in a hopper with a diameter of 1.2 Φ mm at the head of an extruder attached to an extrusion die with a diameter of 2.2 Φ mm. While passing through the tin-plated wire, cylinder 1 is extruded at a rate of 22 kg/hour under temperature conditions of 105°C, cylinder 2 at 110°C, cylinder 3 at 115°C, extrusion head at 115°C, and extrusion die at 120°C. An insulated wire is manufactured by passing it through a vulcanization tube maintained at 15 atmospheres at a speed of 30 m/min, then the two strands of the manufactured insulated wire are assembled, and a set is formed by stranding 7 strands of the insulated wire taped with polyethylene terephthalate. The stranded wire and the polypropylene yarn filling are passed together through the taping column of a cable taping machine, taped with polyethylene terephthalate tape, and then braided with tin plating with a diameter of 0.2 mm to form a common shielding layer.

The cold-resistant, high-flammability polymer composite is injected into the hopper and the extrusion head of a single-screw extruder equipped with a 15.2mm extrusion die (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃). The inner covering layer is formed by extruding the bundled wire with the cavity shielding layer formed to a thickness of 1.2 mm while supplying at a rate of 20 kg/hour, forming a reinforcing layer by braiding it with a copper clad steel wire with a diameter of 0.3 mm, and then a 17 mm extrusion die is attached. The cold-resistant, high-flammability polymer composite is injected into the hopper of a single-screw extruder (cylinder 1 at 160℃, cylinder 2 at 170℃, cylinder 3 at 180℃, die 175℃) and extruded to a thickness of 0.9mm at a speed of 20kg/hour. Then, the outer covering layer was formed to complete the production of the cable.

Comparative Example 1-1

The production of the cable was completed in the same manner as in Example 1, except that the siloxane-modified thermoplastic elastomer was not used in manufacturing the cold-resistant, highly flame-resistant polymer composite of Example 1.

Comparative Example 1-2

The production of the cable was completed in the same manner as in Example 1, except that polyolefin elastomer was not used in manufacturing the cold-resistant, highly flame-resistant polymer composite of Example 1.

Comparative Example 1-3

The production of the cable was completed in the same manner as in Example 1, except that the siloxane-modified thermoplastic elastomer was not used in manufacturing the cold-resistant, highly flame-resistant polymer composite of Example 1.

The thermoplastic elastomer composition prepared in this way was manufactured into a 1.5 mm thick specimen at 170°C using a hot press, and the oxygen index, tensile strength, elongation, and oil resistance were measured, and the manufactured polar shipping cable was subjected to a cold bend. (cold bend) was tested and the results are shown in <Table 1>.

Measurement results of each experiment according to the examples

Test Items Example 1 Example 2 Example 3 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Cold Bend (-70℃) pass pass pass fail fail fail Oxygen index (%) 34.5 35.1 35.5 33.1 33 30 Tensile properties Strength (MPa) 14.1 13.9 14.2 13.2 13.3 12.6 Elongation (%) 630 610 607 512 463 455 Oil resistance (IRM oil, 70℃, after 4 hours aging, ±40%) Robbery residual rate (%) 92 93 94 92 80 82 Kidney residual rate (%) 83 81 85 83 72 75

As shown in <Table 1>, it can be confirmed that the cold bend, oxygen index, tensile strength, elongation, icing resistance, oil resistance, etc. of the examples according to the present invention are superior to the comparative examples.

The cold-resistant, high-flammability polymer composite using the siloxane-modified thermoplastic elastomer of the present invention and the polar shipping cable coated with the same maximize the dispersion characteristics of the inorganic filler, so that even if the content of the flame retardant is minimized when mixing the thermoplastic elastomer composition, it has excellent flexibility and flexibility without deteriorating flame retardancy. In addition to being cold-resistant, when applied as an insulating coating for polar ship cables, it has the effect of improving constructability and productivity in addition to electrical, mechanical, and chemical properties, so it has great industrial value.

Claims (7)

A siloxane-modified thermoplastic elastomer manufacturing step of manufacturing a siloxane-modified thermoplastic elastomer by vacuum drying the polymer solution;
A polyolefin elastomer manufacturing step of manufacturing polyolefin elastomer;
A compatibilizer manufacturing step of cooling and recrystallizing the mixture to produce a compatibilizer;
A cold-resistant, highly flammable polymer composite manufacturing step of manufacturing a cold-resistant, highly flammable polymer composite;
A step of manufacturing insulating composition pellets;
A cross-linked insulating composition manufacturing step of manufacturing a cross-linked insulating composition;
The cross-linked insulating composition prepared in the cross-linked insulating composition manufacturing step is administered to a hopper, and then passed through a conductor through the head of an extruder equipped with an extrusion die for 10 to 40 hours. The insulated wire is extruded at a rate of ㎏/hour and passed through a continuous vulcanization pipe maintained at 80~120℃ and 10~20 atmospheres at a speed of 20~50m/min, and the insulating layer is formed through the extrusion vulcanization step. an insulated wire manufacturing step;
A bundled strand manufacturing step of manufacturing a bundled stranded wire by stranding the insulated wire manufactured in the insulated wire manufacturing stage with a bundler;
Joint shielding is performed by passing the aggregate strand manufactured in the aggregate strand manufacturing step and the filler together, and taping the outer periphery with metal tape or metal coating film, or braiding it with metal wire of metal wire, metal plated wire, or alloy wire. A common shielding layer forming step of forming a layered joint line;
The stranded wire with the common shielding layer manufactured in the common shielding layer forming step is passed through a taping column of a cable taping machine and is applied with a binder tape selected from polymer tapes. A taping step of taping;
In an extruder with a molding die attached to the outer periphery of the insulated wire on which the binder tape layer prepared in the taping step is formed, the cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is processed at 5 to 50 kg/hour. An inner coating layer forming step of forming the inner coating layer by extruding at a speed of;
An external reinforcement layer forming step of forming a reinforcement layer by plying and braiding one to two or more types of metal wire, inorganic fiber yarn, or aramid fiber yarn around the outer periphery of the insulated wire on which the inner coating layer is formed in the inner coating layer forming step;
In an extruder in which an extrusion die is attached to the outer periphery of the insulated wire on which the reinforcing layer manufactured in the external reinforcement layer forming step is formed, the cold-resistant, high-flammability polymer composite manufactured in the cold-resistant, high-flammability polymer composite manufacturing step is 5 to 50 kg/kg. A method of manufacturing a polar sailing ship cable coated with a cold-resistant, highly flammable polymer composite using a siloxane-modified thermoplastic elastomer, comprising: an outer coating layer forming step of extruding at the speed of time to form the outer coating layer. A siloxane-modified thermoplastic elastomer manufacturing step of manufacturing a siloxane-modified thermoplastic elastomer by vacuum drying the polymer solution;
A polyolefin elastomer manufacturing step of manufacturing polyolefin elastomer;
A compatibilizer manufacturing step of cooling and recrystallizing the mixture to produce a compatibilizer;
A cold-resistant, highly flammable polymer composite manufacturing step of manufacturing a cold-resistant, highly flammable polymer composite;
A step of manufacturing insulating composition pellets;
A cross-linked insulating composition manufacturing step of manufacturing a cross-linked insulating composition;
10,000 parts by weight of ethylene copolymer, 500 to 2,000 parts by weight of electrically conductive filler, 43 to 64 parts by weight of antioxidant, and 25 to 40 parts by weight of metal stearate lubricant are sequentially added to a mixing mixer in Kneader, Henschel, or Banbury to produce 100 parts by weight. A semiconducting elastomer that produces 3-5mm sized semiconducting elastomer pellets with a surface resistance of 105-108 Ω through extrusion molding by transferring a lump of dough kneaded for 10-60 minutes at a temperature of ~140℃ to a single-screw or twin-screw extruder. Pellet manufacturing step;
Add 10,568 to 12,104 parts by weight of the semiconducting elastomer pellets and 95 to 150 parts by weight of the organic peroxide to a separate mixing mixer of Kneader, Henschel or Banbury and knead at a temperature of 60 to 100°C for 10 to 60 minutes to obtain a crosslinked semiconducting composition. A cross-linked semiconducting composition manufacturing step;
The semiconducting elastomer pellets prepared in the semiconducting elastomer pellet manufacturing step are placed in a first hopper, and the crosslinked insulating composition prepared in the crosslinked insulating composition manufacturing step are placed in a second hopper. The cross-linked semiconducting composition prepared in the step is injected into the third hopper and then passed through the conductor through the head of the extruder equipped with a co-extrusion die at 10 to 40 kg/hour. Peninsula manufactures insulated wires with a semiconducting layer formed through the extrusion vulcanization step by extruding at a speed of 80~120℃ and passing through a continuous vulcanization pipe maintained at 10~20 atm at a speed of 20~50m/min. A step of manufacturing an insulated wire in which all layers are formed;
A shielding layer forming step of forming a shielding layer by taping a metal tape or a metal coating film or braiding it with a metal wire or metal wire around the outer periphery of the insulated wire with the semiconducting layer formed in the insulated wire manufacturing step;
A taping step of passing an insulated wire with a plurality of combined shielding layers and a filler through the taping column of a cable taping machine with a binder tape;
In an extruder with a molding die attached to the outer periphery of the insulated wire on which the binder tape layer prepared in the taping step is formed, the cold-resistant, high-flammability polymer composite prepared in the cold-resistant, high-flammability polymer composite manufacturing step is processed at 5 to 50 kg/hour. An inner coating layer forming step of forming the inner coating layer by extruding at a speed of;
An external reinforcement layer forming step of forming a reinforcement layer by plying and braiding one to two or more types of metal wire, inorganic fiber yarn, or aramid fiber yarn on the outer peripheral edge of the insulated wire on which the internal coating layer prepared in the inner coating layer forming step is formed; ;
In an extruder in which an extrusion die is attached to the outer periphery of the insulated wire on which the reinforcing layer manufactured in the external reinforcement layer forming step is formed, the cold-resistant, high-flammability polymer composite manufactured in the cold-resistant, high-flammability polymer composite manufacturing step is 5 to 50 kg/kg. A method of manufacturing a polar sailing ship cable coated with a cold-resistant, high-flammability polymer composite using a siloxane-modified thermoplastic elastomer, comprising the step of forming an outer coating layer by extruding at the speed of time. According to claim 1 or 2,
The siloxane-modified thermoplastic elastomer manufacturing step of manufacturing the siloxane-modified thermoplastic elastomer by vacuum drying the polymer solution involves a reactor equipped with a stirrer, a temperature controller, a dropping funnel, and a condenser. After adding 1,000 parts by weight of α,ω-hydrogensiloxane, the reactor temperature was raised to 60-100°C while stirring at a speed of 100-500 RPM, and then 0.002-2.0 weight of catalyst was added. parts and supplying 20 to 200 parts by weight of allyl glycidyl ether through a dropping funnel mounted on the reactor for 10 to 60 minutes while maintaining the reactor temperature at 60 to 100°C for 60 to 240 minutes. After proceeding with the reaction, 1,000 parts by weight of alcohol and 100 to 400 parts by weight of amino polyalkylene oxide were added to the reactor, the temperature of the reactor was maintained at 60 to 100°C, and the reactor was reacted at a speed of 100 to 500 RPM. The reaction was allowed to proceed for 60 to 240 minutes while stirring;
In the polyolefin elastomer manufacturing step, purge gas is continuously supplied to a flow reactor equipped with a stirrer and a temperature controller at a rate of 0.5 to 8 L/hour. Zirconium compound is supplied and discharged at a rate of 20,000 to 25,000 g/hour of polymerization solvent, 2,000 to 4,000 g/hour of ethene, and 1,000 to 3,000 g/hour of alkene monomer. A polymerization catalyst selected from 0.01 to 0.1 mmol/hour and an auxiliary catalyst are added at a rate of 0.10 to 0.50 mmol/hour, maintaining the reactor pressure at 1.5 to 2 atmospheres and the temperature at 80 to 110°C. After the polymerization reaction was conducted for 20 hours, alcohol was added to the polymerization reaction liquid extracted from the bottom of the continuous reactor to terminate the reaction, and the reaction mixture was subjected to steam stripping to separate the copolymer from the solvent. Next, drying under reduced pressure at 60-100°C for 12-48 hours;
The compatibilizer production step of manufacturing a compatibilizer by cooling and recrystallizing the mixture involves circulating nitrogen in a reactor equipped with a stirrer, temperature controller, and nitrogen purging equipment, and dissolving the aromatic solvent. After adding 1,000 parts by weight of solvent and 100 to 500 parts by weight of polyolefin resin, the temperature of the reactor is raised to 80 to 150°C and stirred at a speed of 100 to 500 RPM. When the polyolefin resin is completely dissolved, it is added to the reactor. 1 to 15 parts by weight of an anhydride selected from acrylic anhydride, methacrylic anhydride, and maleic anhydride, and a peroxide comound. 1 to 15 parts by weight were added and reacted for 1 to 3 hours;
In the cold-resistant, high-flammability polymer composite manufacturing step, 100,000 parts by weight of polyethylene resin in a mixing mixer, 100,000 to 180,000 parts by weight of polyolefin elastomer prepared in the polyolefin elastomer manufacturing step, and glass transition. 200,000 to 500,000 parts by weight of ethylene-octene block copolymer with a glass transition temperature of -65°C or lower and a tensile strength of 3 to 5 MPa, and 60,000 to 60,000 parts by weight of compatibilizer prepared in the compatibilizer manufacturing stage. 100,000 parts by weight, metal oxide flame retardant surface-treated with silane or fatty acid 400,000 to 800,000 parts by weight, siloxane-modified thermoplastic elastomer manufactured in the manufacturing stage 10,000 to 40,000 parts by weight, silane 80 to 80 parts by sequentially adding 3,000 to 15,000 parts by weight, polysiloxane 12,000 to 35,000 parts by weight, antioxidant 5,000 to 9,000 parts by weight, pigment 10,000 to 40,000 parts by weight, and lubricant 1,500 to 4,000 parts by weight. ~170 A lump of melt-mixed dough is transferred to a single-screw or twin-screw extruder for 10 to 60 minutes at a temperature of ℃ to produce composition pellets of 2 to 5 mm in size through extrusion, and then dried in an oven at 60 to 80 ℃ and adjusted to particle size. Going through a selection process;
In the step of manufacturing the insulating composition pellets, 100,000 parts by weight of ethylene polymer or ethylene copolymer in a mixing mixer of Kneader, Henschel, or Banbury, and surface-treated with silane or fatty acid. 60,000 to 100,000 parts by weight of metal oxide flame retardant, 100 to 12,000 parts by weight of reinforcing agent, 50 to 200 parts by weight of antioxidant, and 100 to 1,200 parts by weight of lubricant are sequentially administered and kneaded for 5 to 60 minutes at a temperature of 80 to 130℃. or transferring to a twin-screw extruder to produce insulation composition pellets of 3 to 5 mm in size through extrusion molding;
In the crosslinked insulating composition manufacturing step, 100,000 parts by weight of the insulating composition pellets and organic peroxide or irradiation crosslinking agent are added to a separate kneader, Henschel, or Banbury mixing mixer. Cold resistance and high flame resistance using siloxane-modified thermoplastic elastomer, which is characterized by administering 1,000 to 20,000 parts by weight of a crosslinking agent selected from silane-crosslinking catalysts and kneading for 10 to 60 minutes at a temperature of 60 to 100°C. Method for manufacturing polar navigation ship cable coated with polymer composite. A siloxane-modified thermoplastic elastomer obtained by vacuum drying the polymer solution;
A polyolefin elastomer obtained by separating/drying the copolymer from a solvent;
A compatibilizer that cooled and recrystallized the mixture;
A cold-resistant, highly flame-resistant polymer composite;
Insulating composition pellets;
A cross-linked insulating composition;
The cross-linked insulating composition is injected into a hopper and then extruded at a rate of 10 to 40 kg/hour while passing a conductor through the head of an extruder equipped with an extrusion die to insulate. a layered insulated wire;
a bundled wire in which the insulated wire is twisted with a bundler;
A common shielding layer formed by passing the collective strand and the filler together and taping the outer circumference thereof with a metal tape or a metal coating film or braiding it with a metal wire of a metal wire, metal plated wire, or alloy wire;
A taping step of taping the combined wire on which the common shielding layer is formed with a polymer tape using a taping column of a cable taping machine;
an inner coating layer formed on the outer periphery of the tape layer by extruding a cold-resistant, high-flammability polymer composite at a rate of 5 to 50 kg/hour;
An external reinforcing layer made of metal wire, inorganic fiber yarn, or aramid fiber yarn, individually or two or more, and braided on the outer periphery of the inner coating layer;
Covered with a cold-resistant, highly flammable polymer composite using a siloxane-modified thermoplastic elastomer, characterized in that it consists of an outer coating layer formed by extruding a cold-resistant, highly flammable polymer composite on the outer periphery of the outer reinforcing layer at a rate of 5 to 50 kg / hour. Polar navigation ship cable. A siloxane-modified thermoplastic elastomer obtained by vacuum drying the polymer solution;
A polyolefin elastomer obtained by separating/drying the copolymer from a solvent;
A compatibilizer that cooled and recrystallized the mixture;
A cold-resistant, highly flame-resistant polymer composite;
Insulating composition pellets;
Cross-linked insulating composition;.
10,000 parts by weight of ethylene copolymer, 500 to 2,000 parts by weight of electrically conductive filler, 43 to 64 parts by weight of antioxidant, and 25 to 40 parts by weight of metal stearate lubricant are kneaded into a lump of dough with a surface resistance of 105 to 108 Ω. Semiconducting elastomer pellets made of semiconducting elastomer pellets with a size of ~5 mm;
A crosslinked semiconducting composition obtained by mixing 10,568 to 12,104 parts by weight of the semiconducting elastomer pellet and 95 to 150 parts by weight of organic peroxide;
The semiconducting elastomer pellets prepared in the semiconducting elastomer pellet manufacturing step are placed in a first hopper, and the crosslinked insulating composition prepared in the crosslinked insulating composition manufacturing step are placed in a second hopper. The cross-linked semiconducting composition prepared in the step is injected into the third hopper and then passed through the conductor through the head of the extruder equipped with a co-extrusion die at 10 to 40 kg/hour. An insulated wire with a semiconducting layer formed by extruding at a speed of 80 to 120°C and passing through a continuous vulcanization pipe maintained at 10 to 20 atm at a speed of 20 to 50 m/min;
The outer periphery of the insulated wire on which the semiconducting layer is formed is taped with a metal tape or metal coating film or braided with a metal wire or metal wire to form a shielding layer, and the outer periphery taped with a binder tape is manufactured in the highly flammable polymer composite manufacturing step. An inner coating layer formed by extruding a cold-resistant, highly flame-resistant polymer composite at a rate of 5 to 50 kg/hour;
An external reinforcing layer made of single or two or more types of metal wire, inorganic fiber yarn, or aramid fiber yarn, and braided on the outer peripheral edge of the inner coating;
It is a cold-resistant, highly flammable polymer composite using siloxane-modified thermoplastic elasticity, characterized in that it consists of an outer coating layer in which a cold-resistant, highly flammable polymer composite is extruded at a rate of 5 to 50 kg/hour on the outer periphery of the external reinforcement layer to form the outer coating layer. Sheathed polar operating ship cables. According to clause 4 or 5,
The siloxane-modified thermoplastic elastomer contains 1,000 parts by weight of α,ω-hydrogensiloxane, 0.002 to 2.0 parts by weight of catalyst, and 20 to 200 parts by weight of allyl glycidyl ether. A polymer solution obtained by stirring 1,000 parts by weight of alcohol and 100 to 400 parts by weight of polyalkylene oxide was vacuum dried;
The polyolefin elastomer obtained by separating/drying the copolymer from the solvent is discharged by continuously supplying purge gas at a rate of 0.5 to 8 L/hour, while discharging 20,000 to 25,000 g/hour of polymerization solvent and ethene ( ethene) 2,000 to 4,000 g/hour, alkene monomer 1,000 to 3,000 g/hour, polymerization catalyst selected from zirconium compound 0.01 to 0.1 mmol/hour and cocatalyst. After the polymerization reaction was carried out by adding at a rate of 0.10 to 0.50 mmol/hour, the reaction was terminated by adding alcohol, and the reaction mixture was subjected to steam stripping;
The compatibilizer obtained by cooling and recrystallizing the mixture is dissolved in 1,000 parts by weight of an aromatic solvent and 100 to 500 parts by weight of polyolefin resin, and then dissolved in acrylic anhydride or methacrylic anhydride. 1 to 15 parts by weight of an anhydride selected from methacrylic anhydride and maleic anhydride and 1 to 15 parts by weight of a peroxide compound were added and reacted;
The cold-resistant, high-flammability polymer composite includes 100,000 parts by weight of polyethylene resin and 100,000 to 180,000 parts by weight of polyolefin elastomer, a glass transition temperature of -65°C or lower, and ethylene with a tensile strength of 3 to 5 MPa. - 200,000 to 500,000 parts by weight of ethylene-octene block copolymer, 60,000 to 100,000 parts by weight of compatibilizer, 400,000 to 800,000 parts by weight of metal oxide flame retardant surface treated with silane or fatty acid, siloxane 10,000 to 40,000 parts by weight of siloxane-modified thermoplastic elastomer, 3,000 to 15,000 parts by weight of silane, 12,000 to 35,000 parts by weight of polysiloxane, 5,000 to 9,000 parts by weight of antioxidant, and pigment ) 10,000 to 40,000 parts by weight and 1,500 to 4,000 parts by weight of lubricant are melt-mixed;
The insulating composition pellets include 100,000 parts by weight of ethylene polymer or ethylene copolymer, 60,000 to 100,000 parts by weight of a metal oxide flame retardant surface-treated with silane or fatty acid, 100 to 12,000 parts by weight of reinforcing agent, and antioxidant. A lump of dough kneaded with 50 to 200 parts by weight and 100 to 1,200 parts by weight of lubricant was manufactured into pellets with a size of 3 to 5 mm;
The crosslinked insulating composition is a mixture of 100,000 parts by weight of insulating composition pellets and 1,000 to 20,000 parts by weight of a crosslinking agent selected from organic peroxide, irradiation crosslinking agent, and silane-crosslinking catalyst. A polar sailing ship cable coated with a cold-resistant, high-flammability polymer composite using siloxane-modified thermoplastic elasticity. According to clause 6,
The polymerization catalyst is bis(indenyl)zirconium dichloride, dimethylsilylene bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride [dimethylsilylene bis( 4,5,6,7- tetrahydroindenyl)zirconium dichloride], bis(1-methyl, 3-n-butylcyclopentadienyl)zirconium dichloride[bis(1-methyl,3-n-butylcyclpentadienyl)zirconium dichloride], Dimethylsilylene bis(indenyl)zirconium dichloride [dimethylsilylene bis(indenyl)zirconium dichloride], dimethylsilylene bis(2-methylindenyl)zirconium dichloride [dimethylsilylene bis(2-methyl indenyl)zirconium dichloride], ethylene bis selected from zirconium compounds such as ethylenebisindenylzirconium dichloride and bis(2-propylindenyl)zirconium dichloride;
The cocatalyst is selected from organoaluminoxanes such as methylaluminoxane and methylisobutylaluminoxane;
The anhydride may be selected from acrylic anhydride, methacrylic anhydride, and maleic anhydride;
The peroxide compound is selected from benzoyl peroxide, dichlorobenzoyl peroxide, and dicumyl peroxide;
The silane is tetramethoxy silane, methyltrimethoxysilane, propyltrimethoxy silane, tetraethoxy silane, or methyltriethoxysilane. being selected from;
The polysiloxane is selected from polydimethylsiloxane, polydiphenylsiloxane, polymethylhydrogensiloxane, polymethylphenylsiloxane, etc.;
The antioxidant of the cold-resistant, high-flammability polymer composite is octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate [octadecyl-3-(3,5-di-tert) -butyl-4-hydroxyphenyl)propionate], 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-meta-cresol)[4,4', 4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol)], 6,6'-di-tert-butyl-4,4'-butylidenedi-meta-cresol [6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl ) propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane{3,9-Bis{2-[3-(3-tert-butyl-4 -hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane}, 1,3,5-tris(3,5-di-tert-butyl- 4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene [1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene], etc. or two or more types are selected;
The metal stearate lubricant is selected from calcium stearate, magnesium stearate, etc.;
The ethylene polymer or ethylene copolymer is polyethylene, ethylene-propylene copolymer, or ethylene-propylene-diene copolymer. being chosen;
The reinforcing agent is selected from silica, carbon black, magnesium carbonate, aluminum silicate, magnesium silicate, and diatomaceous earth;
The antioxidant of the insulating composition pellet is thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][thiodiethylene bis(3-(3,5-di) -tert-butyl-4-hydroxyphenyl)propionate], thiodipropionic acid dioctadecylester, distearyl thiodipropionate, 3-mercaptopropionic acid A polar sailing ship cable coated with a cold-resistant, highly flammable polymer composite using siloxane-modified thermoplastic elasticity, characterized in that it is composed of sulfur compounds such as (3-mercaptopropionic acid) used alone or in a mixture of two or more types.