A high antioxidant network power supply integrated cable

Abstract

The present invention discloses a high-oxidation-resistant network power integrated cable, which relates to the technical field of cables. First, ethyl imidazole-4-carboxylate and 4-acetylimidazole are used to react to form a β-diketone-based diimidazolylmethane compound, which is bridged with acetylacetone to obtain a binuclear nickel complex. This is used as a chemical vapor deposition precursor to perform a pre-infiltration treatment on the surface of a copper wire conductor, and then a segmented heating treatment is carried out to form a nickel protective layer, improving the oxidation resistance of the conductor. And during the segmented heating treatment, the ambient gas atmosphere is continuously changed, so that during the subsequent plasma treatment process, a carbon film can be formed to further improve the oxidation resistance of the conductor. Finally, a pressure treatment is carried out to obtain oxidation-resistant copper wires. Using these as the cable cores, a power cable and a network cable are respectively manufactured, and then the two are stranded into a wire core. The double-layer co-extrusion technology is adopted to coat a flame-retardant foaming layer and a sheath layer on its surface.

Description

Technical Field

[0001] The present invention relates to the technical field of cables, and specifically to a highly antioxidant network power integrated cable. Background Art

[0002] With the rapid development of economy and society, more and more communities and office buildings use the network, and the network cables used are gradually increasing. However, the common network cables on the market still need to be equipped with power cables separately, which are not suitable for narrow environments, and it is easy to get messy and difficult to repair when multiple lines are used crosswise.

[0003] As a commonly used line material, cables are widely used in daily production and life. During daily use, the usage environment of cables is extremely variable. Therefore, in actual use, it is also very easy to be damaged in various ways due to environmental changes. When encountering water or other situations during use, the conductor is extremely likely to be oxidized, thereby causing damage to the conductor and affecting its actual use. Summary of the Invention

[0004] The purpose of the present invention is to provide a highly antioxidant network power integrated cable to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions: A highly antioxidant network power integrated cable, and the preparation method of the highly antioxidant network power integrated cable includes the following steps:

[0006] (1) Stranding 2 power cables and 1 network cable to form a core;

[0007] (2) Heating and melting 100 - 220 parts of cross-linked polyethylene resin and 80 - 120 parts of low-density polyethylene at 120 - 130 °C, adding 30 - 45 parts of additives, 10 - 15 parts of polyethylene wax, and stirring at 1000 - 1500 rpm for 20 - 30 min to obtain a sheath material fluid; heating and melting 60 - 80 parts of low-density polyethylene and 80 - 100 parts of high-density polyethylene at 140 - 165 °C, then adding 0.6 - 1.2 parts of zinc stearate, 1 - 2 parts of antioxidant 1010, 0.3 - 0.7 parts of talcum powder, and 30 - 40 parts of flame retardant to obtain a pre-foaming fluid; using a double-layer co-extrusion machine, feeding the sheath material fluid into the feeding port of the outer mold, feeding the pre-foaming fluid into the feeding port of the inner mold, and installing opposing CO 2 inflation heads at the end of the extrusion port of the inner mold, starting to run the wire, and at the same time starting the feeding of the inner and outer layers. The wire running speed is 80 - 100 m / min, the extrusion temperature is 145 - 205 °C, and after extrusion is completed, keep it warm at 155 - 180 °C for 15 - 30 min to obtain the highly antioxidant network power integrated cable.

[0008] Further, the core of the power cable in step (1) is composed of 40 to 60 antioxidant copper wires with a diameter of 0.12 to 0.20 mm, which are stranded in a regular arrangement stranding method with a stranding pitch diameter ratio of 10 to 15 times. The outer periphery of the core is coated with a low-density polyethylene insulating layer, and the thickness of the insulating layer is 0.8 to 1.2 mm.

[0009] Further, the core of the network cable in step (1) is stranded by 10 to 15 antioxidant copper wires with a diameter of 0.12 to 0.20 mm, the stranding pitch diameter ratio is 9 to 12 times, and the outer periphery of the core is successively coated with a low-density polyethylene insulating layer and a braided layer. The thickness of the insulating layer is 1.0 to 1.4 mm.

[0010] Further, the braided layer uses antioxidant copper wires with a diameter of 0.10 to 0.12 mm, the braiding coverage rate is 92 to 95%, and the braiding angle is 30 to 50°.

[0011] Further, the preparation method of the antioxidant copper wire is as follows:

[0012] a. Heat 100 to 120 parts of ethyl imidazole-4-carboxylate and 8 to 14 parts of 4-acetylimidazole to 160 to 163 °C under stirring at 50 rpm, add 50 to 60 parts of ethanol solution within 2 h. The mass ratio of absolute ethanol to metallic sodium in the ethanol solution is 47:3.5. After the dropping is completed, continue to stir until all the ethanol escapes, cool to room temperature, add 15 to 22 parts of deionized water, continue to stir for 10 to 30 min, then add 22 to 30 parts of 10% sulfuric acid solution, continue to stir for 20 to 45 min, add 5% sodium bicarbonate solution until the pH of the reaction solution is 7 to 8, separate the liquid, separate the oil layer, wash the organic phase with 40 to 50 parts of deionized water, then extract with anhydrous ether, take the organic phase, dry it with anhydrous sodium sulfate for 3 to 5 h, filter, place it in a 50 °C water bath, distill for 40 to 50 min, and then dry at 85 °C under a vacuum of 1.1×10 3 Pa and dry for 2 to 3 h to obtain the diimidazoleformylmethane compound;

[0013] b. Mix 12 to 13 parts of the diimidazoleformylmethane compound, 6 to 7 parts of acetylacetone, 16 to 20 parts of nickel perchlorate, 880 to 950 parts of methanol, and 310 to 420 parts of deionized water, stir at 80 to 100 rpm for 30 min, add 8 drops of triethylamine, react at 55 to 62 °C for 4 to 6 h, then cool to room temperature, filter, take the filtrate, wash it 3 times with deionized water and methanol respectively, and dry at 60 °C for 6 h to obtain the binuclear nickel complex;

[0014] c. Polish the surface of the pure copper wire until it is shiny, and then successively place it in acetone, ethanol, and hydrochloric acid with a mass fraction of 5% for ultrasonic cleaning. The ultrasonic power is 400 - 600 W, and the cleaning time for each time is 10 - 20 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 1 - 5 Pa. Connect a gas source bottle outside the carbon dioxide plasma generator, place the binuclear nickel complex in the gas source bottle, heat the gas source bottle to a temperature of 185 °C, and then introduce argon and the binuclear nickel complex into the cavity at a flow rate of 120 mL / min and 60 mL / min respectively until the pressure in the cavity is 350 - 450 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min, and at the same time heat up at a rate of 8 - 15 °C / min to 300 - 350 °C. After maintaining the temperature for 30 min, stop introducing argon, oxygen, and the binuclear nickel complex, start pumping air, and at the same time introduce carbon dioxide at a flow rate of 100 mL / min and maintain it for 30 - 40 min. Stop introducing carbon dioxide, evacuate to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity is 600 - 700 Pa and maintain it for 1 - 3 min. Then evacuate to a vacuum degree of 80 Pa and process it at a power of 200 - 300 W for 20 - 30 min. Then heat-treat it at 650 - 680 °C for 25 - 35 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 65 - 85%, and the wire drawing temperature is 320 - 380 °C to obtain the antioxidant copper wire.

[0015] Further, the auxiliary agent in step (2) includes 8 - 15 parts of barium - zinc composite stabilizer, 0.6 - 1.4 parts of stearic acid, 5 - 9 parts of carbon black, 1 - 3 parts of curing agent DCP, 10 - 15 parts of vinyltrimethoxysilane, and 1 - 2 parts of antioxidant 1010.

[0016] Further, the flame retardant in step (2) includes 10 - 15 parts of 800 - mesh expanded graphite, 10 - 15 parts of 800 - mesh zeolite powder, 6 - 9 parts of hexaisopropoxycyclotriphosphazene, 0.1 - 0.5 parts of isopropyltris(dioctylpyrophosphato)titanate, 1 - 3 parts of vinyltrimethoxysilane, 10 - 20 parts of polybutyl methacrylate, 10 - 25 parts of vinyl silicone oil, and 8 - 12 parts of molybdenum oxide.

[0017] Further, the model of the low - density polyethylene is LDPE1C7A, and the melt index of the high - density polyethylene is 0.5 ± 0.05 g / 10 min.

[0018] Further, the CO 2 charging pressure in step (2) is 20 - 30 MPa, and the mass percentage of CO 2 in the pre - foaming fluid is 2 - 3%.

[0019] Furthermore, the sheath thickness of the highly anti-oxidation network power integrated cable is 0.8 to 1.3 cm, and the thickness of the foaming layer is 3 to 5 cm.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] The present invention twists two power cables and one network cable to form a wire core, and adopts double-layer co-extrusion technology to cover the surface with a flame-retardant foaming layer and a sheath layer to improve the flame retardancy and mechanical properties of the cable. Both the power cable and the network cable use anti-oxidation copper wire as the cable core, thereby achieving an anti-oxidation effect.

[0022] First, the flame retardant foam layer is made of polyethylene, nucleating agent, foaming aid, and flame retardant, which are extruded outward in a molten state, and the inner wall of the extrusion port is connected with CO 2 The inflation mechanism cooperates with the extrusion of the extruder head to make the carbon dioxide foam rapidly inside the polyethylene, forming a foaming layer on the surface of the wire core, making the wire core diameter rounded, and at the same time, enhancing the mechanical properties of the cable.

[0023] Secondly, the present invention grinds and polishes the copper wire conductor, performs acetone degreasing and hydrochloric acid activation in sequence, and then uses imidazole-4-carboxylic acid ethyl ester and 4-acetylimidazole to react to form a β-diketone diimidazole formyl methane compound, and uses the diketone structure of the compound to bridge with acetylacetone to obtain a binuclear nickel complex, which is used as a chemical vapor deposition precursor, and the temperature and vapor pressure are controlled to ensure the volatility and thermal stability of the precursor, and a pre-infiltration treatment is performed on the surface of the copper wire conductor to diffusely deposit a layer of nickel-containing precursor on the surface. Polar groups such as N and O and unsaturated π bonds in the molecular structure of the nickel-containing precursor can enter the empty orbit of copper to form a coordination bond, thereby being adsorbed on the surface of the copper wire conductor. At the same time, relying on the molecular structure effect of the nickel-containing precursor, it can be evenly dispersed on the surface of the copper wire conductor, improving the problem of uneven dispersion of nickel elements on the surface of the copper wire conductor during the traditional deposition process. Then, a segmented heating treatment is performed to decompose and form a nickel protective layer to improve the oxidation resistance of the conductor. In the segmented heating treatment process, the ambient gas atmosphere is continuously changed, so that in the subsequent plasma treatment process, a carbon film is formed on the surface of the nickel protective layer, further improving the oxidation resistance of the conductor while ensuring the conductivity of the conductor. Finally, a pressurization treatment is performed to increase the densification of the conductor surface, while promoting the reaction and fusion of the Cu, Ni, and C elements, further improving the oxidation resistance of the conductor. DETAILED DESCRIPTION

[0024] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0025] In order to more clearly illustrate the method provided by the present invention, the following embodiments are used for detailed description. The test methods for each index of the antioxidant copper wire produced in the following embodiments are as follows:

[0026] Antioxidation: The resistivity is tested according to GB / T2039, and then a salt spray test is carried out for 48h to observe its oxidation degree.

[0027] Example 1

[0028] (1) 100 parts of ethyl imidazole-4-carboxylate and 8 parts of 4-acetylimidazole are heated to 160 °C under stirring at 50 rpm. 5 parts of an ethanol solution are added within 2 h. The mass ratio of absolute ethanol to metallic sodium in the ethanol solution is 47:3.5. After the dropping is completed, stirring is continued until all the ethanol escapes. It is cooled to room temperature, 15 parts of deionized water are added, and stirring is continued for 10 min. Then 22 parts of a 10% sulfuric acid solution by mass is added, and stirring is continued for 20 min. A 5% sodium bicarbonate solution by mass is added until the pH of the reaction solution is 7. Liquid separation is carried out, and the oil layer is separated out. The organic phase is washed with 40 parts of deionized water, and then extracted with anhydrous ether. The organic phase is taken, dried with anhydrous sodium sulfate for 3 h, filtered, placed in a water bath at 50 °C, distilled for 40 min, and then dried at a vacuum degree of 1.1×10 3 Pa and 85 °C for 2 h to obtain a diimidazoleformylmethane compound;

[0029] (2) 12 parts of the diimidazoleformylmethane compound, 6 parts of acetylacetone, 16 parts of nickel perchlorate, 880 parts of methanol, and 310 parts of deionized water are mixed, stirred at 80 rpm for 30 min, 8 drops of triethylamine are added, and after reacting at 55 °C for 4 h, it is cooled to room temperature, filtered, and the filtrate is taken and washed 3 times with deionized water and methanol respectively, and dried at 60 °C for 6 h to obtain a binuclear nickel complex;

[0030] (3) Polish the surface of the pure copper wire until it is shiny. Then, place it successively in acetone, ethanol, and 5% hydrochloric acid for ultrasonic cleaning. The ultrasonic power is 400 W, and the cleaning time for each time is 10 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 1 Pa. Connect a gas source bottle outside the carbon dioxide plasma generator, place the binuclear nickel complex in the gas source bottle, heat the gas source bottle to a temperature of 185 °C, and then introduce argon and the binuclear nickel complex into the cavity at a flow rate of 120 mL / min and 60 mL / min respectively until the pressure in the cavity is 350 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min, and at the same time heat up to 300 °C at a rate of 8 °C / min. After holding for 30 min, stop introducing argon, oxygen, and the binuclear nickel complex, start pumping, and at the same time introduce carbon dioxide at a flow rate of 100 mL / min and maintain for 30 min. Stop introducing carbon dioxide, evacuate to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity is 600 Pa, maintain for 1 min, then evacuate to a vacuum degree of 80 Pa, process for 20 min at a power of 200 W, then heat-treat at 650 °C for 25 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 65%, and the wire drawing temperature is 320 °C to obtain the antioxidant copper wire;

[0031] (4) Strands 40 antioxidant copper wires with a diameter of 0.20 mm in a regular arrangement stranding method, and the stranding pitch diameter ratio is 10 times to obtain the power cable core. Then, coat the outer periphery of the core with a low-density polyethylene insulation layer with a thickness of 0.8 mm to obtain the power cable;

[0032] (5) Strands 10 antioxidant copper wires with a diameter of 0.20 mm to obtain the network cable core. The stranding pitch diameter ratio is 9 times. The outer periphery of the network cable core is successively coated with a low-density polyethylene insulation layer with a thickness of 1 mm and a braided layer to obtain the network cable; the braided layer uses antioxidant copper wires with a diameter of 0.1 mm, the braiding coverage rate is 92%, and the braiding angle is 30°;

[0033] (6) Strands 2 power cables and 1 network cable to form a core;

[0034] (7) Heat and melt 100 parts of cross-linked polyethylene resin and 80 parts of low-density polyethylene at 120 °C, add 30 parts of additives and 10 parts of polyethylene wax, and stir at 1000 rpm for 20 min to obtain the sheath material fluid; heat and melt 60 parts of low-density polyethylene and 80 parts of high-density polyethylene at 140 °C, and then add 0.6 part of zinc stearate, 1 part of antioxidant 1010, 0.3 part of talc powder, and 30 parts of flame retardant to obtain the pre-foaming fluid; use a double-layer co-extrusion machine to send the sheath material fluid into the inlet of the outer mold, and send the pre-foaming fluid into the inlet of the inner mold. An opposing CO 2 inflation head is installed at the end of the extrusion port of the inner mold, CO2 The charging pressure is 20 MPa, and CO is charged. 2 It accounts for 2% of the mass percentage of the pre-expanded fluid. Start the wire routing, and at the same time turn on the feeding of the inner and outer layers. The wire routing speed is 80 m / min, and the extrusion temperature is 145 - 205 °C. After extrusion is completed, keep it at 155 °C for 30 min to obtain a highly antioxidant network power integrated cable with a sheath thickness of 0.8 cm and a foaming layer thickness of 3 cm; the auxiliaries include 8 parts of barium-zinc composite stabilizer, 0.6 part of stearic acid, 5 parts of carbon black, 1 part of vulcanizing agent DCP, 10 parts of vinyltrimethoxysilane, and 1 part of antioxidant 1010; the flame retardant includes 10 parts of 800-mesh expanded graphite, 10 parts of 800-mesh zeolite powder, 6 parts of hexaisopropoxycyclotriphosphazene, 0.1 part of isopropyltri(dioctylpyrophosphato)titanate, 1 - 3 parts of vinyltrimethoxysilane, 10 parts of polybutyl methacrylate, 10 parts of vinyl silicone oil, and 8 parts of molybdenum oxide.

[0035] Example 2

[0036] (1) Heat 110 parts of ethyl imidazole-4-carboxylate and 11 parts of 4-acetylimidazole to 161 °C with stirring at 50 rpm, add 55 parts of ethanol solution within 2 h. The mass ratio of absolute ethanol to metallic sodium in the ethanol solution is 47:3.5. After the dropping is completed, continue stirring until all the ethanol escapes, cool to room temperature, add 19 parts of deionized water, continue stirring for 20 min, then add 26 parts of 10% sulfuric acid solution by mass, continue stirring for 33 min, add 5% sodium bicarbonate solution by mass until the pH of the reaction solution is 7.5, separate the layers, separate the oil layer, wash the organic phase with 45 parts of deionized water, then extract with anhydrous ether, take the organic phase, dry it with anhydrous sodium sulfate for 4 h, filter, place it in a 50 °C water bath, distill for 45 min, and then dry at a vacuum of 1.1×10 3 Pa and 85 °C for 2.5 h to obtain the compound of diimidazolylmethane.

[0037] (2) Mix 12.5 parts of the compound of diimidazolylmethane, 6.5 parts of acetylacetone, 16 - 20 parts of nickel perchlorate, 915 parts of methanol, and 388 parts of deionized water, stir at 90 rpm for 30 min, add 8 drops of triethylamine, react at 59 °C for 5 h, then cool to room temperature, filter, take the filtrate, wash it 3 times with deionized water and methanol respectively, and dry at 60 °C for 6 h to obtain the binuclear nickel complex.

[0038] (3) Polish the surface of the pure copper wire until it is shiny. Then, successively place it in acetone, ethanol, and 5% hydrochloric acid by mass for ultrasonic cleaning. The ultrasonic power is 500 W, and the cleaning time for each time is 15 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 3 Pa. Connect a gas source bottle outside the carbon dioxide plasma generator, place the binuclear nickel complex in the gas source bottle, heat the gas source bottle to a temperature of 185 °C, and then introduce argon and the binuclear nickel complex into the cavity at a flow rate of 120 mL / min and 60 mL / min respectively until the pressure in the cavity reaches 400 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min, and at the same time heat it up to 325 °C at a rate of 11 °C / min. After holding for 30 min, stop introducing argon, oxygen, and the binuclear nickel complex, start pumping air, and at the same time introduce carbon dioxide at a flow rate of 100 mL / min and maintain it for 35 min. Stop introducing carbon dioxide, evacuate to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity reaches 650 Pa and maintain it for 2 min. Then evacuate to a vacuum degree of 80 Pa and process it at a power of 250 W for 25 min. Then heat-treat it at 665 °C for 30 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 70%, and the wire drawing temperature is 360 °C to obtain the antioxidant copper wire;

[0039] (4) Strangle 50 antioxidant copper wires with a diameter of 0.16 mm in a regular arrangement stranding method, and the stranding pitch diameter ratio is 12 times to obtain the power cable core. Then, coat the outer circumference of the core with a low-density polyethylene insulating layer with a thickness of 1 mm to obtain the power cable;

[0040] (5) Strangle 12 antioxidant copper wires with a diameter of 0.16 mm to obtain the network cable core. The stranding pitch diameter ratio is 10 times. The outer circumference of the network cable core is successively coated with a low-density polyethylene insulating layer with a thickness of 1.2 mm and a braided layer to obtain the network cable; the braided layer uses antioxidant copper wires with a diameter of 0.11 mm, the braiding coverage rate is 95%, and the braiding angle is 40°;

[0041] (6) Strangle 2 power cables and 1 network cable to form a wire core;

[0042] (7) Heat and melt 180 parts of cross-linked polyethylene resin and 100 parts of low-density polyethylene at 126 °C, add 38 parts of additives and 12 parts of polyethylene wax, and stir at 1200 rpm for 25 min to obtain the sheath material fluid; heat and melt 70 parts of low-density polyethylene and 90 parts of high-density polyethylene at 152 °C, and then add 0.9 part of zinc stearate, 1.5 parts of antioxidant 1010, 0.5 part of talc powder, and 35 parts of flame retardant to obtain the pre-foaming fluid; use a double-layer co-extrusion machine to send the sheath material fluid into the inlet of the outer mold and the pre-foaming fluid into the inlet of the inner mold. The end of the extrusion port of the inner mold is equipped with opposing CO 2Inflatable head, CO 2 The charging pressure is 25 MPa, and CO is charged 2 It accounts for 2.5% of the mass percentage of the pre-expanded fluid. Start the wire feeding, and at the same time turn on the inner and outer layer feeding. The wire feeding speed is 90 m / min, and the extrusion temperature is 145 - 205 °C. After extrusion is completed, keep it warm at 162 °C for 24 min to obtain a highly antioxidant network power integrated cable with a sheath thickness of 1.1 cm and a foaming layer thickness of 4 cm; The additives include 11 parts of barium zinc composite stabilizer, 1 part of stearic acid, 7 parts of carbon black, 2 parts of vulcanizing agent DCP, 12 parts of vinyltrimethoxysilane, and 1.5 parts of antioxidant 1010; The flame retardant includes 12 parts of 800-mesh expanded graphite, 13 parts of 800-mesh zeolite powder, 8 parts of hexaisopropoxycyclotriphosphazene, 0.3 part of isopropyltri(dioctylpyrophosphato)titanate, 2 parts of vinyltrimethoxysilane, 15 parts of polybutyl methacrylate, 18 parts of vinyl silicone oil, and 10 parts of molybdenum oxide.

[0043] Example 3

[0044] (1) Heat 120 parts of ethyl imidazole-4-carboxylate and 14 parts of 4-acetylimidazole to 163 °C with stirring at 50 rpm. Add 60 parts of ethanol solution within 2 h. The mass ratio of absolute ethanol to sodium metal in the ethanol solution is 47:3.5. After the dropping is completed, continue stirring until all the ethanol escapes. Cool to room temperature, add 22 parts of deionized water, continue stirring for 30 min, then add 30 parts of 10% sulfuric acid solution by mass fraction, continue stirring for 45 min, add 5% sodium bicarbonate solution by mass fraction until the pH of the reaction solution is 8, separate the liquid, separate the oil layer, wash the organic phase with 50 parts of deionized water, then extract with anhydrous ether, take the organic phase, dry it with anhydrous sodium sulfate for 5 h, filter, place it in a 50 °C water bath, distill for 50 min, and then dry at a vacuum degree of 1.1×10 3 Pa and 85 °C for 3 h to obtain the compound of diimidazoleformylmethane;

[0045] (2) Mix 13 parts of diimidazoleformylmethane compound, 7 parts of acetylacetone, 20 parts of nickel perchlorate, 950 parts of methanol, and 420 parts of deionized water, stir at 100 rpm for 30 min, add 8 drops of triethylamine, react at 62 °C for 6 h, then cool to room temperature, filter, take the filtrate, wash it 3 times with deionized water and methanol respectively, and dry at 60 °C for 6 h to obtain the binuclear nickel complex;

[0046] (3) Polish the surface of the pure copper wire until it is shiny. Then, successively place it in acetone, ethanol, and 5% hydrochloric acid by mass for ultrasonic cleaning. The ultrasonic power is 600 W, and the cleaning time for each time is 20 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 5 Pa. The carbon dioxide plasma generator is externally connected to a gas source bottle, and the binuclear nickel complex is placed in the gas source bottle. The heating temperature of the gas source bottle is 185 °C. Then, introduce argon and the binuclear nickel complex into the cavity at a flow rate of 120 mL / min and 60 mL / min respectively until the pressure in the cavity is 450 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min, and at the same time, raise the temperature to 350 °C at a rate of 15 °C / min. After holding for 30 min, stop introducing argon, oxygen, and the binuclear nickel complex, start pumping air, and at the same time, introduce carbon dioxide at a flow rate of 100 mL / min and maintain for 40 min. Stop introducing carbon dioxide, evacuate to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity is 700 Pa and maintain for 3 min. Then, evacuate to a vacuum degree of 80 Pa and process at a power of 300 W for 30 min. Then, perform heat treatment at 680 °C for 35 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 85%, and the wire drawing temperature is 380 °C to obtain the antioxidant copper wire;

[0047] (4) Strands 60 antioxidant copper wires with a diameter of 0.12 mm in a regular arrangement stranding method, and the stranding pitch diameter ratio is 15 times to obtain the power cable core. Then, coat the outer periphery of the core with a low-density polyethylene insulation layer with a thickness of 1.2 mm to obtain the power cable;

[0048] (5) Strands 15 antioxidant copper wires with a diameter of 0.12 mm to obtain the network cable core. The stranding pitch diameter ratio is 12 times. The outer periphery of the network cable core is successively coated with a low-density polyethylene insulation layer with a thickness of 1.4 mm and a braided layer to obtain the network cable; the braided layer uses antioxidant copper wires with a diameter of 0.12 mm, the braiding coverage rate is 95%, and the braiding angle is 50°;

[0049] (6) Strands 2 power cables and 1 network cable to form a wire core;

[0050] (7) Heat 220 parts of cross-linked polyethylene resin and 120 parts of low-density polyethylene to melt at 130 °C, add 45 parts of additives and 15 parts of polyethylene wax, and stir at 1500 rpm for 30 min to obtain the sheath material fluid; heat 80 parts of low-density polyethylene and 100 parts of high-density polyethylene to melt at 165 °C, and then add 1.2 parts of zinc stearate, 2 parts of antioxidant 1010, 0.7 part of talc powder, and 40 parts of flame retardant to obtain the pre-foaming fluid; use a double-layer co-extrusion machine to send the sheath material fluid into the inlet of the outer mold, and send the pre-foaming fluid into the inlet of the inner mold. The end of the extrusion port of the inner mold is equipped with opposing CO 2Inflatable head, CO 2 The filling pressure is 30 MPa, and CO is filled 2 It accounts for 3% of the mass percentage of the pre-foamed fluid. Start wire threading, and at the same time turn on the inner and outer layer feeding. The wire threading speed is 100 m / min, and the extrusion temperature is 145 - 205 °C. After extrusion is completed, keep it at 180 °C for 30 min to obtain a highly antioxidant network power integrated cable with a sheath thickness of 1.3 cm and a foaming layer thickness of 5 cm; the additives include 15 parts of barium-zinc composite stabilizer, 1.4 parts of stearic acid, 9 parts of carbon black, 3 parts of vulcanizing agent DCP, 15 parts of vinyltrimethoxysilane, and 2 parts of antioxidant 1010; the flame retardant includes 15 parts of 800-mesh expanded graphite, 15 parts of 800-mesh zeolite powder, 9 parts of hexaisopropoxycyclotriphosphazene, 0.5 part of isopropyltri(dioctylpyrophosphato)titanate, 3 parts of vinyltrimethoxysilane, 20 parts of polybutyl methacrylate, 25 parts of vinyl silicone oil, and 12 parts of molybdenum oxide.

[0051] Comparative Example 1

[0052] The difference between Comparative Example 1 and Example 2 is that steps (1) and (2) are absent, and step (3) is changed to: Polish the surface of the pure copper wire until it is shiny, and sequentially place it in acetone, ethanol, and 5% hydrochloric acid by mass for ultrasonic cleaning. The ultrasonic power is 500 W, and the cleaning time for each time is 15 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 3 Pa. The carbon dioxide plasma generator is externally connected to a gas source bottle, and nickel acetylacetonate is placed in the gas source bottle. The heating temperature of the gas source bottle is 185 °C. Then, argon and nickel acetylacetonate are respectively introduced into the cavity at a flow rate of 120 mL / min and 60 mL / min until the pressure in the cavity is 400 Pa. Keep the argon flow rate unchanged, adjust the nickel acetylacetonate flow rate to 20 mL / min, and then introduce oxygen at a flow rate of 50 mL / min. At the same time, heat it at a rate of 11 °C / min to 325 °C, keep it warm for 30 min, then stop introducing argon, oxygen, and nickel acetylacetonate, start pumping air, and at the same time introduce carbon dioxide at a flow rate of 100 mL / min and maintain it for 35 min. Stop introducing carbon dioxide, evacuate to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity is 650 Pa and maintain it for 2 min. Then evacuate to a vacuum degree of 80 Pa and treat it at a power of 250 W for 25 min. Then heat-treat it at 665 °C for 30 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 70%, and the wire drawing temperature is 360 °C to obtain antioxidant copper wire; the remaining steps are the same as those in Example 2.

[0053] Comparative Example 2

[0054] The difference between Comparative Example 2 and Example 2 lies in step (3). Step (3) is modified as follows: Polish the surface of the pure copper wire until it is shiny with sandpaper, then successively place it into acetone, ethanol, and hydrochloric acid with a mass fraction of 5% for ultrasonic cleaning. The ultrasonic power is 500 W, and the cleaning time for each time is 15 min. Dry it with nitrogen, place it into a carbon dioxide plasma generator, and pump it to a vacuum degree of 3 Pa. A gas source bottle is connected outside the carbon dioxide plasma generator, and the binuclear nickel complex is placed in the gas source bottle. The heating temperature of the gas source bottle is >240 °C. Then, argon and the binuclear nickel complex are respectively introduced into the cavity at a flow rate of 120 mL / min and 60 mL / min until the pressure in the cavity reaches 400 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min, and at the same time, increase the temperature to 325 °C at a rate of 11 °C / min. After holding for 30 min, stop introducing argon, oxygen, and the binuclear nickel complex, start pumping, and at the same time, introduce carbon dioxide at a flow rate of 100 mL / min and maintain it for 35 min. Stop introducing carbon dioxide, pump the vacuum to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity reaches 650 Pa and maintain it for 2 min. Then pump the vacuum to a vacuum degree of 80 Pa, process it at a power of 250 W for 25 min, then perform heat treatment at 665 °C for 30 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 70%, and the wire drawing temperature is 360 °C to obtain the antioxidant copper wire; the remaining steps are the same as those in Example 2.

[0055] Comparative Example 3

[0056] The difference between Comparative Example 3 and Example 2 lies in step (3). Step (3) is modified as follows: Polish the surface of the pure copper wire until it is shiny with sandpaper, then successively place it into acetone, ethanol, and hydrochloric acid with a mass fraction of 5% for ultrasonic cleaning. The ultrasonic power is 500 W, and the cleaning time for each time is 15 min. Dry it with nitrogen, place it into a carbon dioxide plasma generator, and pump it to a vacuum degree of 3 Pa. A gas source bottle is connected outside the carbon dioxide plasma generator, and the binuclear nickel complex is placed in the gas source bottle. The heating temperature of the gas source bottle is 185 °C. Then, argon and the binuclear nickel complex are respectively introduced into the cavity at a flow rate of 120 mL / min and 60 mL / min until the pressure in the cavity reaches 400 Pa. Then increase the temperature to 325 °C at a rate of 11 °C / min. After holding for 30 min, stop introducing argon and the binuclear nickel complex, start pumping, and at the same time, introduce carbon dioxide at a flow rate of 100 mL / min and maintain it for 35 min. Stop introducing carbon dioxide, pump the vacuum to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity reaches 650 Pa and maintain it for 2 min. Then pump the vacuum to a vacuum degree of 80 Pa, process it at a power of 250 W for 25 min, then perform heat treatment at 665 °C for 30 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 70%, and the wire drawing temperature is 360 °C to obtain the antioxidant copper wire; the remaining steps are the same as those in Example 2.

[0057] Comparative Example 4

[0058] The difference between Comparative Example 4 and Example 2 lies in step (3). Step (3) is changed to: Polish the surface of the pure copper wire with sandpaper until it is shiny. Then, successively place it in acetone, ethanol, and hydrochloric acid with a mass fraction of 5% for ultrasonic cleaning. The ultrasonic power is 500 W, and the cleaning time for each time is 15 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 3 Pa. Connect a gas source bottle outside the carbon dioxide plasma generator, place the binuclear nickel complex in the gas source bottle, and heat the gas source bottle to a temperature of 185°C. Then, introduce argon and the binuclear nickel complex into the cavity at a flow rate of 120 mL / min and 60 mL / min respectively until the pressure in the cavity reaches 400 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min, and at the same time, heat it to 325°C at a rate of 11°C / min, keep it warm for 30 min, then heat-treat it at 665°C for 30 min, and then draw it into a wire drawing die. The wire drawing deformation rate is 70%, and the wire drawing temperature is 360°C to obtain the antioxidant copper wire; the remaining steps are the same as those in Example 2.

[0059] Comparative Example 5

[0060] The difference between Comparative Example 5 and Example 2 lies in step (3). Step (3) is changed to: Polish the surface of the pure copper wire with sandpaper until it is shiny. Then, successively place it in acetone, ethanol, and hydrochloric acid with a mass fraction of 5% for ultrasonic cleaning. The ultrasonic power is 500 W, and the cleaning time for each time is 15 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 3 Pa. Connect a gas source bottle outside the carbon dioxide plasma generator, place the binuclear nickel complex in the gas source bottle, and heat the gas source bottle to a temperature of 185°C. Then, introduce argon and the binuclear nickel complex into the cavity at a flow rate of 120 mL / min and 60 mL / min respectively until the pressure in the cavity reaches 400 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min, and at the same time, heat it to 325°C at a rate of 11°C / min. After keeping it warm for 30 min, stop introducing argon, oxygen, and the binuclear nickel complex, start pumping air, and at the same time, introduce carbon dioxide at a flow rate of 100 mL / min and maintain it for 35 min. Stop introducing carbon dioxide, evacuate to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity reaches 650 Pa and maintain it for 2 min, then evacuate to a vacuum degree of 80 Pa and treat it at a power of 250 W for 25 min to obtain the antioxidant copper wire; the remaining steps are the same as those in Example 2.

[0061] Effect Example

[0062] The performance analysis results of the high antioxidant network power integrated cable using Embodiments 1 to 3 of the present invention are given in Table 1 below, and the performance analysis results of the antioxidant copper wires using Embodiment 2 of the present invention and Comparative Examples 1 to 5 are given in Table 2 below.

[0063] Table 1

[0064]

[0065] Table 2

[0066] Resistivity (Ω·m) Degree of oxidation Example 2 <![CDATA[3.6×10 -7 > No visible oxidation to the naked eye Comparative Example 1 <![CDATA[4.3×10 -6 > Mostly oxidized Comparative Example 2 <![CDATA[4.2×10 -6 > Mostly oxidized Comparative Example 3 <![CDATA[7.9×10 -7 > Partially oxidized Comparative Example 4 <![CDATA[5.1×10 -7 > Slightly oxidized spots Comparative Example 5 <![CDATA[4.6×10 -7 > Slightly oxidized spots

[0067] From the comparison of the experimental data of the examples and the comparative examples, it can be found that the present invention uses ethyl imidazole-4-carboxylate and 4-acetylimidazole to react to form a β-diketone-based diimidazolylmethane compound, which can be bridged with acetylacetone to obtain a binuclear nickel complex. The binuclear nickel complex can adhere to the surface of the copper wire conductor. After heat treatment, it decomposes to form a nickel protection layer, improving the antioxidant property of the conductor. And during the segmented heating treatment process, the ambient gas atmosphere is continuously changed, so that during the subsequent plasma treatment process, a carbon film is formed, further improving the antioxidant property of the conductor, while ensuring the conductivity of the conductor. Finally, pressure treatment is carried out to promote the mutual reaction and fusion of various elements, further improving the antioxidant performance of the conductor.

[0068] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, in any regard, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, it is intended to embrace all changes within the meaning and scope of the equivalent elements of the claims in the present invention. Any reference signs in the claims should not be regarded as limiting the claimed claim.

Claims

1. A high antioxidant network power integrated cable, Characterized in that, The preparation method of the high antioxidant network power integrated cable comprises the following steps: (1) Stranding 2 power cables and 1 network cable to form a core; the cores and braided layers of the power cables and network cables are made of antioxidant copper wires; (2) Heat 100 - 220 parts of cross-linked polyethylene resin and 80 - 120 parts of low-density polyethylene to melt at 120 - 130 °C, add 30 - 45 parts of additives, 10 - 15 parts of polyethylene wax, and stir at 1000 - 1500 rpm for 20 - 30 min to obtain a sheath material fluid; Heat 60 - 80 parts of low-density polyethylene and 80 - 100 parts of high-density polyethylene to melt at 140 - 165 °C, then add 0.6 - 1.2 parts of zinc stearate, 1 - 2 parts of antioxidant 1010, 0.3 - 0.7 parts of talc powder, and 30 - 40 parts of flame retardant to obtain a pre-foamed fluid; Use a double-layer co-extrusion machine to send the sheath material fluid into the feeding port of the outer mold and the pre-foamed fluid into the feeding port of the inner mold. An opposing CO 2 inflation head is installed at the end of the extrusion port of the inner mold. Start wire routing, and at the same time, turn on the feeding of the inner and outer layers. The wire routing speed is 80 - 100 m / min, the extrusion temperature is 145 - 205 °C. After extrusion is completed, keep it at 155 - 180 °C for heat preservation for 15 - 30 min to obtain a highly antioxidant network power integrated cable; The preparation method of the antioxidant copper wire is as follows: polish the surface of the pure copper wire, ultrasonic clean it, dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate, connect a gas source bottle outside the carbon dioxide plasma generator, place the binuclear nickel complex in the gas source bottle, heat the gas source bottle, introduce argon and the binuclear nickel complex until the pressure in the cavity is 350 - 450 Pa, keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex, then introduce oxygen, and at the same time raise the temperature to 300 - 350 °C, keep warm for 30 min, then stop introducing argon, oxygen and the binuclear nickel complex, start pumping air, and at the same time introduce carbon dioxide, maintain for 30 - 40 min, stop introducing carbon dioxide, evacuate, then introduce carbon dioxide until the pressure in the cavity is 600 - 700 Pa, maintain for 1 - 3 min, then evacuate again, process at a power of 200 - 300 W for 20 - 30 min, then heat-treat at 650 - 680 °C for 25 - 35 min, then draw it into a wire drawing die, the wire drawing deformation rate is 65 - 85%, and the wire drawing temperature is 320 - 380 °C to obtain the antioxidant copper wire; The binuclear nickel complex is formed by the reaction of ethyl imidazole - 4 - carboxylate and 4 - acetylimidazole to form a β - diketone - type bisimidazoleformylmethane compound, and is prepared by bridging with acetylacetone using its diketone structure.

2. A high antioxidant network power integrated cable according to claim 1, Characterized in that, The core of the power cable in step (1) is stranded by 40 - 60 antioxidant copper wires with a diameter of 0.12 - 0.20 mm in a regular arrangement stranding method, the stranding pitch - diameter ratio is 10 - 15 times, and the outer periphery of the core is coated with a low - density polyethylene insulating layer, and the thickness of the insulating layer is 0.8 - 1.2 mm.

3. A high antioxidant network power integrated cable according to claim 1, Characterized in that, The core of the network cable in step (1) is stranded by 10 - 15 antioxidant copper wires with a diameter of 0.12 - 0.20 mm, the stranding pitch - diameter ratio is 9 - 12 times, and the outer periphery of the core is successively coated with a low - density polyethylene insulating layer and a braided layer, and the thickness of the insulating layer is 1.0 - 1.4 mm.

4. A high antioxidant network power integrated cable according to claim 3, Characterized in that, The braided layer uses antioxidant copper wires with a diameter of 0.10 - 0.12 mm, the braiding coverage rate is 92 - 95%, and the braiding angle is 30 - 50°.

5. A high antioxidant network power integrated cable according to claim 1, Characterized in that, The preparation method of the antioxidant copper wire is: a. Add 100 - 120 parts of ethyl imidazole - 4 - carboxylate and 8 - 14 parts of 4 - acetylimidazole. Heat the mixture to 160 - 163 °C with stirring at 50 rpm. Add 50 - 60 parts of an ethanol solution within 2 h. The mass ratio of absolute ethanol to sodium metal in the ethanol solution is 47:3.

5. After the dropping is completed, continue stirring until all the ethanol escapes. Cool to room temperature, add 15 - 22 parts of deionized water, continue stirring for 10 - 30 min, then add 22 - 30 parts of a 10% sulfuric acid solution, continue stirring for 20 - 45 min. Add a 5% sodium bicarbonate solution until the pH of the reaction solution is 7 - 8. Separate the layers, separate the oil layer, wash the organic phase with 40 - 50 parts of deionized water, then extract with anhydrous ether. Take the organic phase, dry it with anhydrous sodium sulfate for 3 - 5 h, filter, place it in a 50 °C water bath, distill for 40 - 50 min, and then at a vacuum of 1.1×10 3 Pa. Dry at 85 °C for 2 - 3 h to obtain the diimidazoleformylmethane compound; b. Mix 12 - 13 parts of bis(imidazolylmethyl)methane compound, 6 - 7 parts of acetylacetone, 16 - 20 parts of nickel perchlorate, 880 - 950 parts of methanol, and 310 - 420 parts of deionized water. Stir at 80 - 100 rpm for 30 min, add 8 drops of triethylamine, react at 55 - 62 °C for 4 - 6 h, then cool to room temperature, filter, take the filtrate, wash it with deionized water and methanol three times respectively, and dry at 60 °C for 6 h to obtain the binuclear nickel complex; c. Polish the surface of the pure copper wire with sandpaper until it is shiny. Then put it into acetone, ethanol, and 5% hydrochloric acid successively for ultrasonic cleaning. The ultrasonic power is 400 - 600 W, and the cleaning time for each time is 10 - 20 min. Dry it with nitrogen, put it into a carbon dioxide plasma generator, evacuate to a vacuum degree of 1 - 5 Pa. Connect a gas source bottle outside the carbon dioxide plasma generator. Place the binuclear nickel complex in the gas source bottle. The heating temperature of the gas source bottle is 185 °C. Then introduce argon and the binuclear nickel complex into the cavity at a flow rate of 120 mL / min and 60 mL / min respectively until the pressure in the cavity is 350 - 450 Pa. Keep the argon flow rate unchanged, adjust the flow rate of the binuclear nickel complex to 20 mL / min, then introduce oxygen at a flow rate of 50 mL / min. At the same time, heat up at a rate of 8 - 15 °C / min to 300 - 350 °C, keep warm for 30 min, then stop introducing argon, oxygen, and the binuclear nickel complex, start pumping air, and at the same time introduce carbon dioxide at a flow rate of 100 mL / min and maintain for 30 - 40 min. Stop introducing carbon dioxide, evacuate to a vacuum degree of 50 Pa, then introduce carbon dioxide at a flow rate of 100 mL / min until the pressure in the cavity is 600 - 700 Pa and maintain for 1 - 3 min. Then evacuate to a vacuum degree of 80 Pa and treat at a power of 200 - 300 W for 20 - 30 min. Then heat - treat at 650 - 680 °C for 25 - 35 min, and then draw it into a wire - drawing die. The wire - drawing deformation rate is 65 - 85%, and the wire - drawing temperature is 320 - 380 °C to obtain the antioxidant copper wire.

6. A high - antioxidant network power integrated cable according to claim 1, characterized in that, the auxiliary agent in step (2) includes 8 - 15 parts of barium - zinc composite stabilizer, 0.6 - 1.4 parts of stearic acid, 5 - 9 parts of carbon black, 1 - 3 parts of curing agent DCP, 10 - 15 parts of vinyltrimethoxysilane, and 1 - 2 parts of antioxidant 1010.

7. A high - antioxidant network power integrated cable according to claim 1, characterized in that, the flame retardant in step (2) includes 10 - 15 parts of 800 - mesh expanded graphite, 10 - 15 parts of 800 - mesh zeolite powder, 6 - 9 parts of hexaisopropoxycyclotriphosphazene, 0.1 - 0.5 parts of isopropyltris(dioctylpyrophosphato)titanate, 1 - 3 parts of vinyltrimethoxysilane, 10 - 20 parts of polybutyl methacrylate, 10 - 25 parts of vinyl silicone oil, and 8 - 12 parts of molybdenum oxide.

8. A high - antioxidant network power integrated cable according to claim 1, characterized in that, The model of the low-density polyethylene is LDPE1C7A, and the melt index of the high-density polyethylene is 0.5 ± 0.05 g / 10 min.

9. A highly antioxidant network power integrated cable according to claim 1, characterized in that The CO described in step (2) 2 is filled at a pressure of 20 to 30 MPa, and the CO 2 accounts for 2 to 3% of the mass percentage of the pre-foaming fluid.

10. A highly antioxidant network power integrated cable according to claim 1, characterized in that the sheath thickness of the highly antioxidant network power integrated cable is 0.8 - 1.3 cm, and the foam layer thickness is 3 - 5 cm.

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