A waterproof, impact-resistant fireproof cable and its preparation method

Abstract

The present invention discloses a waterproof and impact-resistant fireproof cable and a preparation method thereof, relating to the technical field of cables. First, the present invention uses 2-bromo-1,5-hexadiene, trimethoxysilane, and trioctyldecylamine to form a silicon hydroxide compound, which can undergo a hydrolysis reaction with the infiltrated moisture to hinder the invasion of moisture; uses ultraviolet-assisted electrospinning to form a first waterproof layer on the surface of the insulating layer; then introduces zinc nitrate water vapor to react with the first waterproof layer to obtain a second waterproof layer, enhancing the waterproof effect of the cable; after coating the shielding layer and the inner sheath layer, diallyldiethoxysilane and graphene are sequentially sprayed to form an aerogel protective layer, which has a fireproof effect; then aluminum sulfate is sprayed to form aluminum hydroxide coated on the surface of the aerogel pores, and then triethoxysilyl butyraldehyde and malonic acid are sequentially sprayed and grafted on the surface of the aerogel, enhancing the fireproof effect of the cable. The cable prepared by the present invention has the effects of waterproof and fireproof.

Description

Technical Field

[0001] The present invention relates to the technical field of cables, and particularly to a waterproof, impact-resistant fireproof cable and a preparation method thereof. Background Art

[0002] As is well known, with the rapid development of the national economy and the continuous update of power facilities, the usage amount of various wires and cables has increased significantly, driving the demand for various cable materials, with a large increase in quantity. Therefore, higher requirements are put forward for the production cost and quality of cable materials. Polyvinyl chloride has advantages such as low cost, convenient processing, excellent mechanical properties, corrosion resistance, and good insulation. When combined with linear low-density polyethylene, poly-1-butene, etc., it has good plasticity and impact strength. However, since plastic resins are flammable, once on fire, it is easy to cause property losses and harm to personnel. Currently, at home and abroad, mainly antimony trioxide or chlorinated paraffin, etc. are added as flame retardants, which increases the toxicity index of the product. In addition, the price is very expensive, ranging from 180,000 to 250,000 yuan per ton, and the market is difficult to accept.

[0003] In addition, the cable is exposed to sunlight, wind and rain for a long time and is extremely vulnerable to rain erosion. The existing waterproof means mostly adopt the radial waterproof method of pure paper-wrapped insulating glue, with poor waterproof performance and extremely easy to cause cable corrosion and aging. Summary of the Invention

[0004] The purpose of the present invention is to provide a waterproof, impact-resistant fireproof cable and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A waterproof, impact-resistant fireproof cable, the waterproof, impact-resistant fireproof cable includes a cable core, a self-made waterproof layer, a shielding layer, an inner sheath layer, and a self-made fireproof layer.

[0006] Further, the cable core includes a tinned copper wire core material and a cross-linked polyethylene insulating layer.

[0007] Further, the self-made waterproof layer includes a first waterproof layer and a second waterproof layer; the first waterproof layer is prepared by the following method: mixing N,N-dimethylformamide, tetrahydrofuran, and a silane hydroxide compound to obtain a spinning solution, electrospinning on the cable core, and then placing it under a high-pressure mercury lamp for irradiation; the second waterproof layer is prepared by the following method: placing the cable core of the first waterproof layer in a container, sealing it, and introducing zinc nitrate water vapor for reaction for a period of time.

[0008] Further, the silicon hydroxide compound is prepared by the following method: 2-bromo-1,5-hexadiene, phenothiazine, chloroplatinic acid, isopropyl alcohol, and octamethylcyclotetrasiloxane are mixed, heated and the temperature is raised, then trimethoxysilane is added, and a silicon oxide compound is obtained through reaction; the silicon oxide compound and trioctyldecylamine are mixed, heated and reacted, petroleum ether is added, filtration is carried out by suction, then ethanol and ethyl acetate are added, after stirring for a period of time, filtration is carried out by suction and drying is carried out to obtain a quaternary ammonium compound, and then exchange is carried out through a strongly basic anion exchange resin.

[0009] Further, the self-made fireproof layer is prepared by the following method: the inner sheath layer cable core is placed under a high-pressure mercury lamp, diallyldiethoxysilane is sprayed, after irradiation, the temperature is raised, then a graphene oxide solution is sprayed, after reacting for a period of time, it is placed in an atmosphere of water-alcohol vapor, allowed to stand, and freeze-dried to obtain an aerogel cable core; an aluminum sulfate solution 0.2 to 0.4 times the mass of the aerogel cable core is applied to the aerogel cable core, after reacting for a period of time, sulfuric acid is sprayed, after ultrasonic treatment, washing and drying are carried out, and then a malonic acid reaction solution is sprayed.

[0010] Further, a preparation method of a waterproof and impact-resistant fireproof cable includes the following preparation steps:

[0011] (1) N,N-dimethylformamide, tetrahydrofuran, and the silicon hydroxide compound are mixed according to a mass ratio of 1:1:0.1 to 1:1:0.2, stirred and dissolved to obtain a spinning solution, electrospun onto the cable core until the film layer thickness is 0.1 to 0.3 mm, then placed under a 2 kW high-pressure mercury lamp at a distance of 200 mm, irradiated for 30 to 60 s to obtain a first waterproof layer cable core;

[0012] (2) The first waterproof layer cable core is placed in a container, sealed, and zinc nitrate water vapor at 180 °C is introduced at 20 mL / h, after reacting for 15 to 18 h, it is taken out, cooled to room temperature, and dried at 80 °C for 7 to 10 h to obtain a self-made waterproof layer cable core;

[0013] (3) A shielding layer with a thickness of 0.1 to 0.3 mm is woven on the surface of the self-made waterproof layer cable core by using tinned copper wire to obtain a shielding layer cable core;

[0014] (4) Crosslinked polyethylene, polyvinyl chloride resin, linear low-density polyethylene, poly-1-butene, γ-aminopropyltriethoxysilane, silicon dioxide, antioxidant 264, calcium stearate, zinc stearate, and epoxy soybean oil are mixed according to a mass ratio of 1:2:1:1.8:0.1:0.2:0.08:0.1:0.05:1, stirred at 100 °C and 2000 rpm for 1 to 6 min, and then extruded onto the shielding layer cable core at 145 to 160 °C to obtain an inner sheath layer cable core;

[0015] (5) Place the inner sheath layer cable core under a 2 kW high-pressure mercury lamp at a distance of 200 mm, spray diallyldiethoxysilane which is 0.5 - 0.8 times the mass of the inner sheath layer cable core, after irradiating for 44 - 58 s, raise the temperature to 60 °C, spray a graphene oxide solution which is 88 - 100 times the mass of the inner sheath layer cable core. The mass ratio of graphene oxide, deionized water, and ascorbic acid in the graphene oxide solution is 1:200:0.1 - 1:500:0.5. After reacting for 7 - 10 h, place it in an atmosphere of water-alcohol vapor where the mass ratio of deionized water to absolute ethanol in the water-alcohol vapor is 1:9. After standing for 10 - 13 h, freeze at -15 °C for 4 - 7 h to obtain an aerogel cable core;

[0016] (6) Place the aerogel cable core in a container, spray an aluminum sulfate solution which is 0.2 - 0.4 times the mass of the aerogel cable core. After reacting at 160 °C for 35 - 48 min, spray sulfuric acid with a mass fraction of 8.9% which is 0.01 - 0.03 times the mass of the aerogel cable core, ultrasonic at 30 kHz for 31 - 43 min, wash with deionized water 6 - 8 times, dry at 100 °C for 9 - 13 h, then spray a malonic acid reaction solution which is 0.4 - 0.7 times the mass of the aerogel cable core, react for 4.5 - 7 h, wash with deionized water 6 - 8 times, dry at 60 °C for 10 - 14 h to obtain a fireproof cable with waterproof and impact resistance.

[0017] Further, the preparation method of the silicon hydroxide compound described in step (1) is:

[0018] A. Mix 2-bromo-1,5-hexadiene, phenothiazine, chloroplatinic acid, isopropanol, and octamethylcyclotetrasiloxane according to a mass ratio of 1:0.01:0.001:0.004:0.0006 - 1:0.02:0.002:0.006:0.0008. After stirring evenly, raise the temperature to 90 - 95 °C, add trimethoxysilane which is 0.8 - 1.1 times the mass of 2-bromo-1,5-hexadiene, and react for 2 - 4.5 h to obtain a silicon oxide compound;

[0019] B. Mix the silicon oxide compound and trioctylamine according to a mass ratio of 1:1.5 - 1:2.0, heat to 78 °C, after reacting for 40 - 44 h, add petroleum ether which is 1.5 - 2.0 times the mass of the silicon oxide compound, stir evenly, filter by suction, then add ethanol which is 2 - 4 times the mass of the silicon oxide compound and ethyl acetate which is 1.1 - 2.3 times the mass of the silicon oxide compound, stir at 80 rpm for 15 - 24 min, filter by suction, and dry at 60 °C for 4 - 7 h to obtain a quaternary ammonium compound;

[0020] C. Place the strongly basic anion exchange resin in an ion exchange column, and add a quaternary ammonium compound solution that is 1.0 - 1.5 times the mass of the strongly basic anion exchange resin at a rate of 50 mL / h. The mass ratio of the quaternary ammonium compound to absolute ethanol in the quaternary ammonium compound solution is 1:3. Then wash it with absolute ethanol 2 - 4 times, perform rotary evaporation at 300 rpm and 80 °C for 60 - 72 min, and then dry it at 70 °C for 3 - 6 h.

[0021] Further, the electrospinning conditions in step (1) are as follows: the spinning voltage is 15 kV, the spinning distance is 18 cm, the spinning speed is 0.4 mL / h, both ends of the cable core are fixed, and the rotation speed is 60 rpm.

[0022] Further, the zinc nitrate water vapor in step (2) is prepared by mixing zinc nitrate hexahydrate and deionized water at a mass ratio of 1:13.4.

[0023] Further, the preparation method of the aluminum sulfate solution in step (6) is as follows: mix aluminum sulfate and deionized water at a mass ratio of 1:2.6, and add sodium hydroxide until the pH of the solution is 9 - 10; the preparation method of the malonic acid reaction solution is as follows: mix triethoxysilyl butyraldehyde, malonic acid, N,N - dimethylformamide, and pyridine at a mass ratio of 1:1.1:3:0.2 - 1:1.6:5:0.4, heat it to 90 °C, react for 7 - 10 h, then cool it to room temperature, add ice water that is 9 - 13 times the mass of triethoxysilyl butyraldehyde, and then add hydrochloric acid until the pH of the solution is 1 - 2, perform suction filtration to obtain a filter cake, and then add deionized water that is 2 - 4 times the mass of the filter cake.

[0024] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0025] In the present invention, a self - made waterproof layer, a shielding layer, an inner sheath layer, and a self - made fireproof layer are sequentially coated on the surface of the cable core to achieve the effects of waterproofing and flame retardancy.

[0026] First, the present invention utilizes the addition reaction of the double bond of 2-bromo-1,5-hexadiene with the silicon-hydrogen bond of trimethoxysilane. Then, the bromide ion undergoes a quaternization reaction with trioctyldecylamine. Subsequently, through a strong-base anion exchange resin, it is hydroxylated to obtain a silane hydroxide compound, which can undergo a hydrolysis reaction with the infiltrated moisture to eliminate the internal moisture and fill the micropores in the water tree area, preventing the re-invasion of moisture and endowing the cable with waterproof performance. By means of electrospinning, a first waterproof layer is formed on the surface of the insulating layer, and ultraviolet irradiation is supplemented during the electrospinning process, enabling the remaining double bonds of the silane hydroxide compound to undergo a free radical reaction with the cross-linked polyethylene insulating layer, tightly cross-linking the first waterproof layer with the insulating layer to prevent water molecules from infiltrating. At the same time, hydrophobic long chains are introduced on the surface to enhance the waterproof property of the cable. Then, zinc nitrate water vapor is introduced, and the zinc ions react with the hydroxide ions of the first waterproof layer, depositing on the surface of the first waterproof layer and forming zinc oxide through thermal oxidation. It gradually grows and accumulates to form a second waterproof layer with an onion-like structure, and the first and second waterproof layers are tightly cross-linked, which is beneficial to improving the waterproof effect of the cable.

[0027] Secondly, the present invention conducts the first spraying, supplemented by ultraviolet irradiation, to cause free radical polymerization of diallyldiethoxysilane with the cross-linked polyethylene of the inner sheath layer. Then, the second spraying is carried out. Utilizing the silicon-oxygen bond of diallyldiethoxysilane, graphene is deposited on the surface of the inner sheath layer and undergoes hydrothermal reduction to form an aerogel protective layer, which slows down the spread of the flame, isolates heat, and endows the cable with fireproof performance. Then, the third spraying is carried out. Utilizing capillary action, aluminum sulfate is adsorbed and hydrolyzed to form aluminum hydroxide, which coats the surface of the aerogel pores. During the coating process, the hydroxyl groups on the surface of graphene can react with aluminum hydroxide to form bonds, firmly fixing aluminum hydroxide in the aerogel. When heated, it decomposes to absorb a large amount of heat, reducing the flame temperature. At the same time, the decomposition products fill the pores of the aerogel, isolating oxygen and enhancing the fireproof effect of the cable. Next, the fourth spraying is carried out. Triethoxysilylbutyraldehyde and malonic acid undergo a condensation reaction, and then are grafted onto the surface of the aerogel using the silicon-oxygen bond. They are vaporized at high temperature, diluting the oxygen concentration in the air and enhancing the fireproof effect of the cable. Detailed implementation manners

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. 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.

[0029] In order to more clearly illustrate the method provided by the present invention, it is described in detail through the following embodiments. The test methods for each index of the waterproof, impact-resistant, and fireproof cable manufactured in the following embodiments are as follows:

[0030] Waterproofness: Cable samples of the examples and comparative examples with the same length and size were taken for waterproofness testing. The cable samples were immersed in tap water at 40°C, and the change rate of dielectric constant was measured after 7 days of immersion.

[0031] Fire resistance: Cable samples of the examples and comparative examples with the same length and size were taken for fire resistance testing. Referring to GB12666.6, the continuous power supply time of the cable under the high temperature of a 1000°C flame was measured. Example 1

[0032] (1) 2-Bromo-1,5-hexadiene, phenothiazine, chloroplatinic acid, isopropanol, and octamethylcyclotetrasiloxane were mixed in a mass ratio of 1:0.01:0.001:0.004:0.0006. After stirring evenly, the temperature was raised to 90°C, and trimethoxysilane 0.8 times the mass of 2-bromo-1,5-hexadiene was added, and the reaction was carried out for 2 h to obtain a silicon oxide compound;

[0033] (2) The silicon oxide compound and trioctylamine were mixed in a mass ratio of 1:1.5, heated to 78°C, and after reacting for 40 h, petroleum ether 1.5 times the mass of the silicon oxide compound was added. After stirring evenly, filtration was carried out, and then ethanol 2 times the mass of the silicon oxide compound and ethyl acetate 1.1 times the mass of the silicon oxide compound were added, and stirring was carried out at 80 rpm for 15 min, followed by filtration and drying at 60°C for 4 h to obtain a quaternary ammonium compound;

[0034] (3) The strongly basic anion exchange resin was placed in an ion exchange column, and a quaternary ammonium compound solution 1 time the mass of the strongly basic anion exchange resin was added at 50 mL / h. The mass ratio of the quaternary ammonium compound to absolute ethanol in the quaternary ammonium compound solution was 1:3. Then, it was washed 2 times with absolute ethanol, rotary evaporated at 300 rpm and 80°C for 60 min, and dried at 70°C for 3 h to obtain a silicon hydroxide compound;

[0035] (4) N,N-Dimethylformamide, tetrahydrofuran, and the silicon hydroxide compound were mixed in a mass ratio of 1:1:0.1, and stirred and dissolved to obtain a spinning solution. Electrospinning was carried out on the cable core until the film layer thickness reached 0.1 mm, and then it was placed under a 2 kW high-pressure mercury lamp at a distance of 200 mm and irradiated for 30 s to obtain a cable core with a first waterproof layer; the electrospinning conditions were: the spinning voltage was 15 kV, the spinning distance was 18 cm, the spinning speed was 0.4 mL / h, the two ends of the cable core were fixed, and the rotation speed was 60 rpm;

[0036] (5) The cable core with the first waterproof layer was placed in a container, sealed, and zinc nitrate water vapor at 180°C was introduced at 20 mL / h. The mass ratio of zinc nitrate hexahydrate to deionized water in the zinc nitrate water vapor was 1:13.4. After reacting for 15 h, it was taken out, cooled to room temperature, and dried at 80°C for 7 h to obtain a self-made cable core with a waterproof layer;

[0037] (6) A shielding layer with a thickness of 0.1 mm was woven on the surface of the self-made waterproof layer cable core using tinned copper wire to obtain a shielded cable core;

[0038] (7) Crosslinked polyethylene, polyvinyl chloride resin, linear low-density polyethylene, poly-1-butene, γ-aminopropyltriethoxysilane, silica, antioxidant 264, calcium stearate, zinc stearate, and epoxy soybean oil were mixed in a mass ratio of 1:2:1:1.8:0.1:0.2:0.08:0.1:0.05:1. After stirring at 100 °C and 2000 rpm for 1 min, an inner sheath layer was extruded onto the shielded cable core at 145 - 160 °C to obtain an inner sheath layer cable core;

[0039] (8) The inner sheath layer cable core was placed under a 2 kW high-pressure mercury lamp at a distance of 200 mm, and diallyldiethoxysilane with a mass 0.5 times that of the inner sheath layer cable core was sprayed. After irradiation for 44 s, the temperature was raised to 60 °C, and a graphene oxide solution with a mass 88 times that of the inner sheath layer cable core was sprayed. The mass ratio of graphene oxide, deionized water, and ascorbic acid in the graphene oxide solution was 1:200:0.1. After reacting for 7 h, it was placed in an atmosphere of water-alcohol vapor, where the mass ratio of deionized water to absolute ethanol in the water-alcohol vapor was 1:9. After standing for 10 h, it was frozen at -15 °C for 4 h to obtain an aerogel cable core;

[0040] (9) Triethoxysilyl butyraldehyde, malonic acid, N,N-dimethylformamide, and pyridine were mixed in a mass ratio of 1:1.1:3:0.2. After heating to 90 °C and reacting for 7 h, it was cooled to room temperature, 9 times the mass of ice water based on triethoxysilyl butyraldehyde was added, and then hydrochloric acid was added until the pH of the solution was 1. Filtration was carried out to obtain a filter cake, and then 2 times the mass of deionized water based on the filter cake was added to obtain a malonic acid reaction solution;

[0041] (10) Aluminum sulfate and deionized water were mixed in a mass ratio of 1:2.6, and sodium hydroxide was added until the pH of the solution was 9 to obtain an aluminum sulfate solution. The aerogel cable core was placed in a container, and an aluminum sulfate solution with a mass 0.2 times that of the aerogel cable core was sprayed. After reacting at 160 °C for 35 min, sulfuric acid with a mass fraction of 8.9% and a mass 0.01 times that of the aerogel cable core was sprayed. After ultrasonic treatment at 30 kHz for 31 min, it was washed 6 times with deionized water, dried at 100 °C for 9 h, and then a malonic acid reaction solution with a mass 0.4 times that of the aerogel cable core was sprayed. After reacting for 4.5 h, it was washed 6 times with deionized water and dried at 60 °C for 10 h to obtain a waterproof, impact-resistant fireproof cable. Example 2

[0042] (1) Mix 2-bromo-1,5-hexadiene, phenothiazine, chloroplatinic acid, isopropanol, and octamethylcyclotetrasiloxane in a mass ratio of 1:0.015:0.0015:0.005:0.0007. After stirring evenly, heat to 92 °C, and add trimethoxysilane in an amount 0.95 times the mass of 2-bromo-1,5-hexadiene, and react for 3.3 h to obtain a silicon oxide compound;

[0043] (2) Mix the silicon oxide compound and trioctylamine in a mass ratio of 1:1.8, heat to 78 °C, react for 42 h, then add petroleum ether in an amount 1.8 times the mass of the silicon oxide compound. After stirring evenly, perform suction filtration, and then add ethanol in an amount 3 times the mass of the silicon oxide compound and ethyl acetate in an amount 1.7 times the mass of the silicon oxide compound, stir at 80 rpm for 19 min, perform suction filtration, and dry at 60 °C for 5.5 h to obtain a quaternary ammonium compound;

[0044] (3) Place the strongly basic anion exchange resin in an ion exchange column, add a quaternary ammonium compound solution in an amount 1.25 times the mass of the strongly basic anion exchange resin at a rate of 50 mL / h. The mass ratio of the quaternary ammonium compound to absolute ethanol in the quaternary ammonium compound solution is 1:3. Then wash with absolute ethanol 3 times, perform rotary evaporation at 300 rpm and 80 °C for 66 min, and dry at 70 °C for 4.5 h to obtain a silane hydroxide compound;

[0045] (4) Mix N,N-dimethylformamide, tetrahydrofuran, and the silane hydroxide compound in a mass ratio of 1:1:0.15, stir to dissolve to obtain a spinning solution, electrospin onto the cable core until the film layer thickness is 0.2 mm, and then place it under a 2 kW high-pressure mercury lamp at a distance of 200 mm and irradiate for 45 s to obtain a first waterproof layer cable core; The electrospinning conditions are: the spinning voltage is 15 kV, the spinning distance is 18 cm, the spinning speed is 0.4 mL / h, both ends of the cable core are fixed, and the rotation speed is 60 rpm;

[0046] (5) Place the first waterproof layer cable core in a container, seal it, and introduce zinc nitrate water vapor at 180 °C at a rate of 20 mL / h. The mass ratio of zinc nitrate hexahydrate to deionized water in the zinc nitrate water vapor is 1:13.4. After reacting for 16.5 h, take it out, cool to room temperature, and dry at 80 °C for 8.5 h to obtain a self-made waterproof layer cable core;

[0047] (6) Use tinned copper wire to braid a shielding layer with a thickness of 0.2 mm on the surface of the self-made waterproof layer cable core to obtain a shielding layer cable core;

[0048] (7) Mix cross-linked polyethylene, polyvinyl chloride resin, linear low-density polyethylene, poly-1-butene, γ-aminopropyltriethoxysilane, silica, antioxidant 264, calcium stearate, zinc stearate, and epoxy soybean oil in a mass ratio of 1:2:1:1.8:0.1:0.2:0.08:0.1:0.05:1. After stirring at 100 °C and 2000 rpm for 3 min, extrude the inner sheath layer onto the shielded core at 145 - 160 °C to obtain the inner sheath core;

[0049] (8) Place the inner sheath core under a 2 kW high-pressure mercury lamp at a distance of 200 mm, spray 0.65 times the mass of the inner sheath core of diallyldiethoxysilane, irradiate for 51 s, then raise the temperature to 60 °C, and spray a graphene oxide solution with a mass 94 times that of the inner sheath core. The mass ratio of graphene oxide, deionized water, and ascorbic acid in the graphene oxide solution is 1:350:0.3. After reacting for 8.5 h, place it in an atmosphere of water-alcohol vapor where the mass ratio of deionized water to absolute ethanol in the water-alcohol vapor is 1:9. After standing for 11.5 h, freeze at -15 °C for 5.5 h to obtain the aerogel core;

[0050] (9) Mix triethoxysilylbutyraldehyde, malonic acid, N,N-dimethylformamide, and pyridine in a mass ratio of 1:1.4:4:0.3, raise the temperature to 90 °C, react for 8.5 h, then cool to room temperature, add ice water with a mass 11 times that of triethoxysilylbutyraldehyde, and then add hydrochloric acid until the pH of the solution is 1.5. Filter to obtain a filter cake, and then add deionized water with a mass 3 times that of the filter cake to obtain the malonic acid reaction solution;

[0051] (10) Mix aluminum sulfate and deionized water in a mass ratio of 1:2.6, add sodium hydroxide until the pH of the solution is 9.5 to obtain an aluminum sulfate solution; place the aerogel core in a container, spray 0.3 times the mass of the aerogel core of the aluminum sulfate solution, react at 160 °C for 41 min, then spray 0.02 times the mass of the aerogel core of sulfuric acid with a mass fraction of 8.9%, ultrasonicate at 30 kHz for 37 min, wash 7 times with deionized water, dry at 100 °C for 11 h, then spray 0.55 times the mass of the aerogel core of the malonic acid reaction solution, react for 5.8 h, wash 7 times with deionized water, and dry at 60 °C for 12 h to obtain a waterproof and impact-resistant fireproof cable. Example 3

[0052] (1) Mix 2-bromo-1,5-hexadiene, phenothiazine, chloroplatinic acid, isopropanol, and octamethylcyclotetrasiloxane in a mass ratio of 1:0.02:0.002:0.006:0.0008. After stirring evenly, raise the temperature to 95 °C, and add trimethoxysilane with a mass 1.1 times that of 2-bromo-1,5-hexadiene, and react for 4.5 h to obtain a silicon oxide compound;

[0053] (2) Mix silicon oxide and trioctylamine in a mass ratio of 1:2.0, heat to 78 °C, after reacting for 44 h, add petroleum ether which is 2.0 times the mass of silicon oxide, stir evenly, then carry out suction filtration, and then add ethanol which is 4 times the mass of silicon oxide and ethyl acetate which is 2.3 times the mass of silicon oxide, stir at 80 rpm for 24 min, carry out suction filtration, and dry at 60 °C for 7 h to obtain a quaternary ammonium compound;

[0054] (3) Place the strong-base anion exchange resin in an ion exchange column, add a quaternary ammonium compound solution which is 1.5 times the mass of the strong-base anion exchange resin at a rate of 50 mL / h. The mass ratio of the quaternary ammonium compound to absolute ethanol in the quaternary ammonium compound solution is 1:3, then wash 4 times with absolute ethanol, carry out rotary evaporation at 300 rpm and 80 °C for 72 min, and then dry at 70 °C for 6 h to obtain a silane hydroxide compound;

[0055] (4) Mix N,N-dimethylformamide, tetrahydrofuran, and the silane hydroxide compound in a mass ratio of 1:1:0.2, stir and dissolve to obtain a spinning solution, electrospin onto the cable core until the film layer thickness is 0.3 mm, and then place it under a 2 kW high-pressure mercury lamp at a distance of 200 mm and irradiate for 60 s to obtain a first waterproof layer cable core; The electrospinning conditions are: the spinning voltage is 15 kV, the spinning distance is 18 cm, the spinning speed is 0.4 mL / h, both ends of the cable core are fixed, and the rotation speed is 60 rpm;

[0056] (5) Place the first waterproof layer cable core in a container, seal it, and introduce zinc nitrate water vapor at 180 °C at a rate of 20 mL / h. The mass ratio of zinc nitrate hexahydrate to deionized water in the zinc nitrate water vapor is 1:13.4. After reacting for 18 h, take it out, cool to room temperature, and dry at 80 °C for 10 h to obtain a self-made waterproof layer cable core;

[0057] (6) Use tinned copper wire to braid a shielding layer with a thickness of 0.3 mm on the surface of the self-made waterproof layer cable core to obtain a shielding layer cable core;

[0058] (7) Mix cross-linked polyethylene, polyvinyl chloride resin, linear low-density polyethylene, poly-1-butene, γ-aminopropyltriethoxysilane, silicon dioxide, antioxidant 264, calcium stearate, zinc stearate, and epoxy soybean oil in a mass ratio of 1:2:1:1.8:0.1:0.2:0.08:0.1:0.05:1, stir at 100 °C and 2000 rpm for 6 min, and then extrude an inner sheath layer onto the shielding layer cable core at 145 - 160 °C to obtain an inner sheath layer cable core;

[0059] (8) Place the inner sheath layer cable core under a 2 kW high-pressure mercury lamp at a distance of 200 mm, spray diallyldiethoxysilane with a mass 0.8 times that of the inner sheath layer cable core, after irradiating for 58 s, raise the temperature to 60 °C, spray a graphene oxide solution with a mass 100 times that of the inner sheath layer cable core. The mass ratio of graphene oxide, deionized water, and ascorbic acid in the graphene oxide solution is 1:500:0.5. After reacting for 7 - 10 h, place it in an atmosphere of water-alcohol vapor. The mass ratio of deionized water and absolute ethanol in the water-alcohol vapor is 1:9. After standing for 13 h, freeze at -15 °C for 7 h to obtain an aerogel cable core;

[0060] (9) Mix triethoxysilyl butyraldehyde, malonic acid, N,N-dimethylformamide, and pyridine in a mass ratio of 1:1.6:5:0.4, raise the temperature to 90 °C, after reacting for 10 h, cool to room temperature, add ice water with a mass 13 times that of triethoxysilyl butyraldehyde, then add hydrochloric acid until the pH of the solution is 2, filter by suction to obtain a filter cake, and then add deionized water with a mass 4 times that of the filter cake to obtain a malonic acid reaction solution;

[0061] (10) Mix aluminum sulfate and deionized water in a mass ratio of 1:2.6, add sodium hydroxide until the pH of the solution is 10 to obtain an aluminum sulfate solution. Place the aerogel cable core in a container, spray an aluminum sulfate solution with a mass 0.4 times that of the aerogel cable core. After reacting at 160 °C for 48 min, spray sulfuric acid with a mass fraction of 8.9% and a mass 0.03 times that of the aerogel cable core, ultrasonicate at 30 kHz for 43 min, wash 8 times with deionized water, dry at 100 °C for 13 h, then spray a malonic acid reaction solution with a mass 0.7 times that of the aerogel cable core, react for 7 h, wash 8 times with deionized water, and dry at 60 °C for 14 h to obtain a waterproof and impact-resistant fireproof cable.

[0062] Comparative Example 1

[0063] The difference between Comparative Example 1 and Example 2 is that step (1) is absent, and step (2) is changed to: Mix trimethoxysilane and trioctylamine in a mass ratio of 1:1.8, heat to 78 °C, after reacting for 42 h, add petroleum ether with a mass 1.8 times that of trimethoxysilane, stir evenly, then filter by suction, and then add ethanol with a mass 3 times that of trimethoxysilane and ethyl acetate with a mass 1.7 times that of trimethoxysilane, stir at 80 rpm for 19 min, filter by suction, and dry at 60 °C for 5.5 h to obtain a quaternary ammonium compound. The remaining steps are the same as those in Example 2.

[0064] Comparative Example 2

[0065] The difference between Comparative Example 2 and Example 2 lies in the absence of step (3), and step (4) is changed to: Mix N,N-dimethylformamide, tetrahydrofuran, and quaternary ammonium compound in a mass ratio of 1:1:0.15, stir and dissolve to obtain a spinning solution, electrospin onto the cable core until the film layer thickness is 0.2 mm, then place it under a 2 kW high-pressure mercury lamp at a distance of 200 mm and irradiate for 45 s to obtain a first waterproof layer cable core; the electrospinning conditions are: the spinning voltage is 15 kV, the spinning distance is 18 cm, the spinning speed is 0.4 mL / h, both ends of the cable core are fixed, and the rotation speed is 60 rpm. The remaining steps are the same as those in Example 2.

[0066] Comparative Example 3

[0067] The difference between Comparative Example 3 and Example 2 lies in the difference in step (8). Step (8) is changed to: Place the inner sheath layer cable core in a container, heat it to 60 °C, spray a graphene oxide solution 94 times the mass of the inner sheath layer cable core. The mass ratio of graphene oxide, deionized water, and ascorbic acid in the graphene oxide solution is 1:350:0.3. After reacting for 8.5 h, place it in a water-alcohol vapor atmosphere, and the mass ratio of deionized water and absolute ethanol in the water-alcohol vapor is 1:9. After standing for 11.5 h, freeze at -15 °C for 5.5 h to obtain an aerogel cable core. The remaining steps are the same as those in Example 2.

[0068] Comparative Example 4

[0069] The difference between Comparative Example 4 and Example 2 lies in the difference in step (8). Step (8) is changed to: Place the inner sheath layer cable core under a 2 kW high-pressure mercury lamp at a distance of 200 mm, spray a diallyldiethoxysilane solution 0.65 times the mass of the inner sheath layer cable core, and irradiate for 51 s to obtain an aerogel cable core. The remaining steps are the same as those in Example 2.

[0070] Comparative Example 5

[0071] The difference between Comparative Example 5 and Example 2 lies in the difference in step (10). Step (10) is changed to: Place the aerogel cable core in a container, spray a malonic acid reaction solution 0.55 times the mass of the aerogel cable core, react for 5.8 h, wash 7 times with deionized water, and dry at 60 °C for 12 h to obtain a waterproof and impact-resistant fireproof cable. The remaining steps are the same as those in Example 2.

[0072] Comparative Example 6

[0073] The difference between Comparative Example 6 and Example 2 is that step (9) is absent, and step (10) is changed to: mixing aluminum sulfate and deionized water at a mass ratio of 1:2.6, adding sodium hydroxide until the pH of the solution is 9.5 to obtain an aluminum sulfate solution; placing the aerogel cable core in a container, spraying an aluminum sulfate solution 0.3 times the mass of the aerogel cable core, reacting at 160 °C for 41 min, then spraying sulfuric acid with a mass fraction of 8.9% 0.02 times the mass of the aerogel cable core, performing ultrasonic treatment at 30 kHz for 37 min, washing 7 times with deionized water, and drying at 100 °C for 11 h to obtain a fireproof cable with waterproof and impact-resistant properties. The remaining steps are the same as those in Example 2.

[0074] Effect Example

[0075] Table 1 below gives the performance analysis results of the fireproof cables with waterproof and impact-resistant properties of Examples 1 to 3 and Comparative Examples 1 to 6 of the present invention.

[0076] Table 1

[0077]

[0078] From the comparison of the experimental data of the continuous power supply time between the examples and the comparative examples, it can be found that the present invention uses diallyldiethoxysilane to firmly fix graphene on the surface of the inner sheath layer. Through hydrothermal reduction, an aerogel protective layer is formed to slow down the spread of flames and isolate heat, enabling the cable to have a fireproof effect; spraying and adsorbing aluminum sulfate, using the capillary effect to fill the pores of the aerogel, and then forming aluminum hydroxide to coat the surface of the aerogel pores and generate a bonding effect, reducing the flame temperature and isolating oxygen at the same time, enhancing the fireproof effect of the cable; then, grafting triethoxysilyl butyraldehyde and malonic acid on the surface of the aerogel, which is preferentially vaporized when encountering fire, diluting the oxygen concentration in the air and enhancing the fireproof effect of the cable; from the comparison of the experimental data of the dielectric constant change rate between the examples and the comparative examples, it can be found that the present invention uses 2-bromo-1,5-hexadiene, trimethoxysilane, and trioctylamine to form a silicon hydroxide compound, which can undergo a hydrolysis reaction with the infiltrated moisture to eliminate the internal moisture; using ultraviolet irradiation-electrospinning to tightly crosslink on the surface of the insulating layer to form a first waterproof layer; then introducing zinc nitrate water vapor to react with the first waterproof layer to form zinc oxide, constituting a second waterproof layer with an onion-like structure, which is beneficial to improving the waterproof effect of the cable.

[0079] 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 can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, 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, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claimed rights.

Claims

1. A waterproof and impact-resistant fireproof cable, characterized in that, The waterproof and impact-resistant fireproof cable includes a cable core, a self-made waterproof layer, a shielding layer, an inner sheath layer, and a self-made fireproof layer; The preparation method of the waterproof and impact-resistant fireproof cable includes the following preparation steps: (1) Mix N,N-dimethylformamide, tetrahydrofuran, and a silane hydroxide compound in a mass ratio of 1:1:0.1 to 1:1:0.2, stir and dissolve to obtain a spinning solution, electrospin onto the cable core until the film thickness is 0.1 to 0.3 mm, and then place it under a 2 kW high-pressure mercury lamp at a distance of 200 mm and irradiate for 30 to 60 s to obtain a first waterproof layer cable core; (2) Place the first waterproof layer cable core in a container, seal it, introduce zinc nitrate water vapor at 180 °C at a rate of 20 mL / h, react for 15 to 18 h, take it out, cool to room temperature, and dry at 80 °C for 7 to 10 h to obtain a self-made waterproof layer cable core; (3) Weave a shielding layer with a thickness of 0.1 to 0.3 mm on the surface of the self-made waterproof layer cable core using tinned copper wire to obtain a shielding layer cable core; (4) Mix cross-linked polyethylene, polyvinyl chloride resin, linear low-density polyethylene, poly-1-butene, γ-aminopropyltriethoxysilane, silicon dioxide, antioxidant 264, calcium stearate, zinc stearate, and epoxy soybean oil in a mass ratio of 1:2:1:1.8:0.1:0.2:0.08:0.1:0.05:1, stir at 100 °C and 2000 rpm for 1 to 6 min, and then extrude an inner sheath layer onto the shielding layer cable core at 145 to 160 °C to obtain an inner sheath layer cable core; (5) Place the inner sheath layer cable core under a 2 kW high-pressure mercury lamp at a distance of 200 mm, spray diallyldiethoxysilane with a mass 0.5 to 0.8 times that of the inner sheath layer cable core, irradiate for 44 to 58 s, then raise the temperature to 60 °C, spray a graphene oxide solution with a mass 88 to 100 times that of the inner sheath layer cable core. The mass ratio of graphene oxide, deionized water, and ascorbic acid in the graphene oxide solution is 1:200:0.1 to 1:500:0.

5. After reacting for 7 to 10 h, place it in an atmosphere of water-alcohol vapor, where the mass ratio of deionized water to absolute ethanol in the water-alcohol vapor is 1:

9. After standing for 10 to 13 h, freeze at -15 °C for 4 to 7 h to obtain an aerogel cable core; (6) Place the aerogel cable core in a container, spray an aluminum sulfate solution with a mass 0.2 to 0.4 times that of the aerogel cable core, react at 160 °C for 35 to 48 min, then spray sulfuric acid with a mass fraction of 8.9% and a mass 0.01 to 0.03 times that of the aerogel cable core, ultrasonically treat at 30 kHz for 31 to 43 min, wash with deionized water 6 to 8 times, dry at 100 °C for 9 to 13 h, then spray a malonic acid reaction solution with a mass 0.4 to 0.7 times that of the aerogel cable core, react for 4.5 to 7 h, wash with deionized water 6 to 8 times, and dry at 60 °C for 10 to 14 h to obtain the waterproof and impact-resistant fireproof cable; The preparation method of the silane hydroxide compound is: A. Mix 2-bromo-1,5-hexadiene, phenothiazine, chloroplatinic acid, isopropyl alcohol, and octamethylcyclotetrasiloxane in a mass ratio of 1:0.01:0.001:0.004:0.0006 to 1:0.02:0.002:0.006:0.0008. After stirring evenly, heat to 90 - 95 °C, and add trimethoxysilane in an amount 0.8 - 1.1 times the mass of 2-bromo-1,5-hexadiene, and react for 2 - 4.5 h to obtain a silicon oxide compound; B. Mix the silicon oxide compound and trioctyl decylamine in a mass ratio of 1:1.5 to 1:2.0, heat to 78 °C, and after reacting for 40 - 44 h, add petroleum ether in an amount 1.5 - 2.0 times the mass of the silicon oxide compound. After stirring evenly, perform suction filtration, then add ethanol in an amount 2 - 4 times the mass of the silicon oxide compound and ethyl acetate in an amount 1.1 - 2.3 times the mass of the silicon oxide compound, stir at 80 rpm for 15 - 24 min, perform suction filtration, and dry at 60 °C for 4 - 7 h to obtain a quaternary ammonium compound; C. Place the strongly basic anion exchange resin in an ion exchange column, add a quaternary ammonium compound solution in an amount 1.0 - 1.5 times the mass of the strongly basic anion exchange resin at a rate of 50 mL / h. The mass ratio of the quaternary ammonium compound to absolute ethanol in the quaternary ammonium compound solution is 1:

3. Then wash with absolute ethanol 2 - 4 times, perform rotary evaporation at 300 rpm and 80 °C for 60 - 72 min, and dry at 70 °C for 3 - 6 h; The preparation method of the aluminum sulfate solution is as follows: Mix aluminum sulfate and deionized water in a mass ratio of 1:2.6, and add sodium hydroxide until the pH of the solution is 9 - 10; The preparation method of the malonic acid reaction solution is as follows: Mix triethoxysilyl butyraldehyde, malonic acid, N,N-dimethylformamide, and pyridine in a mass ratio of 1:1.1:3:0.2 to 1:1.6:5:0.4, heat to 90 °C, and after reacting for 7 - 10 h, cool to room temperature, add ice water in an amount 9 - 13 times the mass of triethoxysilyl butyraldehyde, then add hydrochloric acid until the pH of the solution is 1 - 2, perform suction filtration to obtain a filter cake, and then add deionized water in an amount 2 - 4 times the mass of the filter cake.

2. The fireproof cable with waterproof and impact-resistant properties according to claim 1, characterized in that, The cable core includes a tinned copper wire core material and a cross-linked polyethylene insulating layer.

3. A waterproof and impact-resistant fireproof cable according to claim 1, characterized in that, The electrospinning conditions in step (1) are as follows: The spinning voltage is 15 kV, the spinning distance is 18 cm, the spinning speed is 0.4 mL / h, both ends of the cable core are fixed, and the rotation speed is 60 rpm.

4. A waterproof and impact-resistant fireproof cable according to claim 1, characterized in that, The zinc nitrate water vapor in step (2) is prepared by mixing zinc nitrate hexahydrate and deionized water in a mass ratio of 1:13.4.

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