Fireproof composite low-voltage cable and preparation method thereof

Abstract

The present application relates to a kind of fireproof composite low-voltage cable, it is related to composite cable preparation technical field, including cable line A, signal line B, tape layer C and outer sheath D;The outer sheath D is made of polyurethane cable material, polyurethane cable material includes following weight parts raw materials: thermoplastic polyurethane 45-55 parts, ethylene-vinyl acetate copolymer 10-15 parts, modified flame retardant 15-25 parts, antioxidant 3-5 parts, lubricant 2-4 parts, light stabilizer 1-3 parts and modified filler 10-12 parts.The modified flame retardant molecule includes sodium sulfonate base, phosphoramide structure, cinnamic amide structure, improves the flame retardance and rat resistance of cable.The modified filler molecule includes nano calcium carbonate, sorbate base, fluorine-containing alkane long chain, etc., improves the mechanical property, antibacterial property and waterproofness of cable.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite cable preparation, and particularly relates to a fireproof composite low-voltage cable and a preparation method thereof. BACKGROUND

[0002] With the rapid development of data communication and information technology, the performance requirements of cables are also increasingly high. The cable integrating signal lines and power lines is widely used, which can not only transmit current but also transmit optical signals and other signals. For such a composite cable, not only effective shielding between the power transmitted by the power line and the signal transmitted by the signal line is needed, but also the outside interference signal is shielded during the signal transmission through the line, and the signal in the line should also avoid interfering with the outside environment. In the composite cable, an insulating layer is usually coated on the outer periphery of the power conductor in the power line, and a shielding layer, a heat insulation layer, etc. are coated on the outer periphery of the signal line. The outer sheath is located at the outermost layer of the composite cable and is coated on the outer periphery of the signal line and the power line. The protection of the cable outer sheath is extremely important for maintaining the performance of the composite cable.

[0003] Thermoplastic polyurethane materials are widely used in cable sheath materials due to their excellent wear resistance, oil resistance, low-temperature flexibility and elasticity. However, when used in harsh environments such as water bubbles, riverbanks and wharfs, the cable sheath material is prone to bacterial and mold growth under humid and hot conditions, resulting in a sharp decrease in mechanical properties. If cracks occur in the cable sheath, bacteria and mold will further enter the sheath and destroy the structure, thereby reducing the safety of the cable and shortening the service life of the cable. In addition, the flame retardant performance of polyurethane materials is not good, and the cable outer sheath made of polyurethane material is located at the outermost layer, which is easily gnawed by mice and insects, resulting in a decrease in the protective performance of the outer sheath. Therefore, it is urgent to develop a suitable modification method to improve the antibacterial property, water resistance, flame retardancy and rat resistance of the thermoplastic polyurethane sheath material, so as to obtain a composite cable with excellent comprehensive performance, which can meet the increasingly stringent use requirements. SUMMARY

[0004] The object of the present application can be achieved by the following technical solutions:

[0005] A fireproof composite low-voltage cable comprises a cable line, a signal line, a tape layer and an outer sheath. A plurality of cable lines and a plurality of signal lines are uniformly placed in the tape layer, the tape layer is coated on the outer periphery of the cable line and the signal line, and the outer sheath is coated on the outer periphery of the tape layer.

[0006] The innermost layer of the cable line is a copper conductor, and the outer periphery of the copper conductor is coated with an insulating layer; the insulating layer is made of cross-linked polyethylene material;

[0007] The innermost layer of the signal line is an optical fiber core bundle, the outer periphery of the optical fiber core bundle is sequentially covered with a shielding layer, a thermal insulation layer and an optical cable sheath pipe; the shielding layer is made of electric shielding wires and magnetic shielding wires woven into a mesh structure, the electric shielding wires are copper wires, and the magnetic shielding wires are iron wires; the thermal insulation layer is made of silicone rubber, and the optical cable sheath pipe is a nylon loose sleeve pipe;

[0008] The tape wrapping layer is obtained by wrapping polyester tape;

[0009] The outer sheath is made of polyurethane cable material, and the polyurethane cable material comprises the following raw materials in parts by weight: 45-55 parts of thermoplastic polyurethane, 10-15 parts of ethylene-vinyl acetate copolymer, 15-25 parts of modified flame retardant, 3-5 parts of antioxidant, 2-4 parts of lubricant, 1-3 parts of light stabilizer and 10-12 parts of modified filler; the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 618 at a mass ratio of 3:1, the lubricant is polyethylene wax, and the light stabilizer is 2,2'-hydroxy-4-methoxybenzophenone;

[0010] The preparation of the fireproof composite low-voltage cable comprises the following steps:

[0011] Step S1: extruding a crosslinked polyethylene material around the outer periphery of the copper wire to form an insulation layer, thereby obtaining a cable wire;

[0012] Step S2: weaving the copper wire and the iron wire into a mesh structure and then covering the mesh structure around the outer periphery of the optical fiber core bundle to form a shielding layer; then extruding silicone rubber around the outer periphery of the shielding layer to form a thermal insulation layer; and then covering a nylon loose sleeve pipe around the outer periphery of the thermal insulation layer to form an optical cable sheath pipe, thereby obtaining a signal line;

[0013] Step S3: adding ethylene-vinyl acetate copolymer, modified flame retardant, antioxidant, lubricant, light stabilizer and modified filler into a high-speed mixer, stirring at a speed of 250-300 r / min and a temperature of 80-90℃ for 10-20 min to obtain a mixture, transferring the mixture into an internal mixer, adding thermoplastic polyurethane and mixing for 8-10 min to obtain polyurethane cable material;

[0014] Step S4: uniformly placing a plurality of cable wires and a plurality of signal lines, wrapping polyester tape around the outer periphery of the plurality of cable wires and the plurality of signal lines to form a tape wrapping layer, and extruding polyurethane cable material around the outer periphery of the tape wrapping layer to form an outer sheath, thereby obtaining a fireproof composite low-voltage cable.

[0015] The preparation of the modified flame retardant comprises the following steps:

[0016] Step a1: under nitrogen atmosphere, sodium benzaldehyde-2-sulfonate, acetic anhydride were added into a reaction bottle, stirring under reflux, temperature was raised to 150-170℃, then potassium carbonate was added, constant temperature stirring under reflux for 24-26h, extraction, rotary evaporation, drying to obtain alkenyl carboxylic acid; alkenyl carboxylic acid was added into DMF, stirring, dichlorosulfoxide was added, stirring under reflux at 50℃ for 4-5h to obtain acyl chloride product;

[0017] Further, the amount ratio of sodium benzaldehyde-2-sulfonate, acetic anhydride, potassium carbonate was 0.1mol: 0.05-0.07mol: 0.005-0.008mol; the amount ratio of alkenyl carboxylic acid, DMF, dichlorosulfoxide was 0.1mol: 65-75mL: 0.12-0.15mol;

[0018] In the process of step a1 reaction, the aldehyde group of sodium benzaldehyde-2-sulfonate reacted with acetic anhydride to generate alkenyl carboxylic acid containing sulfonate group; the carboxyl group of alkenyl carboxylic acid reacted with dichlorosulfoxide to generate acyl chloride product;

[0019] Step a2: N-aminoethylpiperazine, potassium carbonate and dimethyl sulfoxide were added into a flask to obtain mixed solution 1, then the acyl chloride product was added into dimethyl sulfoxide to obtain mixed solution 2, under 0℃ ice water bath, mixed solution 2 was slowly added into mixed solution 1, after the addition was completed, the temperature was raised to 40℃, constant temperature stirring for 8-10h, then reduced pressure distillation to obtain amide product;

[0020] Further, the amount ratio of N-aminoethylpiperazine, potassium carbonate, dimethyl sulfoxide was 0.1mol: 0.002-0.004mol: 25-35mL; the amount ratio of acyl chloride product, dimethyl sulfoxide was 0.1mol: 75-85mL; the amount ratio of mixed solution 1, mixed solution 2 was 30-40mL: 80-90mL;

[0021] In the process of step a2 reaction, the primary amino group of N-aminoethylpiperazine reacted with acyl chloride product to generate amide product;

[0022] Step a3: phenylphosphonic dichloride was added into toluene, then the amide product was added, stirring at 0-5℃ for 2h, then the temperature was raised to 40-50℃, constant temperature stirring under reflux for 1h, filtration, extraction, drying to obtain modified flame retardant;

[0023] Further, the amount ratio of phenylphosphonic dichloride, toluene, amide product was 0.1mol: 260-270mL: 0.2mol;

[0024] In the process of step a3 reaction, the secondary amino group of amide product reacted with phenylphosphonic dichloride to generate modified flame retardant containing phosphoric amide.

[0025] The modified filler is prepared by the following steps:

[0026] Step b1: nano calcium carbonate was added into ethanol, and after ultrasonic dispersion for 30 min, solution 1 was obtained and added into a three-necked flask; linoleic acid was added into ethanol, and after stirring at 50-60℃ for 35-45 min, solution 2 was obtained and added into the three-necked flask; reflux stirring was started, and the reaction was carried out at 70-80℃ for 1-1.5 h; then, after filtration, drying and grinding, modified calcium carbonate was obtained;

[0027] Further, the amount ratio of nano calcium carbonate to ethanol was 10 g:30-40 mL, the amount ratio of linoleic acid to ethanol was 0.1 mol:60-70 mL, and the amount ratio of solution 1 to solution 2 was 35-45 mL:65-75 mL; the volume fraction of ethanol was 95%;

[0028] During the reaction of step b1, linoleic acid was used to modify nano calcium carbonate by wet method to obtain modified calcium carbonate with long alkyl chains containing unsaturated double bonds on the surface;

[0029] Step b2: modified calcium carbonate was added into dichloromethane, and stirring was started; then, 3-chloroperoxybenzoic acid was added, and the reaction was carried out at room temperature for 4-5 h to obtain an epoxy product; sorbic acid and ethanol were added into a flask under nitrogen atmosphere, and the temperature was raised to 45℃; pyridine was added, and stirring was started; then, the epoxy product was added into the flask, and the reaction was carried out for 8-10 h; then, the temperature was raised to 105-115℃, and stirring was carried out for 1-2 h to obtain an esterification product;

[0030] Further, the amount ratio of modified calcium carbonate to dichloromethane to 3-chloroperoxybenzoic acid was 12-14 g:50-60 mL:0.1 mol; the amount ratio of sorbic acid to ethanol to pyridine to the epoxy product was 0.2 mol:80-90 mL:0.020-0.025 mol:25-27 g; and the volume fraction of ethanol was 95%;

[0031] During the reaction of step b2, the unsaturated carbon-carbon double bonds in the modified calcium carbonate were oxidized into epoxy groups to obtain the epoxy product; the ring-opening reaction of the carboxyl groups in sorbic acid with the epoxy groups in the epoxy product generated an esterification product containing alcohol hydroxyl groups;

[0032] Step b3: the esterification product and isocyanate were mixed, and dilute sulfuric acid solution with a mass fraction of 20% and methanol were added; the reaction was carried out at 50℃ for 4 h to obtain a modified filler;

[0033] Further, the amount ratio of the esterification product to isocyanate to dilute sulfuric acid solution with a mass fraction of 20% to methanol was 30-32 g:0.2 mol:100 mL:300-320 mL; the isocyanate was 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl isocyanate;

[0034] During the reaction of step b3, the alcohol hydroxyl group of the esterification product reacts with the isocyanate to obtain the modified filler.

[0035] The application discloses a fireproof composite low-voltage cable, which comprises a cable line, a signal line, a wrapping layer and an outer sheath.

[0036] The modified flame retardant comprises a sodium sulfonate group, a phosphoramide structure and a cinnamic amide structure; the sulfur element in the sodium sulfonate group generates sulfur dioxide and other non-combustible gases during combustion, dilutes the combustible gas concentration, and is solidified in the carbon layer in the form of sodium sulfate and sodium sulfite compound to form a dense and thick protective carbon layer, reduces the heat transfer of the combustion site, and effectively prevents the further combustion of the substrate in the gas phase and the solid phase, while inhibiting the release of smoke; the phosphoramide structure generates phosphorus-containing compounds during combustion, promotes the formation of a carbon layer, and is coated on the surface of the polymer; the carbon layer is non-combustible, oxygen-proof and poor in thermal conductivity, prevents continuous combustion, and generates non-combustible gases to dilute combustible gases, has a coordinated effect of phosphorus-nitrogen flame retardant, and synergizes with the sodium sulfonate group in the same molecule to quickly prevent combustion from continuing, and has excellent flame retardant performance; the cinnamic amide structure not only does not produce toxic substances and odors harmful to the human body and pollute the environment, but also has long-term mouse repelling effect, prevents mice from gnawing the outer sheath material and losing the protection function of the outer sheath. Therefore, the modified flame retardant makes the cable have excellent flame retardance and rat resistance.

[0037] The modified filler comprises nano calcium carbonate, a sorbate group, a fluorine-containing alkane long chain and an isocyanate group. The hydrophilic and oleophobic property of the surface of the nano calcium carbonate in the modified filler is improved, the nano calcium carbonate is not easy to agglomerate, the dispersion compatibility in the substrate is enhanced, and the mechanical property of the outer sheath is improved; compared with sorbic acid which is difficult to enter the microbial cells due to the formation of ionic state under neutral and alkaline conditions, the sorbate is less affected by the acid and alkali and has stronger affinity with the microbial membrane, and is more likely to penetrate into the microbial cells, so that the antibacterial property is stronger; the fluorine-containing alkane long chain has strong hydrophobicity, can prevent water from penetrating into the outer sheath, and causes the cable insulation property and other properties to be affected; the isocyanate group is similar in structure to the thermoplastic polyurethane, and is helpful to the dispersion of the modified filler in the substrate. Therefore, the modified flame retardant enhances the mechanical property, antibacterial property and water resistance of the cable. BRIEF DESCRIPTION OF DRAWINGS

[0038] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort based on these drawings.

[0039] Figure 1 FIG. 1 is a structural schematic diagram of a fireproof composite low-voltage cable according to the present application.

[0040] In the drawings, the components represented by the numbers are listed as follows:

[0041] A, cable line, A I, copper conductor, A II, copper conductor;

[0042] B, signal line, B I, optical fiber core bundle, B II, shielding layer, B III, thermal insulation layer, B IV, optical cable sheath tube;

[0043] C, tape layer; D, outer sheath; DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the present application will be described clearly and completely in the following with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without any creative effort fall within the scope of protection of the present application.

[0045] Embodiment 1: a modified flame retardant, the preparation thereof comprises the following steps:

[0046] Step a1: under nitrogen atmosphere, sodium benzaldehyde-2-sulfonate and acetic anhydride are added into a reaction bottle, reflux stirring is started, the temperature is raised to 150℃, then potassium carbonate is added, constant temperature reflux stirring is carried out for 24h, extraction, rotary evaporation and drying are carried out to obtain alkenyl carboxylic acid; the alkenyl carboxylic acid is added into DMF, dichlorosulfoxide is added under stirring, reflux stirring is carried out at 50℃ for 4h to obtain acyl chloride product; the amount ratio of sodium benzaldehyde-2-sulfonate, acetic anhydride and potassium carbonate is 0.1mol:0.05mol:0.005mol; the amount ratio of alkenyl carboxylic acid, DMF and dichlorosulfoxide is 0.1mol:65mL:0.12mol;

[0047] Step a2: N-aminoethylpiperazine, potassium carbonate and dimethyl sulfoxide were added into a flask to obtain a mixture 1, and the acyl chloride product was added into dimethyl sulfoxide to obtain a mixture 2, the mixture 2 was slowly added into the mixture 1 under an ice water bath at 0°C, after the addition was completed, the temperature was increased to 40°C, constant temperature stirring reaction was carried out for 8h, and then vacuum distillation was carried out, to obtain the amide product; the amount ratio of N-aminoethylpiperazine, potassium carbonate and dimethyl sulfoxide was 0.1mol:0.002mol:25mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide was 0.1mol:75mL; the amount ratio of the mixture 1 and the mixture 2 was 30mL:80mL;

[0048] Step a3: phenylphosphonic dichloride was added into toluene, and then the amide product was added, after stirring for 2h under 0°C, the temperature was increased to 40°C, constant temperature reflux stirring reaction was carried out for 1h, and then filtration, extraction and drying were carried out, to obtain the modified flame retardant; the amount ratio of phenylphosphonic dichloride, toluene and the amide product was 0.1mol:260mL:0.2mol.

[0049] Example 2: a modified flame retardant, the preparation thereof comprises the following steps:

[0050] Step a1: benzaldehyde-2-sulfonic acid sodium, acetic anhydride were added into a reaction bottle under nitrogen atmosphere, reflux stirring was started, the temperature was increased to 1670°C, potassium carbonate was added, constant temperature reflux stirring reaction was carried out for 25h, and then extraction, rotary evaporation and drying were carried out, to obtain an alkenyl carboxylic acid; the alkenyl carboxylic acid was added into DMF, and dichlorosulfoxide was added under stirring, constant temperature reflux stirring reaction was carried out for 4.5h under 50°C, to obtain the acyl chloride product; the amount ratio of benzaldehyde-2-sulfonic acid sodium, acetic anhydride and potassium carbonate was 0.1mol:0.06mol:0.006mol; the amount ratio of the alkenyl carboxylic acid, DMF and dichlorosulfoxide was 0.1mol:70mL:0.13mol;

[0051] Step a2: N-aminoethylpiperazine, potassium carbonate and dimethyl sulfoxide were added into a flask to obtain a mixture 1, and the acyl chloride product was added into dimethyl sulfoxide to obtain a mixture 2, the mixture 2 was slowly added into the mixture 1 under an ice water bath at 0°C, after the addition was completed, the temperature was increased to 40°C, constant temperature stirring reaction was carried out for 9h, and then vacuum distillation was carried out, to obtain the amide product; the amount ratio of N-aminoethylpiperazine, potassium carbonate and dimethyl sulfoxide was 0.1mol:0.003mol:30mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide was 0.1mol:80mL; the amount ratio of the mixture 1 and the mixture 2 was 35mL:85mL;

[0052] Step a3: phenylphosphonic dichloride was added into toluene, and then the amide product was added, after stirring for 2h under 5°C, the temperature was increased to 45°C, constant temperature reflux stirring reaction was carried out for 1h, and then filtration, extraction and drying were carried out, to obtain the modified flame retardant; the amount ratio of phenylphosphonic dichloride, toluene and the amide product was 0.1mol:265mL:0.2mol.

[0053] Example 3: A modified flame retardant, the preparation comprising the following steps:

[0054] Step a1: under nitrogen atmosphere, sodium benzaldehyde-2-sulfonate, acetic anhydride are added into a reaction bottle, reflux stirring is started, the temperature is raised to 170℃, then potassium carbonate is added, constant temperature reflux stirring is carried out for 26h, extraction, rotary evaporation, drying to obtain alkenyl carboxylic acid; the alkenyl carboxylic acid is added into DMF, dichlorosulfoxide is added under stirring, reflux stirring is carried out at 50℃ for 5h to obtain acyl chloride product; the amount ratio of sodium benzaldehyde-2-sulfonate, acetic anhydride, potassium carbonate is 0.1mol:0.07mol:0.008mol; the amount ratio of alkenyl carboxylic acid, DMF, dichlorosulfoxide is 0.1mol:75mL:0.15mol;

[0055] Step a2: N-aminoethylpiperazine, potassium carbonate and dimethyl sulfoxide are added into a flask to obtain a mixed solution 1, then the acyl chloride product is added into dimethyl sulfoxide to obtain a mixed solution 2, under 0℃ ice water bath, the mixed solution 2 is slowly added into the mixed solution 1, after the addition is completed, the temperature is raised to 40℃, constant temperature stirring is carried out for 10h, reduced pressure distillation to obtain amide product; the amount ratio of N-aminoethylpiperazine, potassium carbonate, dimethyl sulfoxide is 0.1mol:0.004mol:35mL; the amount ratio of acyl chloride product, dimethyl sulfoxide is 0.1mol:85mL; the amount ratio of the mixed solution 1, the mixed solution 2 is 40mL:90mL;

[0056] Step a3: phenylphosphonic dichloride is added into toluene, then the amide product is added, after stirring at 5℃ for 2h, the temperature is raised to 50℃, constant temperature reflux stirring is carried out for 1h, filtration, extraction, drying to obtain modified flame retardant; the amount ratio of phenylphosphonic dichloride, toluene, amide product is 0.1mol:270mL:0.2mol.

[0057] Example 4: A modified filler, the preparation comprising the following steps:

[0058] Step b1: nano calcium carbonate is added into ethanol, after ultrasonic dispersion for 30min, a solution 1 is obtained and added into a three-necked flask, then linoleic acid is added into ethanol, after stirring at 50℃ for 35min, a solution 2 is obtained and added into the three-necked flask, reflux stirring is started at 70℃ for 1h, then filtration, drying, grinding to obtain modified calcium carbonate; the amount ratio of nano calcium carbonate, ethanol is 10g:30mL, the amount ratio of linoleic acid, ethanol is 0.1mol:60mL, the amount ratio of the solution 1, the solution 2 is 35mL:65mL, the volume fraction of ethanol is 95%;

[0059] Step b2: the modified calcium carbonate was added into dichloromethane, and stirring was started, then 3-chloroperoxybenzoic acid was added, and the reaction was stirred at room temperature for 4 h to obtain an epoxy product; sorbic acid and ethanol were added into a flask under nitrogen atmosphere, and the temperature was raised to 45 °C, pyridine was added, and stirring was started, then the epoxy product was added into the flask, and the reaction was stirred for 8 h, then the temperature was raised to 105 °C, and stirring was performed for 1 h to obtain an esterification product; the amount ratio of the modified calcium carbonate, dichloromethane and 3-chloroperoxybenzoic acid was 12 g: 50 mL: 0.1 mol; the amount ratio of sorbic acid, ethanol, pyridine and the epoxy product was 0.2 mol: 80 mL: 0.020 mol: 25 g, and the volume fraction of ethanol was 95%;

[0060] Step b3: after the esterification product and isocyanate were mixed, a 20% mass fraction dilute sulfuric acid solution and methanol were added, and the reaction was performed at 50 °C for 4 h to obtain a modified filler; the amount ratio of the esterification product, isocyanate, 20% mass fraction dilute sulfuric acid solution and methanol was 30 g: 0.2 mol: 100 mL: 300 mL, and the isocyanate was 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl isocyanate.

[0061] Example 5: a modified filler, the preparation of which comprises the following steps:

[0062] Step b1: nano calcium carbonate was added into ethanol, and ultrasonic dispersion was performed for 30 min to obtain solution 1, which was added into a three-necked flask, then linoleic acid was added into ethanol, and stirring was performed at 55 °C for 40 min to obtain solution 2, which was added into the three-necked flask, and reflux stirring was started, and the reaction was performed at 75 °C for 1.3 h, then the modified calcium carbonate was obtained by filtration, drying and grinding; the amount ratio of nano calcium carbonate and ethanol was 10 g: 35 mL, the amount ratio of linoleic acid and ethanol was 0.1 mol: 65 mL, the amount ratio of solution 1 and solution 2 was 40 mL: 70 mL, and the volume fraction of ethanol was 95%;

[0063] Step b2: the modified calcium carbonate was added into dichloromethane, and stirring was started, then 3-chloroperoxybenzoic acid was added, and the reaction was stirred at room temperature for 4.5 h to obtain an epoxy product; sorbic acid and ethanol were added into a flask under nitrogen atmosphere, and the temperature was raised to 45 °C, pyridine was added, and stirring was started, then the epoxy product was added into the flask, and the reaction was stirred for 9 h, then the temperature was raised to 110 °C, and stirring was performed for 1.5 h to obtain an esterification product; the amount ratio of the modified calcium carbonate, dichloromethane and 3-chloroperoxybenzoic acid was 13 g: 55 mL: 0.1 mol; the amount ratio of sorbic acid, ethanol, pyridine and the epoxy product was 0.2 mol: 85 mL: 0.023 mol: 26 g, and the volume fraction of ethanol was 95%;

[0064] Step b3: after mixing the esterification product and the isocyanate, a 20% mass fraction dilute sulfuric acid solution and methanol are added, and the reaction is carried out at 50°C for 4h to obtain the modified filler; the amount ratio of the esterification product, the isocyanate, the 20% mass fraction dilute sulfuric acid solution and methanol is 31g: 0.2mol: 100mL: 310mL, and the isocyanate is 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl isocyanate.

[0065] Example 6: a modified filler, the preparation comprising the following steps:

[0066] Step b1: nano calcium carbonate is added into ethanol, ultrasonic dispersion is carried out for 30min to obtain solution 1, which is added into a three-necked flask, linoleic acid is added into ethanol, stirring is carried out at 60°C for 45min to obtain solution 2, which is added into the three-necked flask, reflux stirring is started, and the reaction is carried out at 80°C for 1.5h, and then the modified calcium carbonate is obtained through filtration, drying and grinding; the amount ratio of nano calcium carbonate and ethanol is 10g: 40mL, the amount ratio of linoleic acid and ethanol is 0.1mol: 70mL, and the amount ratio of solution 1 and solution 2 is 45mL: 75mL, and the volume fraction of ethanol is 95%;

[0067] Step b2: the modified calcium carbonate is added into dichloromethane, stirring is started, 3-chloroperbenzoic acid is added, stirring is carried out at room temperature for 5h to obtain the epoxy product; sorbic acid and ethanol are added into a flask in a nitrogen atmosphere, the temperature is raised to 45°C, pyridine is added, stirring is started, the epoxy product is added into the flask, stirring reaction is carried out for 10h, then the temperature is raised to 115°C, and stirring is carried out for 2h to obtain the esterification product; the amount ratio of the modified calcium carbonate, dichloromethane and 3-chloroperbenzoic acid is 14g: 60mL: 0.1mol; the amount ratio of sorbic acid, ethanol, pyridine and the epoxy product is 0.2mol: 90mL: 0.025mol: 27g, and the volume fraction of ethanol is 95%;

[0068] Step b3: after mixing the esterification product and the isocyanate, a 20% mass fraction dilute sulfuric acid solution and methanol are added, and the reaction is carried out at 50°C for 4h to obtain the modified filler; the amount ratio of the esterification product, the isocyanate, the 20% mass fraction dilute sulfuric acid solution and methanol is 32g: 0.2mol: 100mL: 320mL, and the isocyanate is 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl isocyanate.

[0069] Example 7: as Figure 1The fireproof composite low-voltage cable shown comprises cable lines A, signal lines B, wrapping layers C and outer sheaths D; a plurality of the cable lines A and a plurality of the signal lines B are uniformly placed in the wrapping layers C, the wrapping layers C are wrapped around the outer periphery of the cable lines A and the signal lines B, and the outer sheaths D are wrapped around the outer periphery of the wrapping layers C;

[0070] The innermost layer of the cable line A is a copper wire A I, and the outer periphery of the copper wire A I is wrapped with an insulation layer A II; the insulation layer A II is made of cross-linked polyethylene material; the innermost layer of the signal line B is an optical fiber core bundle B I, and the outer periphery of the optical fiber core bundle B I is wrapped with a shielding layer B II, a heat insulation layer B III and an optical cable sheath pipe B IV in sequence; the shielding layer B II is made of electric shielding wires and magnetic shielding wires woven into a mesh structure, the electric shielding wires are copper wires, and the magnetic shielding wires are iron wires; the heat insulation layer B III is made of silicone rubber, and the optical cable sheath pipe B IV is a nylon loose sleeve pipe; the wrapping layer C is obtained by wrapping with polyester tape; the outer sheath D is made of polyurethane cable material, and the polyurethane cable material comprises the following raw materials in parts by weight: thermoplastic polyurethane 45 parts, ethylene-vinyl acetate copolymer 10 parts, modified flame retardant 15 parts, antioxidant 3 parts, lubricant 2 parts, light stabilizer 1 part and modified filler 10 parts; the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 618 in a mass ratio of 3:1, the lubricant is polyethylene wax, and the light stabilizer is 2,2'-hydroxy-4-methoxybenzophenone;

[0071] The preparation of the fireproof composite low-voltage cable comprises the following steps:

[0072] Step S1: cross-linked polyethylene material is extruded and wrapped around the outer periphery of the copper wire to form an insulation layer, and a cable line is obtained;

[0073] Step S2: copper wires and iron wires are woven into a mesh structure and wrapped around the outer periphery of the optical fiber core bundle to form a shielding layer; then silicone rubber is extruded and wrapped around the outer periphery of the shielding layer to form a heat insulation layer; and then a nylon loose sleeve pipe is wrapped around the outer periphery of the heat insulation layer to form an optical cable sheath pipe, and a signal line is obtained;

[0074] Step S3: ethylene-vinyl acetate copolymer, the modified flame retardant obtained in Example 1, antioxidant, lubricant, light stabilizer and the modified filler obtained in Example 4 are added into a high-speed mixer, stirred at a speed of 250 r / min and a temperature of 80℃ for 10 min to obtain a mixture, and the mixture is transferred into an internal mixer, and thermoplastic polyurethane is added and mixed for 8 min to obtain polyurethane cable material;

[0075] Step S4: eight cable lines and six signal lines are uniformly placed, and polyester tape is wrapped around the outer periphery of the cable lines and the signal lines to form a wrapping layer; and then polyurethane cable material is extruded and wrapped around the outer periphery of the wrapping layer to form an outer sheath, and a fireproof composite low-voltage cable is prepared.

[0076] Embodiment 8: a fireproof composite low-voltage cable as shown in Figure 1 The fireproof composite low-voltage cable comprises cable lines A, signal lines B, a wrapping layer C and an outer sheath D; a plurality of the cable lines A and a plurality of the signal lines B are uniformly placed in the wrapping layer C, the wrapping layer C is wrapped around the outer periphery of the cable lines A and the signal lines B, and the outer sheath D is wrapped around the outer periphery of the wrapping layer C;

[0077] The innermost layer of the cable line A is a copper wire A I, and the outer periphery of the copper wire A I is wrapped with an insulation layer A II; the insulation layer A II is made of cross-linked polyethylene material; the innermost layer of the signal line B is an optical fiber core bundle B I, and the outer periphery of the optical fiber core bundle B I is wrapped with a shielding layer B II, a heat insulation layer B III and an optical cable sheath pipe B IV in sequence; the shielding layer B II is made of a mesh structure woven by an electric shielding wire and a magnetic shielding wire, the electric shielding wire is a copper wire, and the magnetic shielding wire is an iron wire; the heat insulation layer B III is made of silicone rubber, and the optical cable sheath pipe B IV is a nylon loose sleeve; the wrapping layer C is obtained by wrapping a polyester tape; the outer sheath D is made of polyurethane cable material, and the polyurethane cable material comprises the following raw materials in parts by weight: thermoplastic polyurethane 50 parts, ethylene-vinyl acetate copolymer 13 parts, modified flame retardant 20 parts, antioxidant 4 parts, lubricant 3 parts, light stabilizer 2 parts and modified filler 11 parts; the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 618 in a mass ratio of 3:1, the lubricant is polyethylene wax, and the light stabilizer is 2,2'-hydroxy-4-methoxybenzophenone;

[0078] The preparation of the fireproof composite low-voltage cable comprises the following steps:

[0079] Step S1: cross-linked polyethylene material is extruded and wrapped around the outer periphery of the copper wire to form an insulation layer, thereby obtaining a cable line;

[0080] Step S2: the copper wire and the iron wire are woven into a mesh structure and then wrapped around the outer periphery of the optical fiber core bundle to form a shielding layer; then silicone rubber is extruded and wrapped around the outer periphery of the shielding layer to form a heat insulation layer; and then a nylon loose sleeve is wrapped around the outer periphery of the heat insulation layer to form an optical cable sheath pipe, thereby obtaining a signal line;

[0081] Step S3: the ethylene-vinyl acetate copolymer, the modified flame retardant obtained in Embodiment 2, the antioxidant, the lubricant, the light stabilizer and the modified filler obtained in Embodiment 5 are added into a high-speed mixer, stirred at a speed of 270 r / min and a temperature of 85°C for 15 min to obtain a mixture, and the mixture is transferred into a banbury mixer, and the thermoplastic polyurethane is added and banburyed for 9 min to obtain polyurethane cable material;

[0082] Step S4: 9 cable lines and 7 signal lines are uniformly placed, and a polyester tape is wrapped around the outer periphery of the cable lines and the signal lines to form a wrapping layer; and then the polyurethane cable material is extruded and wrapped around the outer periphery of the wrapping layer to form an outer sheath, thereby obtaining the fireproof composite low-voltage cable.

[0083] Example 9: As Figure 1 The fireproof composite low-voltage cable shown includes a cable A, a signal line B, a wrapping layer C, and an outer sheath D; multiple cable A and multiple signal lines B are evenly placed inside the wrapping layer C, the wrapping layer C covers the outer periphery of the cable A and the signal line B, and the outer sheath D covers the outer periphery of the wrapping layer C;

[0084] The innermost layer of cable A is a copper conductor AI, and the outer periphery of copper conductor AI is covered by an insulation layer AI; the insulation layer AI is made of cross-linked polyethylene material; the innermost layer of signal line B is an optical fiber core bundle BⅠ, and the outer periphery of optical fiber core bundle BⅠ is sequentially covered by a shielding layer BⅡ, a heat insulation layer BⅢ, and an optical cable sheath BⅣ; the shielding layer BⅡ is made of an electrical shielding wire and a magnetic shielding wire woven into a mesh structure, the electrical shielding wire is copper wire, and the magnetic shielding wire is iron wire; the heat insulation layer BⅢ is made of silicone rubber, and the optical cable sheath BⅣ is a nylon loose tube; the wrapping tape Layer C is obtained by wrapping with polyester tape; the outer sheath D is made of polyurethane cable material, which includes the following raw materials by weight: 55 parts thermoplastic polyurethane, 15 parts ethylene-vinyl acetate copolymer, 25 parts modified flame retardant, 5 parts antioxidant, 4 parts lubricant, 3 parts light stabilizer, and 12 parts modified filler; the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 618 in a mass ratio of 3:1, the lubricant is polyethylene wax, and the light stabilizer is 2,2'-hydroxy-4-methoxybenzophenone;

[0085] The fire-resistant composite low-voltage cable is manufactured using the following steps:

[0086] Step S1: Extruding cross-linked polyethylene material around the copper conductor to form an insulation layer, thus obtaining a cable;

[0087] Step S2: After braiding copper and iron wires into a mesh structure, wrap it around the outer periphery of the optical fiber core bundle to form a shielding layer; then extrude silicone rubber around the outer periphery of the shielding layer to form a heat insulation layer; then wrap nylon loose tube around the outer periphery of the heat insulation layer to form an optical cable sheath, thus obtaining the signal line.

[0088] Step S3: Add the ethylene-vinyl acetate copolymer, the modified flame retardant obtained in Example 3, the antioxidant, the lubricant, the light stabilizer, and the modified filler obtained in Example 6 to a high-speed mixer, stir at 300 r / min and 90°C for 20 min to obtain a mixture, transfer the mixture to an internal mixer, add thermoplastic polyurethane and internally mix for 10 min to obtain polyurethane cable material;

[0089] Step S4: uniformly placing 10 cable lines and 8 signal lines, wrapping the outer periphery of the cable lines and the signal lines with a polyester tape to form a tape wrapping layer; and extruding a polyurethane cable material outside the tape wrapping layer to form an outer sheath, thereby obtaining the fireproof composite low-voltage cable.

[0090] Comparative Example 1: compared with Example 9, the modified flame retardant is replaced by the amide product obtained in step a2 of Example 3, and the rest is exactly the same as Example 9, thereby obtaining the fireproof composite low-voltage cable.

[0091] Comparative Example 2: compared with Example 9, the modified filler is replaced by the modified calcium carbonate obtained in step b1 of Example 6, and the rest is exactly the same as Example 9, thereby obtaining the fireproof composite low-voltage cable.

[0092] The fireproof composite low-voltage cable prepared in the present application is further tested for effects, and the test results are as follows.

[0093] To test the fireproof composite low-voltage cable prepared in the present application, the polyurethane cable material used for the outer sheath of the fireproof composite low-voltage cable obtained in Examples 7-9 and Comparative Examples 1-2 is tested for performance, the tensile strength and elongation at break are tested according to GB / T2951.11-2008 “General test methods for cable and optical cable insulation and sheath materials”, the oxygen index is tested according to GB / T2406.1-2008 “Plastics - Determination of the burning behavior in an oxygen enrichment”, the rat-proof performance is tested according to GB / T34016-2017 “General requirements for rat and termite resistant electric wires and cables”, the antibacterial property is tested according to GB / T31402-2015 “Test method for antibacterial property of plastics on plastic surface” using E. coli and Staphylococcus aureus as test bacteria, the sample size of the polyurethane cable material is 2mm×40mm×40mm; the waterproof performance test method is as follows: a sample of the fireproof composite low-voltage cable obtained in Examples 7-9 and Comparative Examples 1-2 weighing 150.0g is immersed in water (water temperature 15℃), the two ends of the sample are sealed, the sample is stretched out of the water surface by 300mm, after soaking for one week, the weight after soaking is measured, and the outer sheath is removed after soaking, and the presence or absence of water on the outer surface is observed; the test results are recorded in Table 1.

[0094] Table 1: test results

[0095]

[0096] According to the data in Table 1, the polyurethane cable material used for the outer sheath of the fireproof composite low-voltage cable prepared by the application has excellent mechanical properties, flame retardancy, rat resistance, antibacterial property and water resistance, thereby improving the mechanical properties, flame retardancy, rat resistance, antibacterial property and water resistance of the fireproof composite low-voltage cable. Compared with Comparative Example 1, Example 9 uses a modified flame retardant with a phosphoramide structure, which synergistically retards flame with the sodium sulfonate group in the same molecule, thereby significantly improving the flame retardancy of the cable. Compared with Comparative Example 2, Example 9 uses a modified filler with a sorbate group, an isocyanate group and a fluorine-containing alkane long chain, thereby improving the antibacterial property and water resistance of the cable.

[0097] The above is only an example and a description of the concept of the application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the concept of the application or exceed the scope defined by the claims.

Claims

1. A fire resistant composite low voltage cable, characterized by: The cable line A, the signal line B, the wrapping layer C and the outer sheath D are included. The cable line A and the signal line B are evenly placed in the wrapping layer C, and the wrapping layer C is wrapped on the outer periphery of the cable line A and the signal line B. The innermost layer of the cable line A is a copper wire A I, and the outer periphery of the copper wire A I is wrapped with an insulation layer A II. The innermost layer of the signal line B is an optical fiber core B I, and the outer periphery of the optical fiber core B I is sequentially wrapped with a shielding layer B II, a heat insulation layer B III and an optical cable sheath pipe B IV. The shielding layer B II is made of an electric shielding wire and a magnetic shielding wire and is woven into a mesh structure, the electric shielding wire is a copper wire, and the magnetic shielding wire is an iron wire. The heat insulation layer B III is made of silicone rubber, and the optical cable sheath pipe B IV is a nylon sleeve pipe. The outer sheath D is made of polyurethane cable material, and the polyurethane cable material includes the following raw materials in parts by weight: thermoplastic polyurethane 45-55 parts, ethylene-vinyl acetate copolymer 10-15 parts, modified flame retardant 15-25 parts, antioxidant 3-5 parts, lubricant 2-4 parts, light stabilizer 1-3 parts and modified filler 10-12 parts. The preparation of the modified filler includes the following steps: Step b1: nano calcium carbonate is added into ethanol, ultrasonic dispersion is carried out for 30 min, solution 1 is obtained and added into a three-necked flask, linoleic acid is added into ethanol, stirring is carried out at 50-60℃ for 35-45 min, solution 2 is obtained and added into the three-necked flask, reflux stirring is carried out at 70-80℃ for 1-1.5 h, and then the modified calcium carbonate is obtained through filtration, drying and grinding. Step b2: the modified calcium carbonate is added into dichloromethane, stirring is carried out, 3-chlorine peroxide benzoic acid is added, stirring is carried out at room temperature for 4-5 h, and then the epoxy product is obtained; sorbic acid and ethanol are added into a flask under nitrogen atmosphere, the temperature is raised to 45℃, pyridine is added, stirring is carried out, the epoxy product is added into the flask, stirring reaction is carried out for 8-10 h, then the temperature is raised to 105-115℃, and stirring is carried out for 1-2 h, and then the esterification product is obtained. Step b3: the esterification product and isocyanate are mixed, dilute sulfuric acid solution with a mass fraction of 20% and methanol are added, reaction is carried out at 50℃ for 4 h, and then the modified filler is obtained, the modified filler molecule contains nano calcium carbonate, sorbate group, fluorine-containing alkane long chain and isocyanate group. The modified flame retardant molecule contains sodium sulfonate group, phosphoramide structure and cinnamamide structure, and the mechanical property, flame retardancy, rat resistance, antibacterial property and waterproofness of the fireproof composite low-voltage cable are improved. The preparation of the modified flame retardant includes the following steps: Step a1: under nitrogen atmosphere, benzaldehyde-2-sodium sulfonate and acetic anhydride are added into a reaction bottle, reflux stirring is carried out, the temperature is raised to 150-170℃, potassium carbonate is added, constant temperature reflux stirring is carried out for 24-26 h, extraction, rotary evaporation and drying are carried out, and then the alkenyl carboxylic acid is obtained. The alkenyl carboxylic acid is added into DMF, dichlorosulfoxide is added under stirring, reflux stirring is carried out at 50℃ for 4-5 h, and then the acyl chloride product is obtained. Step a2: N-aminoethyl piperazine, potassium carbonate and dimethyl sulfoxide were added into the flask to obtain a mixture 1, and the acyl chloride product was added into dimethyl sulfoxide to obtain a mixture 2, then the mixture 2 was slowly added into the mixture 1 under ice water bath at 0℃, after the addition was completed, the temperature was increased to 40℃, and the reaction was stirred at constant temperature for 8-10h, and then the amide product was obtained by distillation under reduced pressure; Step a3: benzene phosphonic dichloride was added into toluene, and then the amide product was added, after stirring at 0-5℃ for 2h, the temperature was increased to 40-50℃, and the reaction was stirred at constant temperature under reflux for 1h, and then the modified flame retardant was obtained by filtration, extraction and drying; The antioxidant is prepared by mixing antioxidant 1010 and antioxidant 618 in a mass ratio of 3:1, the lubricant is polyethylene wax, and the light stabilizer is 2,2'-hydroxy-4-methoxybenzophenone.

2. A fire resistant composite low voltage cable according to claim 1, characterized in that: In step a1, the amount ratio of benzaldehyde-2-sulfonic acid sodium, acetic anhydride and potassium carbonate is 0.1mol:0.05-0.07mol:0.005-0.008mol; the amount ratio of alkenyl carboxylic acid, DMF and dichloro sulfoxide is 0.1mol:65-75mL:0.12-0.15mol.

3. A fire resistant composite low voltage cable according to claim 1, characterized in that: In step a2, the amount ratio of N-aminoethyl piperazine, potassium carbonate and dimethyl sulfoxide is 0.1mol:0.002-0.004mol:25-35mL; the amount ratio of acyl chloride product and dimethyl sulfoxide is 0.1mol:75-85mL; the amount ratio of mixture 1 and mixture 2 is 30-40mL:80-90mL.

4. A fire resistant composite low voltage cable according to claim 1, characterized in that: In step a3, the amount ratio of benzene phosphonic dichloride, toluene and amide product is 0.1mol:260-270mL:0.2mol.

5. A fire resistant composite low voltage cable according to claim 1, characterized in that: In step b1, the amount ratio of nano calcium carbonate and ethanol is 10g:30-40mL, the amount ratio of linoleic acid and ethanol is 0.1mol:60-70mL, the amount ratio of solution 1 and solution 2 is 35-45mL:65-75mL, and the volume fraction of ethanol is 95%.

6. A fire resistant composite low voltage cable according to claim 1, characterized in that: In step b2, the amount ratio of modified calcium carbonate, dichloromethane and 3-chloro peroxyl benzoic acid is 12-14g:50-60mL:0.1mol; the amount ratio of sorbic acid, ethanol, pyridine and epoxy product is 0.2mol:80-90mL:0.020-0.025mol:25-27g, and the volume fraction of ethanol is 95%.

7. A fire resistant composite low voltage cable according to claim 1, characterized in that: In step b3, the amount ratio of esterification product, isocyanate, 20% mass fraction of dilute sulfuric acid solution and methanol is 30-32g:0.2mol:100mL:300-320mL, and the isocyanate is 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl isocyanate.

8. The method for preparing a fire-resistant composite low-voltage cable according to claim 1, characterized in that: The method comprises the following steps: Step S1: a cross-linked polyethylene material is extruded and wrapped outside a copper wire to form an insulation layer, thereby obtaining a cable wire; Step S2: after the copper wire and the iron wire are woven into a mesh structure, the mesh structure is wrapped around the outer periphery of the optical fiber core bundle to form a shielding layer; then the silicone rubber is extruded around the outer periphery of the shielding layer to form a thermal insulation layer; then the nylon loose sleeve is wrapped around the outer periphery of the thermal insulation layer to form a cable sheath pipe, and a signal wire is obtained; Step S3: ethylene-vinyl acetate copolymer, modified flame retardant, antioxidant, lubricant, light stabilizer and modified filler are added into a high-speed mixer, stirred at a speed of 250-300 r / min and a temperature of 80-90 DEG C for 10-20 min to obtain a mixture, the mixture is transferred into a banbury mixer, and thermoplastic polyurethane is added and banburyed for 8-10 min to obtain a polyurethane cable material; Step S4: a plurality of cable wires and a plurality of signal wires are uniformly placed, and a polyester tape is wrapped around the outer periphery of the plurality of cable wires and the plurality of signal wires to form a tape wrapping layer; then the polyurethane cable material is extruded around the outer periphery of the tape wrapping layer to form an outer sheath, and a fireproof composite low-voltage cable is prepared.

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