Tensile, wear-resistant and low-temperature-resistant cable material and preparation method thereof

Abstract

The invention discloses a tensile wear-resistant low-temperature-resistant cable material and a preparation method thereof, and belongs to the technical field of cables. The cable material is prepared from the following raw materials in parts by weight: 30 to 40 parts of polyvinyl chloride resin, 20 to 30 parts of ethylene propylene diene monomer, 16 to 28 parts of filler, 1.5 to 3 parts of coupling agent, 10 to 20 parts of ethylene-vinyl acetate copolymer, 7 to 14 parts of flame retardant, 2 to 5 parts of epoxidized soybean oil, 1.3 to 3.2 parts of plasticizer, 0.5 to 1.5 parts of antioxidant and 0.5 to 0.8 part of cross-linking agent. Every two of the filler, the ethylene propylene diene monomer and the flame retardant containing halogen-free flame-retardant elements of nitrogen, phosphorus and silicon and a plurality of long carbon chains have chemical action, and a cross-linked hybrid network structure is formed among the filler, the ethylene propylene diene monomer and the flame retardant; the cable material disclosed by the invention has the advantages of efficient and safe flame-retardant effect, excellent and stable mechanical property, wear resistance, low temperature resistance and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of cables, and in particular relates to a tensile, wear-resistant and low-temperature resistant cable material and a preparation method thereof. Background Art

[0002] Power cables are wires or cables used specifically for the transmission and distribution of electrical energy. They are widely used in power systems, including power plants, transmission systems, distribution systems, and final power terminals. Power cables can carry currents at different voltage levels, from low-voltage household cables to high-voltage long-distance transmission cables. Plastics used for insulation and sheathing of wires and cables are commonly known as cable materials, which include rubber, plastic, nylon and other varieties. Cable materials have broad market development prospects in my country.

[0003] Cables are prone to wear and tear in outdoor environments, especially in hot and humid or acidic and alkaline environments, which causes aging of the lines and greatly shortens the service life of the cables. They are also prone to failures in transmission lines, which poses a great safety hazard to the surrounding residents and causes great losses to the power sector. At the same time, the existing cables have poor low-temperature resistance. In low-temperature environments, the outer sheath of the cable made of cable materials is prone to become brittle, resulting in damage and reducing the service life. In addition, with the frequent occurrence of fire accidents, people's awareness of fire safety is increasing, and the flame retardant problem of wires and cables has gradually attracted everyone's attention. Existing power cables often release harmful gases and toxic smoke such as chlorine when burning, which endangers the health of escapees and firefighters, and pollutes the environment. The large amount of thick smoke produced will seriously affect the line of sight, hindering personnel evacuation and fire rescue. The failure of power cables to quickly char will also cause the melt to drip and ignite other flammable materials near the cable. The large amount of inorganic flame retardants added will also lead to a decrease in the mechanical properties of the cable. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a tensile, wear-resistant and low-temperature resistant cable material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A tensile, wear-resistant and low-temperature resistant cable material comprises the following raw materials in parts by weight: 30-40 parts of polyvinyl chloride resin, 20-30 parts of ethylene propylene rubber, 16-28 parts of filler, 1.5-3 parts of coupling agent, 10-20 parts of ethylene-vinyl acetate copolymer, 7-14 parts of flame retardant, 2-5 parts of epoxy soybean oil, 1.3-3.2 parts of plasticizer, 0.5-1.5 parts of antioxidant and 0.5-0.8 parts of cross-linking agent.

[0007] Furthermore, the filler is one or more of kaolin, carbon black, talcum powder and white carbon black.

[0008] Furthermore, the filler is a mixture of white carbon black, carbon black, talcum powder and kaolin in a mass ratio of 1:2:1:(0-0.5).

[0009] White carbon black can improve the electrical insulation performance of cables, and can also improve the elastic strength, wear resistance and hardness of cables to a certain extent, thereby extending the service life of cables; the role of carbon black in cables mainly includes UV protection, reducing volume resistivity, improving electrical properties and anti-aging properties; the role of talcum powder in cables mainly includes improving insulation performance, enhancing wear resistance, improving heat resistance, preventing adhesion, reducing friction, and improving production efficiency; the role of kaolin in cables is mainly to enhance the insulation performance, mechanical properties and strengthen wear resistance of wires and cables.

[0010] Furthermore, the coupling agent is one or more of 3-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0011] The abundant hydroxyl groups on the surface of the filler can cross-link with the silaneoxy groups of the coupling agent, and then the filler is evenly dispersed in the cable material under the action of the coupling agent, giving full play to its own role and improving the insulation, wear resistance and tensile resistance of the cable. In addition, the coupling agent also introduces unsaturated carbon-carbon double bonds on the surface of the filler, which can react chemically with the double bonds on the surface of the flame retardant under the action of the cross-linking agent, and can also react chemically with the unsaturated double bonds of the side chain of the EPDM rubber. Therefore, the filler of the present invention can be highly dispersed in the cable material, giving the cable material excellent wear resistance, insulation and mechanical physical properties.

[0012] Furthermore, the flame retardant is prepared by the following steps:

[0013] S1. Replace the air in the three-necked reaction bottle with nitrogen at room temperature, then add 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, pyridine and diethyl ether, stir thoroughly until mixed, then slowly add diallylamine, raise the temperature to 60°C after the addition is complete, keep warm for 2 hours, and after the reaction is completed, distill under reduced pressure, purify by column chromatography (a mixed solvent of benzene and ethyl acetate is used as the eluent, and the volume ratio of benzene and ethyl acetate is 8:2), and distill under reduced pressure to obtain intermediate 1; the amount ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, diallylamine, pyridine and diethyl ether is 0.082 mol:0.08 mol:9.7 mL:120 mL;

[0014] Pyridine is used as an acid-binding agent. Under heating conditions, -Cl of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and -NH- of diallylamine undergo a nucleophilic substitution reaction. The reaction process is as follows:

[0015]

[0016] S2, replace the air in the three-necked reaction bottle with nitrogen at room temperature, then add intermediate 1, triethylamine and chloroform, stir until mixed, then slowly add N-methyl-2-hydroxyethylamine, and heat to 70°C after the addition is complete, keep warm for reaction for 3 hours, after the reaction is completed, distill under reduced pressure, purify by column chromatography (the eluent is a mixed solvent of chloroform and ether, the volume ratio of chloroform to ether is 9:1), and distill under reduced pressure to obtain intermediate 2; the amount ratio of intermediate 1, N-methyl-2-hydroxyethylamine, triethylamine and chloroform is 0.07mol:0.072mol:14.5mL:120mL;

[0017] Triethylamine is used as an acid-binding agent. Under heating conditions, -Cl of intermediate 1 and -NH- of N-methyl-2-hydroxyethylamine undergo nucleophilic substitution reaction. The reaction process is as follows:

[0018]

[0019] S3, add dodecanol and tetrahydrofuran dried over anhydrous calcium chloride into a three-necked flask, stir evenly and place in a 0°C ice-water bath, then slowly add phosphorus oxychloride and pyridine under nitrogen protection, react at 0°C for 0.5h, wait for the reaction to be completed, take out the product, centrifuge and separate the product by low-speed centrifuge to obtain intermediate 3; the amount ratio of phosphorus oxychloride, dodecanol, pyridine and tetrahydrofuran is 0.03mol:0.061mol:5.5mL:120mL;

[0020] In an ice-water bath and in the presence of pyridine, phosphorus oxychloride and dodecanol undergo an esterification reaction, and the reaction process is shown below:

[0021]

[0022] S4. Add intermediate 2, triethylamine and DMSO (dimethyl sulfoxide) to a three-necked flask at room temperature and under nitrogen protection, stir evenly, slowly add a mixed solution of intermediate 3 and DMSO under stirring, react at room temperature for 1 hour, and after the reaction, perform vacuum distillation, column chromatography purification (eluent is a mixed solvent of benzene and acetone, the volume ratio of benzene and acetone is 9:1), and vacuum distillation to obtain a flame retardant. The dosage ratio of intermediate 2, intermediate 3, triethylamine and DMSO is 0.031 mol: 0.03 mol: 5 mL: 120 mL.

[0023] Intermediate 2 and intermediate 3 undergo esterification reaction under the action of triethylamine, and the reaction process is as follows:

[0024]

[0025] The flame retardant of the present invention contains halogen-free flame retardant elements of nitrogen, phosphorus and silicon, which act synergistically to endow the cable material with efficient and safe flame retardant properties.

[0026] The flame retardant contains a plurality of long carbon chains. The oil-soluble long carbon chains can increase the compatibility between the flame retardant and other raw materials; the long carbon chains that can freely expand and shrink and rotate can also increase the mechanical properties of the cable material, such as toughness and impact resistance; the flame retardant has no heterocyclic ring and benzene ring, therefore, the long carbon chains on the flame retardant can increase the flexibility of the polyvinyl chloride molecular chain segment, significantly reduce the glass transition temperature, and the synergistic effect of the flame retardant and the plasticizer makes the cable material of the present invention more resistant to low temperatures.

[0027] The flame retardant contains multiple terminal carbon-carbon double bonds. Under the action of the cross-linking agent, it can produce chemical reactions with the double bonds on the surface of the filler, and can also produce chemical reactions with the unsaturated double bonds in the side chains of EPDM rubber. Therefore, the flame retardant can be highly dispersed in the cable material and is not easy to migrate and escape, thereby giving the cable material excellent and stable mechanical properties and efficient and safe flame retardant effects.

[0028] A hybrid cross-linked network structure is formed between the flame retardant, filler and EPDM rubber, which makes the performance of the cable material more stable.

[0029] Furthermore, the plasticizer is compounded by mixing diisononyl cyclohexane 1,2-dicarboxylate and dioctyl sebacate in a mass ratio of (3-5):(1-2).

[0030] Furthermore, the antioxidant is one or more of antioxidant 1076, antioxidant 1010, antioxidant 1035, antioxidant 168, and antioxidant DLTDP.

[0031] Furthermore, the cross-linking agent is one or more of di-tert-butyl peroxide, benzoyl peroxide, and diisopropylbenzene peroxide.

[0032] A method for preparing a tensile, wear-resistant and low-temperature resistant cable material comprises the following steps:

[0033] Weigh the raw materials by weight, mix the polyvinyl chloride resin, EPDM rubber and ethylene-vinyl acetate copolymer, heat to 50-70°C, and stir for 20-30 minutes to obtain A; put the filler into a ball mill, stir and heat to 60-70°C and keep for 10-15 minutes to obtain B; mix A and B, add flame retardant, epoxy soybean oil, coupling agent, plasticizer, antioxidant and cross-linking agent, heat to 80-90°C, continue stirring for 40-60 minutes, and finally send to a twin-screw extruder granulator for extrusion granulation, dry, and obtain the cable material.

[0034] The beneficial effects of the present invention are as follows: there is a chemical reaction between the filler, the EPDM rubber and the flame retardant containing the halogen-free flame retardant elements nitrogen, phosphorus, silicon and multiple long carbon chains, and the three form a mutually cross-linked hybrid network structure. In addition, with the synergistic effect of other raw materials, the cable material of the present invention has high-efficiency and safe flame retardant effect, excellent and stable mechanical properties, wear resistance, low temperature resistance and other properties. DETAILED DESCRIPTION

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] Example 1

[0037] The flame retardant is prepared in the following steps:

[0038] S1. Replace the air in a 250 mL three-necked reaction bottle with nitrogen at room temperature, then add 18.1 mL of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, 9.7 mL of pyridine and 120 mL of ether, stir thoroughly until mixed, then slowly add 9.9 mL of diallylamine, raise the temperature to 60°C after the addition is complete, and keep the temperature to react for 2 hours. After the reaction is completed, distill under reduced pressure, purify by column chromatography (a mixed solvent of benzene and ethyl acetate is used as the eluent, and the volume ratio of benzene and ethyl acetate is 8:2), and distill under reduced pressure to obtain intermediate 1;

[0039] S2, replace the air in a 250mL three-necked reaction flask with nitrogen at room temperature, then add 20.4g of intermediate 1, 14.5mL of triethylamine and 120mL of chloroform, stir until well mixed, then slowly add 5.8mL of N-methyl-2-hydroxyethylamine, raise the temperature to 70°C after the addition is complete, keep the temperature for reaction for 3h, after the reaction is completed, distill under reduced pressure, purify by column chromatography (a mixed solvent of chloroform and ether is selected as the eluent, and the volume ratio of chloroform and ether is 9:1), and distill under reduced pressure to obtain intermediate 2;

[0040] S3, add 13.6 mL of dodecanol and 120 mL of tetrahydrofuran dried over anhydrous calcium chloride into a 250 mL three-necked flask, stir evenly and place in a 0°C ice-water bath, then slowly add 2.8 mL of phosphorus oxychloride and 5.5 mL of pyridine under nitrogen protection, react at 0°C for 0.5 h, after the reaction is completed, take out the product, and separate the product by centrifugal sedimentation using a low-speed centrifuge to obtain intermediate 3;

[0041] S4. At room temperature and under nitrogen protection, add 10.2 g of intermediate 2, 5 mL of triethylamine and 100 mL of DMSO into a 250 mL three-necked flask and stir evenly. Slowly add a mixed solution of 13.6 g of intermediate 3 and 20 mL of DMSO under stirring, and react at room temperature for 1 hour. After the reaction, perform vacuum distillation, column chromatography purification (the eluent is a mixed solvent of benzene and acetone, and the volume ratio of benzene to acetone is 9:1), and vacuum distillation to obtain a flame retardant.

[0042] Example 2

[0043] The specific steps for preparing cable materials are as follows:

[0044] Weigh each raw material by weight, mix 30 parts of polyvinyl chloride resin, 20 parts of ethylene propylene rubber, and 10 parts of ethylene-vinyl acetate copolymer, heat to 50°C, and stir for 20 minutes to obtain A; put 16 parts of talcum powder into a ball mill, stir and heat to 60°C and keep for 10 minutes to obtain B; mix A and B, and add 7 parts of the flame retardant prepared in Example 1, 2 parts of epoxy soybean oil, 1.5 parts of vinyl trimethoxy silane, 0.98 parts of cyclohexane 1,2-dicarboxylic acid diisononyl ester, 0.33 parts of dioctyl sebacate, 0.5 parts of antioxidant 1035 and 0.5 parts of diisopropylbenzene peroxide, heat to 80°C, continue stirring for 40 minutes, and finally send into a twin-screw extruder granulator for extrusion granulation, dry, and obtain a cable material.

[0045] Example 3

[0046] The specific steps for preparing cable materials are as follows:

[0047] Weigh each raw material by weight, mix 35 parts of polyvinyl chloride resin, 26 parts of ethylene propylene rubber, and 18 parts of ethylene-vinyl acetate copolymer, heat to 60°C, and stir for 25 minutes to obtain A; charge 5.3 parts of white carbon black, 10.7 parts of carbon black, 5.3 parts of talc, and 2.7 parts of kaolin into a ball mill, stir and heat to 67°C and keep for 13 minutes to obtain B; mix A and B, and add 10 parts of the flame retardant prepared in Example 1, 3 parts of epoxy soybean oil, 2 parts of 3-(methacryloyloxy)propyltrimethoxysilane, 2.1 parts of cyclohexane 1,2-dicarboxylic acid diisononyl ester, 0.9 parts of dioctyl sebacate, 1 part of antioxidant 1010 and 0.7 parts of benzoyl peroxide, heat to 85°C, continue stirring for 50 minutes, and finally send into a twin-screw extruder granulator for extrusion granulation, dry, and obtain a cable material.

[0048] Example 4

[0049] The specific steps for preparing cable materials are as follows:

[0050] Weigh each raw material by weight, mix 40 parts of polyvinyl chloride resin, 30 parts of ethylene propylene rubber, and 20 parts of ethylene-vinyl acetate copolymer, heat to 70°C, and stir for 30 minutes to obtain A; put 7 parts of white carbon black, 14 parts of carbon black, and 7 parts of talcum powder into a ball mill, stir and heat to 70°C and keep for 15 minutes to obtain B; mix A and B, and add 14 parts of the flame retardant prepared in Example 1, 5 parts of epoxy soybean oil, 3 parts of vinyl triethoxysilane, 2.5 parts of cyclohexane 1,2-dicarboxylic acid diisononyl ester, 0.7 parts of dioctyl sebacate, 0.8 parts of antioxidant 1076, 0.35 parts of antioxidant 168, 0.35 parts of antioxidant DLTDP and 0.8 parts of di-tert-butyl peroxide, heat to 90°C, continue stirring for 60 minutes, and finally send into a twin-screw extruder granulator for extrusion granulation, dry, and obtain a cable material.

[0051] Comparative Example 1

[0052] The specific steps for preparing cable materials are as follows:

[0053] The remaining steps remain unchanged, and the flame retardant in Example 4 is replaced by 7 parts of magnesium hydroxide and 7 parts of zinc borate to prepare a cable material.

[0054] Comparative Example 2

[0055] The specific steps for preparing cable materials are as follows:

[0056] The remaining steps remain unchanged, and the flame retardant in Example 4 is removed to prepare the cable material.

[0057] Performance Testing

[0058] The cable materials obtained in Examples 2-4 and Comparative Examples 1-2 were made into corresponding samples according to different standards, and the following performance tests were carried out: tensile strength and elongation at break were tested according to GB / T1040.3-2006; vertical burning grade was tested according to GB / T2408-2008; limiting oxygen index LOI was tested according to GB / T2406.1-2008; abrasion was tested according to GB / T2951-2008; the test results of all items are shown in the following table:

[0059]

[0060]

[0061] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0062] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A tensile, wear-resistant and low-temperature resistant cable material, characterized in that: The invention comprises the following raw materials in parts by weight: 30-40 parts of polyvinyl chloride resin, 20-30 parts of EPDM rubber, 16-28 parts of filler, 1.5-3 parts of coupling agent, 10-20 parts of ethylene-vinyl acetate copolymer, 7-14 parts of flame retardant, 2-5 parts of epoxy soybean oil, 1.3-3.2 parts of plasticizer, 0.5-1.5 parts of antioxidant and 0.5-0.8 parts of cross-linking agent; Wherein, the flame retardant is prepared by the following steps: S1, after replacing the air in the bottle with nitrogen, add 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, pyridine and diethyl ether, stir, add diallylamine, react at 60°C for 2h, distill under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain intermediate 1; S2, after replacing the air in the bottle with nitrogen, add intermediate 1, triethylamine and chloroform, stir, add N-methyl-2-hydroxyethylamine, react at 70°C for 3h, distill under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain intermediate 2; S3, add dodecanol and dry tetrahydrofuran into a flask, stir and place in a 0°C ice water bath, add phosphorus oxychloride and pyridine, react at 0°C for 0.5h, centrifuge to obtain intermediate 3; S4. Add intermediate 2, triethylamine and DMSO into a flask, stir, add intermediate 3 and DMSO, react at room temperature for 1 hour, distill under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain a flame retardant.

2. The tensile, wear-resistant and low-temperature resistant cable material according to claim 1, characterized in that: The amount ratio of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, diallylamine, pyridine and ether in step S1 is 0.082 mol: 0.08 mol: 9.7 mL: 120 mL; the amount ratio of intermediate 1, N-methyl-2-hydroxyethylamine, triethylamine and chloroform in step S2 is 0.07 mol: 0.072 mol: 14.5 mL: 120 mL; the amount ratio of phosphorus oxychloride, dodecanol, pyridine and tetrahydrofuran in step S3 is 0.03 mol: 0.061 mol: 5.5 mL: 120 mL; the amount ratio of intermediate 2, intermediate 3, triethylamine and DMSO in step S4 is 0.031 mol: 0.03 mol: 5 mL: 120 mL.

3. The tensile, wear-resistant and low-temperature resistant cable material according to claim 1, characterized in that: The filler is one or more of kaolin, carbon black, talcum powder and white carbon black.

4. The tensile, wear-resistant and low-temperature resistant cable material according to claim 3, characterized in that: The filler is a mixture of white carbon black, carbon black, talcum powder and kaolin in a mass ratio of 1:2:1:(0-0.5).

5. The tensile, wear-resistant and low-temperature resistant cable material according to claim 1, characterized in that: The coupling agent is one or more of 3-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.

6. The tensile, wear-resistant and low-temperature resistant cable material according to claim 1, characterized in that: The plasticizer is prepared by compounding diisononyl cyclohexane 1,2-dicarboxylate and dioctyl sebacate in a mass ratio of (3-5):(1-2).

7. The tensile, wear-resistant and low-temperature resistant cable material according to claim 1, characterized in that: The antioxidant is one or more of antioxidant 1076, antioxidant 1010, antioxidant 1035, antioxidant 168, and antioxidant DLTDP.

8. The tensile, wear-resistant and low-temperature resistant cable material according to claim 1, characterized in that: The cross-linking agent is one or more of di-tert-butyl peroxide, benzoyl peroxide, and dicumyl peroxide.

9. The method for preparing a tensile, wear-resistant and low-temperature resistant cable material according to claim 1, characterized in that: The steps include: Weigh the raw materials by weight, mix the polyvinyl chloride resin, EPDM rubber and ethylene-vinyl acetate copolymer, heat to 50-70°C, stir to obtain A; put the filler into a ball mill, stir and heat to 60-70°C to obtain B; mix A and B, add flame retardant, epoxy soybean oil, coupling agent, plasticizer, antioxidant and cross-linking agent, heat to 80-90°C, stir, and finally send into a twin-screw extruder granulator for extrusion granulation, dry to obtain cable material.

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