Antifreeze cable and preparation method thereof

Abstract

The present application relates to the technical field of cable composite materials, in particular to an antifreeze cable and a preparation method thereof. An antifreeze cable comprises a rubber composite outer layer and a conductive wire bundle located within the rubber composite outer layer, with an elastic filling layer filled between the rubber composite outer layer and the conductive wire bundle; the elastic filling layer is formed by a plurality of highly elastic wires; the conductive wire bundle comprises a plurality of conductive branches, which are twisted and melted with a plurality of highly elastic wires to form a conductive wire bundle with an elastic filling layer; a single conductive branch comprises a multi-strand twisted copper wire core and a modified PVC composite protective outer layer coated on the outer wall of the multi-strand twisted copper wire core. The antifreeze cable provided in the present application has good low-temperature toughness and impact toughness, and can be used in severely cold areas in the north (-50°C to 80°C). It also has good flame retardant and fire safety properties, which can improve the safety and stability of the cable.

Description

Technical Field

[0001] The present application relates to the technical field of cable composite materials, and in particular to an antifreeze cable and a preparation method thereof. Background Art

[0002] With the rapid development of new energy vehicles, supporting charging technologies have also made great strides, placing higher performance requirements on cables. Cable structures include single-strand conductors, multi-strand twisted core wires, and a protective outer layer covering the multi-strand twisted core wires. The protective outer layer is generally made of high-insulation PVC material or rubber material for cushioning and shock absorption requirements. Single-strand conductors include multiple strands of twisted copper wire and a PVC sheath covering the outer wall of the twisted copper wires. The existing cable with the above structure has no obvious use problems when used at -5-50℃. However, when it is placed in the extremely cold areas of the north (the operating temperature is below -20℃), the PVC material protective outer layer and PVC sheath of the cable will obviously harden in the low temperature environment. Even if the protective outer layer is made of rubber material, it will be affected by the low temperature hardening of the PVC sheath of the single-strand conductor in the cable. The glass transition temperature of the conventional rubber material protective outer layer is between -25 and -15℃. When the ambient temperature is lower than its glass transition temperature, it will still be affected by the low temperature. As a result, the low-temperature usability of the cable in the prior art is poor, especially it is not convenient to wind and store, which limits its use in the field of new energy vehicle charging cables. To this end, the inventor provides an antifreeze cable and a preparation method thereof. Summary of the Invention

[0003] In order to solve the problems existing in the above technologies, the present application provides an antifreeze cable and a preparation method thereof.

[0004] The antifreeze cable provided in this application is realized by the following technical solutions:

[0005] A frost-proof cable comprises a rubber composite outer layer and a conductive wire bundle located within the rubber composite outer layer, with an elastic filling layer filling the space between the rubber composite outer layer and the conductive wire bundle; the elastic filling layer is formed from a plurality of highly elastic wires; the conductive wire bundle comprises a plurality of conductive branch wires, which are twisted and fused with a plurality of highly elastic wires to form the conductive wire bundle with the elastic filling layer; a single conductive branch wire comprises a multi-strand twisted copper wire core and a modified PVC composite protective outer layer covering the outer wall of the multi-strand twisted copper wire core;

[0006] The modified PVC composite protective outer layer is made of modified PVC resin, which is made of the following raw materials in percentage by weight: 18-26 wt% of polyurethane resin, 0.05-0.25 wt% of cross-linking agent, 0.5-2 wt% of nanofiber, 28-36 wt% of filler composition, 0.5-2 wt% of surface modifier, 0.5-2 wt% of lubricant, 2-5 wt% of heat stabilizer, 1-5 wt% of plasticizer, 0.5-2 wt% of phase change microcapsule, and the balance is PVC resin with a degree of polymerization of 900-1100;

[0007] The polyurethane resin is a thermoplastic polyurethane elastomer with a Shore hardness of 40-65A and a Tg temperature below -40°C;

[0008] The cross-linking agent is 3,3-dimethyl-4,4-diaminodicyclohexylmethane and / or 4,4-diaminodicyclohexylmethane;

[0009] The nanofiber is at least one of nano-aramid fiber, nano-carbon fiber, carbon nanotube, and boron nitride whisker;

[0010] The surface modifier is a siloxane coupling agent and / or a titanate coupling agent;

[0011] The lubricant is at least one of stearate, PE wax, paraffin, stearyl alcohol, and butyl stearate;

[0012] The heat stabilizer is composed of at least one of nano titanium nitride, nano silicon nitride, antioxidant, anti-ultraviolet agent, organic tin stabilizer, calcium zinc composite stabilizer, and isooctanoic acid rare earth;

[0013] The plasticizer is at least one of tributyl 3-propanetricarboxylate and di-n-butyl sebacate;

[0014] The filler composition is composed of a flame retardant filler and an insulating and thermally conductive filler in a mass ratio of (60-75):(25-40);

[0015] The flame retardant filler includes at least one of zinc hydroxystannate, titanate nanotubes, ammonium polyphosphate, diammonium hydrogen phosphate, lithium phosphate, melamine, nano bentonite, nano kaolin, nano montmorillonite, barium metaborate, ammonium metaborate, zinc borate, graphene, expandable graphene, halloysite nanotubes, molybdenum disulfide nanosheets, basic cerium carbonate, nano calcium carbonate, nano magnesium hydroxide, nano aluminum hydroxide, and nano zinc oxide;

[0016] The insulating thermal conductive filler includes at least one of nano-scale aluminum nitride, aluminum oxide, silicon nitride, and boron nitride.

[0017] The antifreeze cable provided in this application has good low-temperature flexibility, impact toughness, and mechanical strength, and can be used in the extremely cold areas of the north (-50°C to 80°C). At the same time, it has good flame retardant and fire safety performance, weather resistance, and high temperature resistance, which can improve the safety and stability of the cable.

[0018] Preferably, the modified PVC composite protective outer layer is made of modified PVC resin, and the modified PVC resin is made of the following raw materials in the following mass percentages: 21-22wt% of polyurethane resin, 0.12-0.18wt% of cross-linking agent, 1.2-1.6wt% of nanofiber, 30-32wt% of filler composition, 0.8-1.2wt% of surface modifier, 0.8-1.2wt% of lubricant, 3.6-4.2wt% of heat stabilizer, 1.6-2.4wt% of plasticizer, 1.6-2.0wt% of phase change microcapsule, and the balance is PVC resin with a degree of polymerization of 900-1100.

[0019] Preferably, the thermal stabilizer is composed of 5-10wt% of nano titanium nitride, 5-20wt% of nano silicon nitride, 25-40wt% of antioxidant 1010, 3-8wt% of antioxidant 168, 5-20wt% of anti-ultraviolet agent UV-P, 5-20wt% of anti-ultraviolet agent UV-531, and 5-20wt% of rare earth isooctanoate.

[0020] Preferably, the flame retardant filler consists of 15-30wt% of ammonium polyphosphate, 5-20wt% of halloysite nanotubes, 5-20wt% of molybdenum disulfide nanosheets, 5-10wt% of basic cerium carbonate, 10-25wt% of nano magnesium hydroxide, and 10-25wt% of nano aluminum hydroxide.

[0021] Preferably, the polyurethane resin is a thermoplastic polyurethane elastomer TPU, having a hard segment content of 30-35wt%, an R value of 0.99-1.02, and a melting temperature of 160-180°C; the raw materials for preparing the thermoplastic polyurethane elastomer TPU include polyols and reactive flame retardants, the polyols being composed of a polyether diol with a molecular weight of 2000-3000, a polycarbonate diol with a molecular weight of 2000-3000, a polyester diol with a molecular weight of 2000-3000, and at least one of hydroxy-terminated polybutadiene-acrylonitrile HTBN with a molecular weight of 2000-4500; the reactive flame retardant includes at least dibromoneopentyl glycol and / or Exolit OP550, and the reactive flame retardant accounts for 0.5-2.5wt% of the total mass of the TPU resin.

[0022] By adopting the above technical solution, it can be ensured that the overall structure has good antifreeze performance while also having good flame retardant and fireproof performance, insulation safety performance, thermal conductivity and mechanical properties.

[0023] Preferably, the preparation method of the modified PVC resin is as follows:

[0024] S1, preparation of polyurethane resin;

[0025] S2, swelling the polyurethane resin and the PVC resin in an organic co-solvent to form a mixed swelling solution, wherein the organic co-solvent accounts for 60-75 wt% of the mass of the obtained mixed swelling solution;

[0026] S3, adding accurately measured filler composition, surface modifier, lubricant, thermal stabilizer, and phase change microcapsules to the mixed swelling liquid, mechanically stirring for 30-60 minutes, then ultrasonically dispersing for 5-30 minutes, and distilling off the organic co-solvent at 0.06-0.08 MPa to obtain a mixed resin;

[0027] S4, heating the obtained resin to 170-175°C, adding accurately measured plasticizer and cross-linking agent, and mixing for 300-320 seconds;

[0028] S5, the obtained banburying mixture is placed in a screw extruder for melt extrusion, drawing, cooling, granulation, and drying. The melt extrusion temperature range is 150-175° C., and the finished modified PVC resin can be obtained.

[0029] The preparation method of the modified PVC resin provided in this application is relatively simple and convenient for batch production.

[0030] Preferably, the modified rubber composite material comprises 64-72 parts of a rubber composition, 28-36 parts of a thermoplastic polyurethane elastomer (TPU), 4-8 parts of a maleic anhydride-modified polyolefin resin, 1-4 parts of a vulcanizing agent, 0.5-2 parts of a vulcanization activator, 1-5 parts of an accelerator, 2-4 parts of an anti-aging agent, 60-80 parts of a functional filler, and 2-6 parts of a dispersant.

[0031] The rubber composition is composed of butyl rubber and / or bromobutyl rubber and fluororubber;

[0032] The maleic anhydride modified polyolefin resin is maleic anhydride modified polyethylene and / or maleic anhydride modified polybutadiene;

[0033] The vulcanizing agent is sulfur and / or colloidal vulcanization; the vulcanization activator is nano zinc oxide;

[0034] The accelerator is at least one of accelerator DM, accelerator DZ, accelerator PZ, and accelerator D;

[0035] The dispersant is a siloxane coupling agent and / or a titanate coupling agent;

[0036] The anti-aging aid includes at least one of an alkylphenol antioxidant, a phenolic antioxidant, and a heterocyclic antioxidant;

[0037] The functional filler is composed of white carbon black doped with carbon nanotubes, flame retardant filler and nano-alumina;

[0038] The flame retardant filler is at least one of ammonium polyphosphate, diammonium hydrogen phosphate, nano-montmorillonite, barium metaborate, ammonium metaborate, halloysite nanotubes, molybdenum disulfide nanosheets, nano-calcium carbonate, nano-magnesium hydroxide, and nano-aluminum hydroxide.

[0039] Preferably, the modified rubber composite material includes 65 parts of a rubber composition, 30 parts of a thermoplastic polyurethane elastomer TPU, 5 parts of maleic anhydride modified polybutadiene, 3-4 parts of a vulcanizing agent, 0.8-1.6 parts of a vulcanization activator, 3-4 parts of an accelerator, 3-4 parts of an anti-aging agent, 68-72 parts of a functional filler, and 3-5 parts of a dispersant.

[0040] By adopting the above technical solution, the rubber composite outer layer is given good antifreeze performance and also has good flame retardant and fireproof performance, insulation safety performance, thermal conductivity and mechanical properties.

[0041] Preferably, the high-elastic wire is made of 60-80 parts by mass of thermoplastic polyurethane elastomer TPU, 25-40 parts of insulating thermal conductive filler, and 1-3 parts of surface modifier; the insulating thermal conductive filler includes at least one of nano-scale aluminum nitride, aluminum oxide, silicon nitride, and boron nitride; the surface modifier is a siloxane coupling agent and / or a titanate coupling agent.

[0042] By adopting the above technical solution, the interface bonding strength between the rubber composite outer layer and the conductive harness is good, ensuring the overall antifreeze performance, flame retardant and fireproof performance, insulation safety performance, thermal conductivity and mechanical properties.

[0043] The present application provides a method for preparing a frost-proof cable, which is achieved through the following technical solutions:

[0044] A method for preparing an antifreeze cable comprises the following steps:

[0045] Step 1: Preparation of modified PVC resin, modified rubber composite material, and high elastic wire;

[0046] Step 2: Melt-extrude the modified PVC resin prepared in step 1 and coat it on the outer wall of the multi-strand twisted copper wire core wire to form a modified PVC composite protective outer layer to obtain a conductive branch line;

[0047] Step 3: twisting the conductive branch wire prepared in step 2 with the high-elastic wire material and melting them to form a conductive wire bundle covered by the elastic filling layer;

[0048] Step 4: Using the modified rubber composite material to prepare an elastic rubber composite casing, i.e., a rubber composite outer layer, the obtained rubber composite outer layer is sleeved on the outer wall of the elastic filling layer to obtain a semi-finished antifreeze cable;

[0049] Step 5: The semi-finished antifreeze cable wire is subjected to heat treatment to obtain a finished antifreeze cable wire.

[0050] The preparation method provided in this application is relatively simple and can be put into production immediately using existing production line equipment, facilitating industrial manufacturing.

[0051] In summary, this application has the following advantages:

[0052] 1. The antifreeze cable provided in this application has good low-temperature flexibility, impact toughness, and mechanical strength, and can be used in the northern cold regions (-50℃ to 80℃). At the same time, it has good flame retardant and fire safety performance, weather resistance, and high temperature resistance, which can improve the safety and stability of the cable.

[0053] 2. The preparation method provided in this application is relatively simple and can be put into production immediately using existing production line equipment, facilitating industrial manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 It is a schematic diagram of the overall structure of the antifreeze cable in this application.

[0055] Figure 2 This is a process flow chart for preparing the antifreeze cable in this application.

[0056] In the figure, 1. rubber composite outer layer; 2. conductive wire harness; 20. conductive branch line; 201. multi-strand twisted copper wire core wire; 202. modified PVC composite protective outer layer; 3. elastic filling layer. DETAILED DESCRIPTION

[0057] In order to further understand the present invention, preferred embodiments of the present invention are described below with reference to examples and comparative examples.

[0058] Example

[0059] refer to Figure 1 A frost-proof cable includes a rubber composite outer layer 1 and a conductive wire bundle 2 positioned within the rubber composite outer layer 1. An elastic filling layer 3 is placed between the rubber composite outer layer 1 and the conductive wire bundle 2. Preferably, the elastic filling layer 3 is filled with fiberglass cloth. The elastic filling layer 3 is formed by fusing a plurality of highly elastic wires. Specifically, the conductive wire bundle 2 includes a plurality of conductive branch wires 20, which are twisted and fused with a plurality of highly elastic wires to form the conductive wire bundle 2 with the elastic filling layer 3.

[0060] refer to Figure 1The single conductive branch line 20 includes a multi-strand twisted copper wire core line 201 and a modified PVC composite protective outer layer 202 coated on the outer wall of the multi-strand twisted copper wire core line 201.

[0061] The modified PVC composite protective outer layer 202 is made of modified PVC resin, and the modified PVC resin is made of the following raw materials in the following mass percentages: 18-26wt% of polyurethane resin, 0.05-0.25wt% of cross-linking agent, 0.5-2wt% of nanofiber, 28-36wt% of filler composition, 0.5-2wt% of surface modifier, 0.5-2wt% of lubricant, 2-5wt% of heat stabilizer, 1-5wt% of plasticizer, 0.5-2wt% of phase change microcapsule, and the balance is PVC resin with a polymerization degree of 900-1100.

[0062] Preferably, the modified PVC composite protective outer layer 202 is made of modified PVC resin, and the modified PVC resin is made of the following raw materials in the following mass percentages: 21-22wt% of polyurethane resin, 0.12-0.18wt% of cross-linking agent, 1.2-1.6wt% of nanofiber, 30-32wt% of filler composition, 0.8-1.2wt% of surface modifier, 0.8-1.2wt% of lubricant, 3.6-4.2wt% of heat stabilizer, 1.6-2.4wt% of plasticizer, 1.6-2.0wt% of phase change microcapsule, and the remainder is PVC resin with a degree of polymerization of 900-1100.

[0063] The polyurethane resin is a thermoplastic polyurethane elastomer with a Shore hardness of 40-65A and a Tg temperature below -40°C.

[0064] Preferably, the polyurethane resin is a thermoplastic polyurethane (TPU) resin, having a hard segment content of 30-35% by weight, an R value of 0.99-1.02, and a melting temperature of 160-180°C. The raw materials used to prepare the TPU include a polyol and a reactive flame retardant. The polyol is composed of a polyether diol with a molecular weight of 2000-3000, a polycarbonate diol with a molecular weight of 2000-3000, a polyester diol with a molecular weight of 2000-3000, or a hydroxy-terminated polybutadiene-acrylonitrile (HTBN) with a molecular weight of 2000-4500. The reactive flame retardant includes at least dibromoneopentyl glycol and / or Exolit OP550, and the reactive flame retardant accounts for 0.5-2.5% by weight of the total mass of the TPU resin.

[0065] The cross-linking agent is surface amino-modified graphene and / or 4,4-diaminodicyclohexylmethane.

[0066] The nanofiber is at least one of nano-aramid fiber, nano-carbon fiber, carbon nanotube, and boron nitride whisker.

[0067] The surface modifier is a siloxane coupling agent and / or a titanate coupling agent.

[0068] The lubricant is at least one of stearate, PE wax, paraffin, stearyl alcohol and butyl stearate.

[0069] The heat stabilizer is composed of at least one of nano titanium nitride, nano silicon nitride, antioxidant, anti-ultraviolet agent, organic tin stabilizer, calcium zinc composite stabilizer and isooctanoic acid rare earth.

[0070] The plasticizer is at least one of tributyl 3-propanetricarboxylate and di-n-butyl sebacate.

[0071] The filler composition is composed of a flame retardant filler and an insulating and thermally conductive filler in a mass ratio of (60-75):(25-40).

[0072] The flame retardant filler includes at least one of zinc hydroxystannate, titanate nanotubes, ammonium polyphosphate, diammonium hydrogen phosphate, lithium phosphate, melamine, nano bentonite, nano kaolin, nano montmorillonite, barium metaborate, ammonium metaborate, zinc borate, graphene, expandable graphene, halloysite nanotubes, molybdenum disulfide nanosheets, basic cerium carbonate, nano calcium carbonate, nano magnesium hydroxide, nano aluminum hydroxide, and nano zinc oxide.

[0073] The insulating thermal conductive filler includes at least one of nano-scale aluminum nitride, aluminum oxide, silicon nitride, and boron nitride.

[0074] Preferably, the thermal stabilizer is composed of 5-10wt% of nano titanium nitride, 5-20wt% of nano silicon nitride, 25-40wt% of antioxidant 1010, 3-8wt% of antioxidant 168, 5-20wt% of anti-ultraviolet agent UV-P, 5-20wt% of anti-ultraviolet agent UV-531, and 5-20wt% of rare earth isooctanoate.

[0075] Preferably, the flame retardant filler consists of 15-30wt% ammonium polyphosphate, 5-20wt% halloysite nanotubes, 5-20wt% molybdenum disulfide nanosheets, 5-10wt% basic cerium carbonate, 10-25wt% nano magnesium hydroxide, and 10-25wt% nano aluminum hydroxide.

[0076] The preparation method of modified PVC resin is as follows:

[0077] S1, preparation of polyurethane resin;

[0078] S2, swelling the polyurethane resin and the PVC resin in an organic co-solvent to form a mixed swelling solution, wherein the organic co-solvent accounts for 60-75 wt% of the mass of the obtained mixed swelling solution;

[0079] S3, adding accurately measured filler composition, surface modifier, lubricant, thermal stabilizer, and phase change microcapsules to the mixed swelling liquid, mechanically stirring for 30-60 minutes, then ultrasonically dispersing for 5-30 minutes, and distilling off the organic co-solvent at 0.06-0.08 MPa to obtain a mixed resin;

[0080] S4, heating the obtained resin to 170-175°C, adding accurately measured plasticizer and cross-linking agent, and mixing for 300-320 seconds;

[0081] S5, the obtained banburying mixture is placed in a screw extruder for melt extrusion, drawing, cooling, granulation, and drying. The melt extrusion temperature range is 150-175° C., and the finished modified PVC resin can be obtained.

[0082] The highly elastic wire is made from 60-80 parts by weight of the thermoplastic polyurethane elastomer (TPU) used in the modified PVC resin, 25-40 parts of an insulating and thermally conductive filler, and 1-3 parts of a surface modifier. The insulating and thermally conductive filler includes at least one of nano-scale aluminum nitride, aluminum oxide, silicon nitride, and boron nitride. The surface modifier is a siloxane coupling agent and / or a titanate coupling agent.

[0083] The rubber composite outer layer is made of a modified rubber composite material, which includes 64-72 parts of a rubber composition, 28-36 parts of a thermoplastic polyurethane elastomer TPU, 4-8 parts of a maleic anhydride modified polyolefin resin, 1-4 parts of a vulcanizing agent, 0.5-2 parts of a vulcanization activator, 1-5 parts of an accelerator, 2-4 parts of an anti-aging agent, 60-80 parts of a functional filler, and 2-6 parts of a dispersant.

[0084] Preferably, the modified rubber composite material includes 65 parts of a rubber composition, 30 parts of a thermoplastic polyurethane elastomer TPU, 5 parts of maleic anhydride modified polybutadiene, 3-4 parts of a vulcanizing agent, 0.8-1.6 parts of a vulcanization activator, 3-4 parts of an accelerator, 3-4 parts of an anti-aging agent, 68-72 parts of a functional filler, and 3-5 parts of a dispersant.

[0085] The rubber composition is composed of butyl rubber and / or bromobutyl rubber and fluororubber.

[0086] The maleic anhydride modified polyolefin resin is maleic anhydride modified polyethylene and / or maleic anhydride modified polybutadiene.

[0087] The vulcanizing agent is sulfur and / or colloidal vulcanization, and the vulcanization activator is nano zinc oxide.

[0088] The accelerator is at least one of accelerator DM, accelerator DZ, accelerator PZ, and accelerator D.

[0089] The dispersant is a siloxane coupling agent and / or a titanate coupling agent.

[0090] The anti-aging aid includes at least one of an alkylphenol antioxidant, a phenol antioxidant, and a heterocyclic antioxidant.

[0091] The functional filler is composed of carbon nanotube-doped modified white carbon black, flame retardant filler and nano-alumina.

[0092] The flame retardant filler is at least one of ammonium polyphosphate, diammonium hydrogen phosphate, nano-montmorillonite, barium metaborate, ammonium metaborate, halloysite nanotubes, molybdenum disulfide nanosheets, nano-calcium carbonate, nano-magnesium hydroxide, and nano-aluminum hydroxide.

[0093] refer to Figure 2 A method for preparing an antifreeze cable comprises the following steps:

[0094] Step 1: Preparation of modified PVC resin, modified rubber composite material, and high elastic wire;

[0095] Step 2: melt-extrude the modified PVC resin prepared in step 1 and coat it on the outer wall of the multi-strand twisted copper wire core wire 201 to form a modified PVC composite protective outer layer 202 to obtain the conductive branch wire 20;

[0096] Step 3: twisting the conductive branch wire 20 prepared in step 2 with the high elastic wire material and melting them to form a conductive wire bundle 2 covered by the elastic filling layer 3;

[0097] Step 4: Using the modified rubber composite material to prepare an elastic rubber composite casing, namely a rubber composite outer layer 1, the obtained rubber composite outer layer 1 is sleeved on the outer wall of the elastic filling layer 3 to obtain a semi-finished antifreeze cable;

[0098] A specific method for preparing a semi-finished antifreeze cable is as follows: first, an elastic rubber composite casing is prepared using a modified rubber composite material, the elastic rubber composite casing is heated to 60-80° C., and then a conductive wire bundle 2 coated with an elastic filling layer 3 is passed through the elastic rubber composite casing to obtain a semi-finished antifreeze cable; the modified rubber composite material is placed in a twin-screw extruder for melt extrusion, and the resulting molten extrudate is coated on the conductive wire bundle 2 coated with the elastic filling layer 3; the molten extrudate coated with the modified rubber composite material is passed through a rounding die to adjust the overall roundness of the cable, and then air-cooled to room temperature to obtain a semi-finished antifreeze cable;

[0099] Step 5: The semi-finished antifreeze cable wire is subjected to heat treatment to obtain a finished antifreeze cable wire.

[0100] Example 1: The modified PVC resin is made of the following raw materials in percentage by mass: 18 wt% of TPU resin (Bayer Ulthera, US-60AU10), 0.1 wt% of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 0.8 wt% of nano-aramid fiber (customized by Xi'an Qiyue Biotechnology Co., Ltd.), 30 wt% of filler composition, 0.8 wt% of KH550 coupling agent, 0.2 wt% of titanate coupling agent KR 9S, 0.8 wt% of zinc stearate, 3.2 wt% of heat stabilizer, 3.6 wt% of plasticizer-di-n-butyl sebacate, 1 wt% of phase change microcapsules (customized by Hefei Xinneng Phase Change New Material Technology Co., Ltd., phase change temperature 24 ° C, particle size 0.5-3 microns, enthalpy value> 180 J / g), and the balance is PVC resin (HANWHA P-1000, South Korea).

[0101] The filler composition is composed of 3wt% of 500-mesh ammonium polyphosphate (brand Kemeisi, CAS: 8333-79-9), 2wt% of 800-mesh zinc borate (CAS: 0361-94-1, brand Xinghai Chemical), 8wt% of nano-aluminum hydroxide ZT-LA20 (average particle size 20nm, brand Zhiti Nanomicro), 4wt% of nano-magnesium hydroxide (brand Zhiti Nanomicro, particle size 30nm~50nm), 1wt% of halloysite nanotubes HNTs (outer tube 10-50nm, inner diameter 5-20nm, length 0.5-3um), and 12wt% of nano-alumina VK-L04R (Xuancheng Jingrui New Materials Co., Ltd., particle size 500nm).

[0102] The thermal stabilizer is composed of 0.2wt% of nano silicon nitride (brand Huaxiang, CAS: 12033-89-5, average particle size 20nm), 0.2wt% of nano titanium nitride (brand Huaxiang, CAS: 25583-20-4, average particle size 20nm), 1wt% of antioxidant 1010, 0.2wt% of antioxidant 168, 0.6wt% of UV-P, 0.6wt% of UV-531, and 0.4wt% of rare earth isooctanoate (active ingredient content 8%, purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd.).

[0103] The high-elastic wire is made from 68 parts by weight of TPU resin (US-60AU10), 32 parts by weight of nano-alumina (DK-A12O3-A3, particle size 300 nm), 0.8% by weight of KH550 coupling agent, and 0.4% by weight of titanate coupling agent KR 9S. The high-elastic wire is produced using this formula combined with a masterbatch spinning method to produce a 2±0.05 mm diameter high-elastic wire. (The inventor developed the formula and subsequently commissioned Jiangsu Shuangliang Spandex Co., Ltd. to produce the 2±0.05 mm diameter high-elastic wire.)

[0104] The modified rubber composite material is made of 60 parts of Yanshan Petrochemical IIR1751, 5 parts of fluororubber (Daikin FKMGBR6005, Japan), 30 parts of TPU resin US-60AU10, 5 parts of maleic anhydride modified polybutadiene (Hubei Langbowan Biomedicine Co., Ltd.), 3.5 parts of sulfur, 0.5 parts of nano zinc oxide (high purity 99.99%, particle size 50 nm, Hebei Teng Bimetallic Materials Co., Ltd.), 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, 3 parts of KH550 coupling agent, and 1 part of titanate coupling agent KR 9S. The functional filler is composed of 30 parts of carbon nanotube-doped modified white carbon black (customized by Rongtai Technology), 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets (MoS2-200nm, brand Yamei Nano), and 10 parts of nano-alumina VK-L04R.

[0105] The preparation method of carbon nanotube-doped modified silica is as follows: Step 1: At room temperature, 0.02 mol of 2-ethyl-4-methylimidazole 2E4MI and 0.01 mol of silver acetate AgAc are added to 400 mL of dichloromethane, and magnetic stirring is performed at a speed of 240 r / min. The magnetic stirring time is controlled at 2 h until the AgAc particles completely disappear to obtain a clear and transparent Ag(2E4MI)2Ac complex solution; Step 2: 0.5 g of CNTs and 0.5 g of PVP are added to the Ag(2E4MI)2Ac complex solution, and ultrasonic dispersion (ultrasonic generator power 1200 W, frequency 20 kHz) is performed for 3 h, and 50 g of silica (AEROSIL 200, Evonik), continue ultrasonic dispersion for 0.5h to obtain a dispersion; step three: subject the dispersion obtained in step two to reduced pressure distillation, remove dichloromethane in the dispersion, and then subject the solid to high-temperature sintering treatment, the high-temperature sintering temperature is controlled at 210°C, and the high-temperature sintering time is 4h to obtain a solid; step four: the solid obtained in step three is placed in a three-roll mill with a roller spacing of 30μm and ground three times, then dispersed in 400mL of ethanol, poured into a basket grinder for grinding, ground at a speed of 2000r / min for 1h, and then filtered and dried to obtain a white carbon black-CNTs hybrid material.

[0106] A method for preparing an antifreeze cable comprises the following steps:

[0107] refer to Figure 2 A method for preparing an antifreeze cable comprises the following steps:

[0108] Step 1: Preparation of modified PVC resin, modified rubber composite material, and high elastic wire;

[0109] The preparation of modified PVC resin is as follows:

[0110] S1.1, drying US-60AU10 polyurethane TPU resin at 85°C for 6 hours;

[0111] S1.2, dissolving the dried US-60AU10 polyurethane (TPU) resin and PVC resin (HANWHA P-1000, Korea) in acetone to form a mixed swelling solution, wherein the organic co-solvent accounts for 65 wt% of the mass of the mixed swelling solution;

[0112] S1.3. Add accurately measured amounts of the filler composition, surface modifier, lubricant, thermal stabilizer, and phase change microcapsules to the mixed swelling solution. Mechanically stir at 200 rpm for 30 minutes, then ultrasonically disperse (40 kHz / 800 W) for 10 minutes. Distill off the acetone at 0.06-0.065 MPa to obtain a mixed resin.

[0113] S1.4. Heat the resulting resin to 175°C, add accurately measured amounts of di-n-butyl sebacate and 3,3-dimethyl-4,4-diaminodicyclohexylmethane, and mix for 300 seconds.

[0114] S1.5. The obtained banburying mixture is placed in a screw extruder for melt extrusion, drawing, cooling, pelletizing, and drying. The melt extrusion temperature range is 150-175°C. Specifically, there are seven heating intervals with set temperatures of 150°C, 160°C, 170°C, 175°C, 175°C, 175°C, and 175°C, respectively. The die temperature is 175°C to obtain the finished modified PVC resin masterbatch.

[0115] The modified rubber composite material was prepared as follows: 3 parts of KH550 coupling agent, 1 part of titanate coupling agent KR 9S and 70 parts of functional filler were dry-kneaded for 30 minutes to obtain a mixture, the mixture was mixed with 60 parts of Yanshan Petrochemical IIR1751, 5 parts of, 30 parts of TPU resin (US-60AU10), 5 parts of maleic anhydride modified polybutadiene, 3.5 parts of sulfur, 0.5 parts of nano zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, and 1 part of antioxidant 1098, and then mixed and heated to 175°C and constant temperature kneaded for 300 seconds to obtain the modified rubber composite material;

[0116] Preparation of high-elastic wire: 68 parts by weight of TPU resin (US-60AU10), 32 parts by weight of nano-alumina (DK-A12O3-A3, particle size 300 nm), 0.8 wt% of KH550 coupling agent, and 0.4 wt% of titanate coupling agent KR 9S were placed in a high-speed stirring kettle and mixed uniformly at 400 rpm. The mixture was then extruded and pelletized in a screw extruder to produce a high-elastic wire TPU masterbatch. The resulting high-elastic wire TPU masterbatch was then fed into a screw extruder and spun using a masterbatch spinning method to produce high-elastic wire with a diameter of 2±0.05 mm.

[0117] Step 2: Place the modified PVC resin masterbatch prepared in step 1 in a screw extruder for melt extrusion. The resulting molten extrudate is coated on the outer wall of the multi-strand twisted copper wire core wire 201, cooled and dried to form a modified PVC composite protective outer layer 202 with a thickness of 0.5±0.05mm, thereby producing a conductive branch wire 20 with an outer diameter of 6±0.05mm;

[0118] Step 3: The conductive branch wire 20 prepared in step 2 is twisted and melted with the high elastic wire to form a semi-finished conductive wire bundle 2. The semi-finished conductive wire bundle 2 is input into a heat treatment mold with a conductive wire bundle channel for melt-wrapping treatment. The temperature of the first section of the heat treatment mold is 120°C (length 4m), the temperature of the second section of the heat treatment mold is 175°C (length 6m), the temperature of the third section of the heat treatment mold is 105°C (length 5m), and the temperature of the fourth section of the heat treatment mold is 60°C (length 5m). The transmission speed of the semi-finished conductive wire bundle 2 is 0.2m / s. After the melt-wrapping treatment, it is naturally cooled to room temperature to obtain a conductive wire bundle 2 with an elastic filling layer 3;

[0119] Step 4: Using the modified rubber composite material to prepare an elastic rubber composite sleeve with a wall thickness of 5±0.05 mm, namely, a rubber composite outer layer 1: the obtained modified rubber composite material is placed in an extruder for extrusion molding, and the extrusion temperature range is 155-160°C. Specifically, there are seven heating intervals, and the set temperatures are 150°C, 155°C, 158°C, 160°C, 160°C, 160°C, and 160°C, respectively. The finished elastic rubber composite sleeve, namely, the rubber composite outer layer 1, is obtained by air cooling. After preheating the finished elastic rubber composite sleeve to 65°C, the conductive wire bundle 2 with the elastic filling layer 3 in step 3 is inserted into the finished elastic rubber composite sleeve, and the semi-finished antifreeze cable is obtained by cooling to room temperature.

[0120] Step 5: The semi-finished antifreeze cable is put into an oven, heat-treated at 120° C. for 1 hour and at 80° C. for 0.5 hour, and then naturally cooled to room temperature to obtain a finished antifreeze cable.

[0121] The difference between Example 2 and Example 1 is that the modified PVC resin is made of the following raw materials in percentage by mass: 22 wt % of TPU resin (Bayer Ulthera, US-60AU10), 0.15 wt % of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 1.6 wt % of nano-aramid fiber, 30 wt % of filler composition, 1 wt % of KH550 coupling agent, 0.4 wt % of titanate coupling agent KR 9S, 1 wt % of zinc stearate, 3.2 wt % of heat stabilizer, 2.4 wt % of plasticizer-di-n-butyl sebacate, 1 wt % of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea).

[0122] The difference between Example 3 and Example 1 is that the modified PVC resin is made of the following raw materials in percentage by mass: 26 wt % of TPU resin (Bayer Ulthera, US-60AU10), 0.2 wt % of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 2 wt % of nano-aramid fiber, 30 wt % of filler composition, 1.4 wt % of KH550 coupling agent, 0.6 wt % of titanate coupling agent KR 9S, 1.2 wt % of zinc stearate, 0.2 wt % of PE wax, 3.2 wt % of heat stabilizer, 1.2 wt % of di-n-butyl sebacate, 1 wt % of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea).

[0123] The difference between Example 4 and Example 2 is that the PVC resin (HANWHA P-1000 from Korea) is replaced by Formosa Plastics Ningbo S-65PVC resin.

[0124] The difference between Example 5 and Example 2 is that the thermal stabilizer is composed of 0.3wt% of nano-silicon nitride (brand Huaxiang, CAS: 12033-89-5, average particle size 20nm), 0.3wt% of nano-titanium nitride (brand Huaxiang, CAS: 25583-20-4, average particle size 20nm), 1.2wt% of antioxidant 1010, 0.2wt% of antioxidant 168, 0.3wt% of UV-P, 0.3wt% of UV-531, and 0.6wt% of rare earth isooctanoate (active ingredient content 8%).

[0125] The difference between Example 6 and Example 2 is that the thermal stabilizer is composed of 0.1wt% of nano-silicon nitride (brand Huaxiang, average particle size 20nm), 0.1wt% of nano-titanium nitride (brand Huaxiang, average particle size 20nm), 1.2wt% of antioxidant 1010, 0.2wt% of antioxidant 168, 0.6wt% of UV-P, 0.6wt% of UV-531, and 0.4wt% of rare earth isooctanoate.

[0126] The difference between Example 7 and Example 2 is that the thermal stabilizer is composed of 0.2wt% of nano-silicon nitride (brand Huaxiang, average particle size 20nm), 0.2wt% of nano-titanium nitride (brand Huaxiang, average particle size 20nm), 1.2wt% of antioxidant 1010, 0.2wt% of antioxidant 168, 0.7wt% of UV-P, and 0.7wt% of UV-531.

[0127] The difference between Example 8 and Example 2 is that the US-60AU10 TPU resin is replaced by a homemade TPU resin.

[0128] The formula of TPU resin is as follows: 134.6g of hexamethylene diisocyanate HDI, 52.50g of hydrogenated MDI, 76.81g of 1,6-hexanediol, 0.04g of bismuth carboxylate DY-20, 0.1g of dibutyltin dilaurate, 400g of polytetramethylene glycol BASF PolyTHF 2000, 160g of polycarbonate diol CD220HL (Dacel Corporation of Japan), 50g of terminal hydroxyl polybutadiene-acrylonitrile HTBN (HTBN IV type of Shandong Zibo Qilong Chemical), 10.85g of dibromoneopentyl glycol, 7g of antioxidant 1010, 1g of antioxidant 168, and 5g of leveling agent - KMT-5514.

[0129] Preparation of TPU resin (commissioned by Zhejiang Hexin Technology Co., Ltd.), the specific method is as follows:

[0130] Step 1: 76.81 g of 1,6-hexanediol and 10.85 g of dibromoneopentyl glycol are put into the first trough of a twin-screw extruder, 400 g of polytetrahydrofuran diol BASF PolyTHF 2000, 160 g of polycarbonate diol CD220HL (Dacel Corporation, Japan), and 50 g of hydroxy-terminated polybutadiene-acrylonitrile HTBN are put into the second trough of the twin-screw extruder, and 134.6 g of hexamethylene diisocyanate HDI, 52.50 g of hydrogenated MDI, 0.04 g of bismuth carboxylate DY-20, 0.1 g of dibutyltin dilaurate, 7 g of antioxidant 1010, and 1 g of ethanol are accurately measured. 168g of antioxidant and 5g of leveling agent - KMT-5514 were stirred evenly and put into the third trough of the twin-screw extruder. The barrel section temperature of the twin-screw extruder was 14 sections, which were 165℃, 170℃, 175℃, 175℃, 170℃, 160℃, 160℃, 155℃, 155℃, 153℃, 150℃, and 150℃ respectively. A gear pump was used to discharge the material from the twin-screw extruder.

[0131] In step 2, the extruded material was water-cooled and granulated. After drying, the resulting pellets were dried in a fluidized bed dryer at 85°C for 10 minutes until the moisture content was less than 0.03%. The pellets were then heat-conditioned at 80°C for 24 hours to produce TPU resin pellets. The resulting TPU resin pellets had a melting temperature of 173.5°C and a glass transition temperature (Tg) of -65.2°C as measured by DSC.

[0132] The preparation of modified PVC resin is as follows:

[0133] S1.1, drying the TPU resin pellets prepared above at 85°C for 6 hours;

[0134] S1.2. The dried TPU resin pellets and PVC resin (HANWHA P-1000, Korea) were dissolved in an organic co-solvent, acetone, to form a mixed swelling solution, wherein the organic co-solvent accounted for 68 wt% of the mass of the mixed swelling solution.

[0135] S1.3. Add accurately measured amounts of the filler composition, surface modifier, lubricant, thermal stabilizer, and phase change microcapsules to the mixed swelling solution. Mechanically stir at 200 rpm for 30 minutes, then ultrasonically disperse (40 kHz / 800 W) for 10 minutes. Distill off the acetone at 0.06-0.065 MPa to obtain a mixed resin.

[0136] S1.4. Heat the resulting resin to 175°C, add accurately measured amounts of di-n-butyl sebacate and 3,3-dimethyl-4,4-diaminodicyclohexylmethane, and mix for 300 seconds.

[0137] S1.5. The obtained mixed mixture is placed in a screw extruder for melt extrusion, wire drawing, cooling, granulation, and drying. The melt extrusion temperature range is 150-175°C. Specifically, there are seven heating intervals, and the set temperatures are 150°C, 160°C, 170°C, 175°C, 175°C, 175°C, and 175°C, respectively. The die temperature is 175°C, and the finished modified PVC resin masterbatch can be obtained.

[0138] The difference between Example 9 and Example 2 is that the formula of TPU resin is as follows: 151.37g of hexamethylene diisocyanate HDI, 26.24g of hydrogenated MDI, 74.45g of 1,6-hexanediol, 0.06g of bismuth carboxylate DY-20, 0.08g of dibutyltin dilaurate, 400g of polytetrahydrofuran diol BASF PolyTHF 2000, 120g of polycarbonate diol CD220HL, 100g of terminal hydroxyl polybutadiene-acrylonitrile HTBN (HTBN IV type of Shandong Zibo Qilong Chemical), 15.20g of dibromoneopentyl glycol, 7g of antioxidant 1010, 1g of antioxidant 168, and 5g of leveling agent -KMT-5514. The melting temperature of the obtained TPU resin pellets was measured by DSC to be 172.4°C, and the glass transition temperature Tg was -66.5°C.

[0139] The difference between Example 10 and Example 2 is that the formula of the TPU resin is as follows: 25.03 g of MDI, 134.55 g of hexamethylene diisocyanate HDI, 26.24 g of hydrogenated MDI, 76.81 g of 1,6-hexanediol, 0.06 g of bismuth carboxylate DY-20, 0.08 g of dibutyltin dilaurate, 360 g of polytetrahydrofuran diol BASF PolyTHF 2000, 200 g of polycaprolactone diol 220N (Dacelide Co., Ltd., Japan), 10.85 g of dibromoneopentyl glycol, 13.2 g of Exolit OP550 flame retardant, 7 g of antioxidant 1010, 1 g of antioxidant 168, and 5 g of leveling agent -KMT-5514. The melting temperature of the obtained TPU resin pellets was measured by DSC to be 174.8°C, and the glass transition temperature Tg was -61.0°C.

[0140] The difference between Example 11 and Example 2 is that the filler composition is composed of 3.6wt% of ammonium polyphosphate (500 mesh, brand Kemeis, CAS: 68333-79-9), 1.8wt% of molybdenum disulfide nanosheets (MoS2-200nm, brand Yamei Nano), 0.9wt% of basic cerium carbonate (brand Wuhan Huaxiang 200 mesh basic cerium carbonate raw material ball milled into 800 mesh sieve material for use), 7.2wt% of nano-aluminum hydroxide (ZT-LA20, average particle size 20nm, brand Zhiti Nanomicro), 3.6wt% of nano-magnesium hydroxide (brand Zhiti Nanomicro, particle size 30nm~50nm), 0.9wt% of halloysite nanotubes (HNTs outer tube is 10-50nm, inner diameter 5-20nm, length 0.5-3um), and 12wt% of nano-alumina VK-L04R.

[0141] The difference between Example 12 and Example 2 is that the filler composition is composed of 5.4wt% of ammonium polyphosphate (500 mesh, brand Kemeis, CAS: 68333-79-9), 0.9wt% of molybdenum disulfide nanosheets (MoS2-200nm, brand Yamei Nano), 0.9wt% of basic cerium carbonate (brand Wuhan Huaxiang 200 mesh basic cerium carbonate raw material ball milled into 800 mesh sieve material for use), 7.2wt% of nano-aluminum hydroxide (ZT-LA20, average particle size 20nm, brand Zhiti Nanomicro), 2.7wt% of nano-magnesium hydroxide (brand Zhiti Nanomicro, particle size 30nm~50nm), 0.9wt% of halloysite nanotubes (HNTs outer tube is 10-50nm, inner diameter 5-20nm, length 0.5-3um), and 12wt% of nano-alumina VK-L04R.

[0142] The difference between Example 13 and Example 2 is that the filler composition is composed of 4.2wt% of ammonium polyphosphate (500 mesh, brand Kemeis, CAS: 68333-79-9), 0.9wt% of molybdenum disulfide nanosheets (MoS2-200nm, brand Yamei Nano), 1.5wt% of basic cerium carbonate sieved through 800 mesh, 7.2wt% of nano-aluminum hydroxide (ZT-LA20, average particle size 20nm), 3.3wt% of nano-magnesium hydroxide (particle size 30nm~50nm), 0.9wt% of halloysite nanotubes (the outer tube of HNTs is 10-50nm, the inner diameter is 5-20nm, and the length is 0.5-3um), and 12wt% of nano-alumina VK-L04R.

[0143] The difference between Example 14 and Example 13 is that the filler composition is composed of 4.2wt% of ammonium polyphosphate (500 mesh, brand Kemeis, CAS: 68333-79-9), 0.9wt% of molybdenum disulfide nanosheets (MoS2-200nm, brand Yamei Nano), 1.5wt% of basic cerium carbonate sieved through 800 mesh, 7.2wt% of nano-aluminum hydroxide (ZT-LA20, average particle size 20nm, brand Zhiti Nanomicro), 3.3wt% of nano-magnesium hydroxide (brand Zhiti Nanomicro, particle size 30nm~50nm), 0.9wt% of halloysite nanotubes (HNTs have an outer tube of 10-50nm, an inner diameter of 5-20nm, and a length of 0.5-3um), 10wt% of nano-aluminum oxide VK-L04R, and 2wt% of nano-aluminum nitride (brand Langbowan, particle size 50nm).

[0144] The difference between Example 15 and Example 2 is that the modified PVC resin is made of the following raw materials in percentage by mass: 22 wt % of TPU resin (Bayer Ulthera, US-60AU10), 0.15 wt % of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 1.6 wt % of nano-aramid fiber, 28 wt % of filler composition, 1 wt % of KH550 coupling agent, 0.4 wt % of titanate coupling agent KR 9S, 1 wt % of zinc stearate, 3.2 wt % of heat stabilizer, 2.4 wt % of plasticizer-di-n-butyl sebacate, 1 wt % of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea). The filler composition is composed of 3wt% of ammonium polyphosphate (500 mesh, brand Kemeis), 2wt% of zinc borate (800 mesh, CAS: 10361-94-1, brand Xinghai Chemical), 8wt% of nano-aluminum hydroxide (ZT-LA20, average particle size 20nm, brand Zhiti Nanomicro), 4wt% of nano-magnesium hydroxide (brand Zhiti Nanomicro, particle size 30nm~50nm), 1wt% of halloysite nanotubes (the outer tube of HNTs is 10-50nm, the inner diameter is 5-20nm, and the length is 0.5-3um), and 10wt% of nano-alumina VK-L04R.

[0145] The difference between Example 16 and Example 2 is that the modified PVC resin is made of the following raw materials in percentage by mass: 22 wt % of TPU resin (Bayer Ulder, US-60AU10), 0.15 wt % of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 1.6 wt % of nano-aramid fiber, 36 wt % of filler composition, 1 wt % of KH550 coupling agent, 0.4 wt % of titanate coupling agent KR 9S, 1 wt % of zinc stearate, 3.2 wt % of heat stabilizer, 2.4 wt % of plasticizer-di-n-butyl sebacate, 1 wt % of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000 from Korea). The filler composition is composed of 3wt% of ammonium polyphosphate (500 mesh, brand Kemeisi, CAS: 68333-79-9), 2wt% of zinc borate (800 mesh, brand Xinghai Chemical), 8wt% of nano aluminum hydroxide (ZT-LA20, average particle size 20nm), 4wt% of nano magnesium hydroxide (particle size 30nm~50nm), 1wt% of halloysite nanotubes (the outer tube of HNTs is 10-50nm, the inner diameter is 5-20nm, and the length is 0.5-3um), and 18wt% of nano alumina VK-L04R.

[0146] Example 17 differs from Example 1 in that the modified rubber composite material is made of 60 parts of Yanshan Petrochemical IIR1751, 5 parts of fluororubber FKM GBR6005, 30 parts of the TPU resin prepared in Example 8, 5 parts of maleic anhydride-modified polybutadiene, 3.5 parts of sulfur, 0.5 parts of nano-zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, 3 parts of KH550 coupling agent, and 1 part of titanate coupling agent KR 9S. The functional filler is composed of 30 parts of carbon nanotube-doped modified silica, 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets, and 10 parts of nano-alumina VK-L04R.

[0147] Example 18 differs from Example 1 in that the modified rubber composite material is made of 60 parts of Yanshan Petrochemical IIR1751, 5 parts of fluororubber FKM GBR6005, 30 parts of the TPU resin prepared in Example 9, 5 parts of maleic anhydride-modified polybutadiene, 3.5 parts of sulfur, 0.5 parts of nano-zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, 3 parts of KH550 coupling agent, and 1 part of titanate coupling agent KR 9S. The functional filler is composed of 30 parts of carbon nanotube-doped modified silica, 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets, and 10 parts of nano-alumina VK-L04R.

[0148] Example 19 differs from Example 1 in that the modified rubber composite material is made of 60 parts of Yanshan Petrochemical IIR1751, 5 parts of fluororubber FKM GBR6005, 30 parts of the TPU resin prepared in Example 10, 5 parts of maleic anhydride-modified polybutadiene, 3.5 parts of sulfur, 0.5 parts of nano-zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, 3 parts of KH550 coupling agent, and 1 part of titanate coupling agent KR 9S. The functional filler is composed of 30 parts of carbon nanotube-doped modified silica, 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets, and 10 parts of nano-alumina VK-L04R.

[0149] Example 20 differs from Example 18 in that the modified rubber composite material is made of 66 parts of Yanshan Petrochemical IIR1751, 6 parts of fluororubber FKM GBR6005, 35 parts of the TPU resin prepared in Example 9, 6 parts of maleic anhydride-modified polybutadiene, 3.6 parts of sulfur, 1.2 parts of nano-zinc oxide, 4 parts of accelerator D, 1 part of accelerator DM, 4 parts of antioxidant RD, 1 part of antioxidant 1098, 80 parts of functional filler, 4 parts of KH550 coupling agent, and 2 parts of titanate coupling agent KR 9S. The functional filler is composed of 35 parts of carbon nanotube-doped modified silica, 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets, and 15 parts of nano-alumina VK-L04R.

[0150] The difference between Example 21 and Example 1 is that the titanate coupling agent KR 9S is not added.

[0151] The modified rubber composite material is made of 60 parts of Yanshan Petrochemical IIR1751, 5 parts of fluororubber FKM GBR6005, 30 parts of TPU resin US-60AU10, 5 parts of maleic anhydride modified polybutadiene, 3.5 parts of sulfur, 0.5 parts of nano zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, and 4 parts of KH550 coupling agent.

[0152] The difference between Example 22 and Example 1 is that the functional filler is composed of 30 parts of carbon black N550 (brand Anlun carbon black), 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets (MoS2-200nm, brand Yamei Nano), and 10 parts of nano alumina VK-L04R.

[0153] The difference between Comparative Example 1 and Example 1 is that the modified PVC resin is made of the following raw materials in percentage by weight: 0.8wt% of nano-aramid fiber, 30wt% of filler composition, 0.8wt% of KH550 coupling agent, 0.2wt% of titanate coupling agent KR 9S, 0.8wt% of zinc stearate, 3.2wt% of heat stabilizer, 15.6wt% of plasticizer-di-n-butyl sebacate, 1wt% of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea).

[0154] The difference between Comparative Example 2 and Example 1 is that the modified PVC resin is made of the following raw materials in percentage by mass: 10 wt% of TPU resin (Bayer Ulder, US-60AU10), 0.05 wt% of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 0.8 wt% of nano-aramid fiber, 30 wt% of filler composition, 0.8 wt% of KH550 coupling agent, 0.2 wt% of titanate coupling agent KR 9S, 0.8 wt% of zinc stearate, 3.2 wt% of heat stabilizer, 4 wt% of plasticizer-di-n-butyl sebacate, 1 wt% of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea).

[0155] The difference between Comparative Example 3 and Example 1 is that the modified PVC resin is made of the following raw materials in percentage by mass: 30wt% of TPU resin (Bayer Ulthera, US-60AU10), 0.25wt% of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 0.8wt% of nano-aramid fiber, 30wt% of filler composition, 0.8wt% of KH550 coupling agent, 0.2wt% of titanate coupling agent KR 9S, 0.8wt% of zinc stearate, 3.2wt% of heat stabilizer, 0.6wt% of plasticizer-di-n-butyl sebacate, 1wt% of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea).

[0156] The difference between Comparative Example 4 and Example 2 is that the thermal stabilizer consists of 1.6 wt % of antioxidant 1010, 0.2 wt % of antioxidant 168, 0.7 wt % of UV-P, and 0.7 wt % of UV-531.

[0157] The difference between Comparative Example 5 and Example 2 is that the thermal stabilizer consists of 1.4 wt % of antioxidant 1010, 0.2 wt % of antioxidant 168, 0.6 wt % of UV-P, 0.6 wt % of UV-531, and 0.4 wt % of rare earth isooctanoate.

[0158] The difference between Comparative Example 6 and Example 2 is that the formula of the TPU resin is as follows: 250.26 g of MDI, 88.63 g of 1,6-hexanediol, 0.04 g of bismuth carboxylate DY-20, 0.08 g of dibutyltin dilaurate, 200 g of polytetramethylene glycol BASF PolyTHF 2000, 200 g of polycarbonate diol CD220HL (Dacelide Co., Ltd., Japan), 6.51 g of dibromoneopentyl glycol, 13.2 g of Exolit OP550 flame retardant, 7 g of antioxidant 1010, 1 g of antioxidant 168, and 5 g of leveling agent -KMT-5514.

[0159] The preparation method of TPU resin is as follows:

[0160] Step 1: put 88.63g of 1,6-hexanediol, 6.51g of dibromoneopentyl glycol, and 13.2g of Exolit OP550 flame retardant into the first trough of the twin-screw extruder, and add 200g of polytetrahydrofuran diol (BASF PolyTHF) 2000, 200g of polycarbonate diol CD220HL (Dacel Corporation of Japan) were put into the second trough of the twin-screw extruder, and 250.26g of MDI, 0.04g of bismuth carboxylate DY-20, 0.08g of dibutyltin dilaurate, 7g of antioxidant 1010, 1g of antioxidant 168, and 5g of leveling agent -KMT-5514 were accurately measured and stirred evenly and then put into the third trough of the twin-screw extruder. The barrel section temperature in the twin-screw extruder was 14 sections, which were 170°C, 175°C, 180°C, 185°C, 185°C, 180°C, 170°C, 170°C, 165°C, 160°C, 160°C, 155°C, 152°C, and 150°C, respectively. The material was discharged from the twin-screw extruder using a gear pump;

[0161] In step 2, the extruded material is granulated by water cooling and dried, and then the obtained pellets are dried in a fluidized bed dryer at 85°C for 10 minutes until the water content is less than 0.03%. Subsequently, the TPU resin pellets are thermally adjusted at 80°C for 24 hours to obtain the TPU resin pellets. The melting temperature of the obtained TPU resin pellets is measured by DSC to be 179.1°C, and the glass transition temperature Tg is -53.4°C.

[0162] The modified PVC resin was prepared as follows: S1.1, the TPU resin pellets prepared above were dried at 85°C for 6 hours; S1.2, the dried TPU resin pellets and PVC resin (HANWHA, Korea) were mixed. P-1000) is swollen in an organic co-solvent - acetone to form a mixed swelling liquid, wherein the organic co-solvent accounts for 68wt% of the mass of the obtained mixed swelling liquid; S1.3, adding an accurately measured filler composition, a surface modifier, a lubricant, a heat stabilizer, and a phase change microcapsule to the mixed swelling liquid, first mechanically stirring at 200 rpm for 30 minutes, and then ultrasonically dispersing (40 kHz / 800 W) for 10 minutes, and distilling off the acetone at 0.06-0.065 MPa to obtain a mixed resin; S1.4, heating the obtained resin to 180°C, adding accurately measured di-n-butyl sebacate and 3,3-dimethyl-4,4-diaminodicyclohexylmethane, and kneading for 180 seconds; S1.5, placing the obtained kneaded mixture in a screw extruder for melt extrusion, drawing, cooling, granulation, and drying, with the melt extrusion temperature range being 150-180°C, to obtain a finished modified PVC resin masterbatch.

[0163] The difference between Comparative Example 7 and Example 2 is that the modified PVC resin is made of the following raw materials in percentage by mass: 22 wt % of TPU resin (Bayer Ulder, US-60AU10), 0.15 wt % of cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 31.6 wt % of filler composition, 1 wt % of KH550 coupling agent, 0.4 wt % of titanate coupling agent KR9S, 1 wt % of zinc stearate, 3.2 wt % of heat stabilizer, 2.4 wt % of plasticizer-di-n-butyl sebacate, 1 wt % of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea).

[0164] The filler composition consists of 3wt% of ammonium polyphosphate (500 mesh, brand Kemeisi, CAS: 68333-79-9), 2wt% of zinc borate (800 mesh, CAS: 10361-94-1, brand Xinghai Chemical), 8wt% of nano-aluminum hydroxide (ZT-LA20, average particle size 20nm, brand Zhiti Nanomicro), 4wt% of nano-magnesium hydroxide (brand Zhiti Nanomicro, particle size 30nm~50nm), 1wt% of halloysite nanotubes (HNTs have an outer tube of 10-50nm, an inner diameter of 5-20nm, and a length of 0.5-3um), and 13.6wt% of nano-alumina VK-L04R.

[0165] The difference between Comparative Example 8 and Example 2 is that the modified PVC resin is made of the following raw materials in percentage by weight: 22 wt% of TPU resin US-60AU10, 1.6 wt% of nano-aramid fiber, 30 wt% of filler composition, 1 wt% of KH550 coupling agent, 0.4 wt% of titanate coupling agent KR 9S, 1 wt% of zinc stearate, 3.2 wt% of heat stabilizer, 2.4 wt% of di-n-butyl sebacate, 1 wt% of phase change microcapsule, and the balance is PVC resin (HANWHA P-1000, Korea).

[0166] The difference between Comparative Example 9 and Example 2 is that the filler composition consists of 3.6 wt % ammonium polyphosphate, 2.4 wt % zinc borate, 0.9 wt % basic cerium carbonate, 7.5 wt % nano-aluminum hydroxide, 3.6 wt % nano-magnesium hydroxide, and 12 wt % nano-aluminum oxide.

[0167] The difference between Comparative Example 10 and Example 13 is that the filler composition consists of 7wt% of ammonium polyphosphate (500 mesh, brand Kemeis, CAS: 68333-79-9), 1.5wt% of molybdenum disulfide nanosheets (MoS2-200nm, brand Yamei Nano), 2.5wt% of basic cerium carbonate sieved through 800 mesh, 12wt% of nano-aluminum hydroxide ZT-LA20, 5.5wt% of nano-magnesium hydroxide (particle size 30nm~50nm), and 1.5wt% of halloysite nanotubes.

[0168] The difference between Comparative Example 11 and Example 13 is that the filler composition consists of 10 wt % of nano-aluminum hydroxide (ZT-LA20, average particle size 20 nm, brand Zhitai Nano) and 20 wt % of nano-aluminum oxide VK-L04R.

[0169] The difference between Comparative Example 12 and Example 1 is that no maleic anhydride-modified polybutadiene is added.

[0170] The modified rubber composite material is made of 65 parts of Yanshan Petrochemical IIR1751, 5 parts of fluororubber FKM GBR6005, 30 parts of TPU resin US-60AU10, 3.5 parts of sulfur, 0.5 parts of nano zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, 3 parts of KH550 coupling agent, and 1 part of titanate coupling agent KR 9S.

[0171] The difference between Comparative Example 13 and Example 1 is that fluororubber FKM GBR6005 is not added.

[0172] The modified rubber composite material is made of 65 parts of Yanshan Petrochemical IIR1751, 30 parts of TPU resin US-60AU10, 5 parts of maleic anhydride modified polybutadiene, 3.5 parts of sulfur, 0.5 parts of nano zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, 3 parts of KH550 coupling agent, and 1 part of titanate coupling agent KR 9S.

[0173] The difference between Comparative Example 14 and Example 1 is that TPU resin US-60AU10 is not added.

[0174] The modified rubber composite material is made of 92.5 parts of Yanshan Petrochemical IIR1751, 7.5 parts of fluororubber FKM GBR6005, 5 parts of maleic anhydride modified polybutadiene, 3.5 parts of sulfur, 0.5 parts of nano zinc oxide, 3 parts of accelerator D, 1 part of accelerator DM, 3 parts of antioxidant RD, 1 part of antioxidant 1098, 70 parts of functional filler, 3 parts of KH550 coupling agent, and 1 part of titanate coupling agent KR9S.

[0175] The difference between Comparative Example 15 and Example 1 is that the TPU resin US-60AU10 is replaced by the TPU resin in Comparative Example 6.

[0176] The difference between Comparative Example 16 and Example 1 is that the functional filler is composed of 30 parts of carbon black N550 (brand Anlun carbon black), 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of 1250 mesh molybdenum disulfide powder (brand Xinbaiyi), and 10 parts of 1250 mesh ultrafine alumina DCA-10S (Dongguan Dongchao New Materials Technology Co., Ltd.).

[0177] Performance Testing: 1. Tensile properties were tested according to ASTM 412, dimensions: 150mm × 20mm × 2mm, tensile rate: 200mm / min. 2. Flame retardancy safety was assessed by measuring the limiting oxygen index, determined according to ASTM D2863. 3. Low-temperature toughness was tested according to ASTM D746, with six repeated tests. The cable's low-temperature brittleness index was <-42°C; the temperature setting was -52°C ± 0.5°C. The test lasted 300 seconds, with a specimen length * width * thickness = 40mm × 6mm × 2mm. The impact velocity was 2m / s. 4. Thermal conductivity was determined according to GB / T 10295-2008, "Thermal Insulation Materials - Determination of Steady-State Thermal Resistance and Related Properties - Heat Flow Meter Method." 5. Electrical strength testing is conducted in accordance with GB / T 1408.1-2006, "Electrical Strength Test Methods for Insulating Materials, Part 1: Power Frequency Tests," using a ZJC-50E breakdown voltage tester with a voltage ramp rate of 0.1 kV / s. Power is disconnected within 0.1 seconds of specimen breakdown. 6. Damping performance (Tanδ) testing: 1.0 mm thick specimens made of modified rubber composites are used. Test conditions: 100 Hz frequency, heating from -105°C to 120°C at a rate of 3°C / min, single cantilever beam deformation mode.

[0178] Table 1: Test parameters of modified PVC resin in Examples 1-16 and Comparative Examples 1-11

[0179]

[0180]

[0181] Combining Example 1 and Comparative Example 1 with Table 1, it can be seen that the modified PVC resin prepared in the present application has good flame retardant properties, low-temperature toughness, tensile properties, electrical strength and insulation thermal conductivity. The TPU resin can act as a plasticizer in the system to reduce the amount of di-n-butyl sebacate, improve the processing performance, low-temperature toughness and tensile properties of the modified PVC resin, and can be combined with the filler system to give the overall excellent flame retardant properties, insulation thermal conductivity and electrical strength.

[0182] Combining Examples 1-4 and Comparative Examples 1-3 with Table 1, it can be seen that the addition amount of the polyurethane resin TPU in the modified PVC resin formula of the present application is preferably controlled at 18-26 wt %, and the preferred addition range of TPU is 20-22 wt %.

[0183] Combining Examples 2, 5-7 and Comparative Examples 4-5 with Table 1, it can be seen that the addition of a heat stabilizer formed by compounding nano-silicon nitride and nano-titanium nitride can improve the processing performance and resistance to thermal oxidation degradation of the modified PVC resin, thereby improving the low-temperature toughness, tensile properties, electrical strength, flame retardancy, and insulation and thermal conductivity of the modified PVC resin.

[0184] From Examples 2, 8-10 and Comparative Example 6 and Table 1, it can be seen that the modified PVC resin prepared using the homemade TPU resin in this application has relatively better low-temperature toughness and tensile properties, and also maintains good flame retardant properties, electrical strength and insulation thermal conductivity, which is more conducive to improving the low-temperature resistance and service life of the antifreeze cable.

[0185] Combining Example 2 and Comparative Example 7 with Table 1, it can be seen that the addition of nano-aramid fibers can effectively improve the modified PVC resin to have relatively better low-temperature toughness and tensile properties.

[0186] From Example 2 and Comparative Examples 7-8 and Table 1, it can be seen that the addition of 3,3-dimethyl-4,4-diaminodicyclohexylmethane can appropriately improve the crosslinking density of the modified PVC resin system, thereby being beneficial to the overall flame retardancy, low-temperature toughness, tensile properties, electrical strength and insulation thermal conductivity, thereby ensuring the quality and safety performance of the prepared antifreeze cable.

[0187] Combining Examples 2, 11-16 and Comparative Examples 9-11 with Table 1, it can be seen that the filler composition in the modified PVC resin formula is preferably controlled at 28-36 wt %, preferably 30 wt %, which can ensure overall comprehensive performance while having good economy.

[0188] Combining Examples 2, 11-16 and Comparative Examples 9-11 with Table 1, it can be seen that the filler composition is composed of a flame retardant filler and an insulating and thermally conductive filler in a mass ratio of (60-75): (25-40), and the prepared modified PVC resin has good comprehensive properties.

[0189] From Examples 2, 11-16, and Comparative Examples 9-11 and Table 1, it can be seen that the filler composition formed by compounding halloysite nanotubes and molybdenum disulfide nanosheets can improve the flame retardant properties, low-temperature toughness, tensile properties, and electrical strength of the prepared modified PVC resin, thereby ensuring the quality and safety performance of the prepared antifreeze cable.

[0190] Table 2: Test parameters of the modified rubber composite materials in Example 1, Examples 17-22 and Comparative Examples 12-16

[0191]

[0192] In combination with Example 1, Examples 17-22 and Comparative Examples 12-16 and Table 2, it can be seen that the rubber composite outer layer prepared by the modified rubber composite material gives the antifreeze cable good wear resistance, shock absorption and damping protection performance, flame retardant performance, low temperature resistance toughness, tensile properties, and insulation and thermal conductivity.

[0193] In combination with Example 1, Examples 17-22 and Comparative Examples 12-16 and Table 2, it can be seen that the use of the homemade TPU resin in this application can improve the shock absorption and damping protection performance, low temperature resistance and toughness of the prepared rubber composite outer layer while also having good tensile properties and insulation and thermal conductivity.

[0194] Combining Example 1, Example 1 and Example 21 with Table 2, it can be seen that adding an appropriate amount of titanate coupling agent KR 9S to the modified rubber composite material formula can improve the uniform dispersion and tensile properties of the filler composition.

[0195] From Example 1, Examples 17-22, and Comparative Example 12 and Table 2, it can be seen that adding an appropriate amount of maleic anhydride-modified polybutadiene to the modified rubber composite material formula can improve the tensile properties, low-temperature toughness, and shock-absorbing and damping protection properties of the prepared rubber composite outer layer.

[0196] From Example 1, Examples 17-22, and Comparative Example 13 and Table 2, it can be seen that adding an appropriate amount of fluororubber FKM GBR6005 to the modified rubber composite material formula can improve the weather resistance of the prepared rubber composite outer layer and ensure good wear resistance, shock absorption and damping protection performance, flame retardancy, low-temperature toughness, tensile properties, and insulation and thermal conductivity.

[0197] Combining Example 1, Examples 17-22, and Comparative Examples 14-15 with Table 2, it can be seen that the rubber composite outer layer prepared by adding about 30 parts of TPU resin (TPU resin US-60AU10 or the homemade TPU resin in Examples 8-10) to the modified rubber composite material formula has good shock absorption and damping protection performance, low temperature resistance toughness, and tensile properties.

[0198] In combination with Example 1, Examples 17-22 and Comparative Example 16 and Table 2, it can be seen that the use of the functional filler provided in this application (30 parts of carbon nanotube-doped modified white carbon black or 30 parts of carbon black N550, 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets, and 10 parts of nano-alumina VK-L04R) can ensure that the prepared rubber composite outer layer has good wear resistance, shock absorption and damping protection performance, flame retardant performance, tensile performance, and insulation and thermal conductivity, thereby ensuring the quality and safety performance of the prepared antifreeze cable.

[0199] By testing the parameter indicators of the modified rubber composite material and the modified PVC resin material and combining the parameters of Example 1-22 and Comparative Example 1-16 in Table 1-2, it can be known that the optimal formula of the modified PVC resin material is as follows: the modified PVC resin is made of the following raw materials in percentage by mass: 22wt% of the TPU resin prepared in Example 9, 0.15wt% of the cross-linking agent-3,3-dimethyl-4,4-diaminodicyclohexylmethane, 1.6wt% of the nano-aramid fiber, 30wt% of the filler composition, 1wt% of the KH550 coupling agent, 0.4wt% of the titanate coupling agent KR 9S, 1wt% of the zinc stearate, 3.2wt% of the heat stabilizer, 2.4wt% of the plasticizer-di-n-butyl sebacate, 1wt% of the phase change microcapsule, and the balance is the PVC resin HANWHA P-1000. The thermal stabilizer is composed of 0.3wt% of nano-silicon nitride with an average particle size of 20nm, 0.3wt% of nano-titanium nitride with an average particle size of 20nm, 1.2wt% of antioxidant 1010, 0.2wt% of antioxidant 168, 0.3wt% of UV-P, 0.3wt% of UV-531, and 0.6wt% of rare earth isooctanoate (active ingredient content 8%). The filler composition is composed of 4.2wt% of 500-mesh ammonium polyphosphate, 0.9wt% of molybdenum disulfide nanosheets MoS2 with a particle size of 200nm, 1.5wt% of basic cerium carbonate sieved through 800-mesh, 7.2wt% of nano-aluminum hydroxide ZT-LA20, 3.3wt% of nano-magnesium hydroxide with a particle size of 30nm to 50nm, 0.9wt% of halloysite nanotubes, 10wt% of nano-aluminum oxide VK-L04R, and 2wt% of nano-aluminum nitride with a particle size of 50nm.

[0200] Table 3: Test parameters of the modified PVC resin material and the optimal formula modified PVC resin material in Example 2

[0201]

[0202] By testing the parameters of the modified rubber composite material and the modified PVC resin material and combining the parameters of Example 1-22 and Comparative Example 1-16 in Table 1-2, it can be seen that the optimal formula of the antifreeze cable is as follows:

[0203] The modified PVC resin is prepared by 22 wt % of the TPU resin prepared in Example 9, 0.15 wt % of a cross-linking agent -3,3-dimethyl-4,4-diaminodicyclohexylmethane, 1.6 wt % of a nano-aramid fiber, 30 wt % of a filler composition, 1 wt % of a KH550 coupling agent, 0.4 wt % of a titanate coupling agent KR 9S, 1 wt % of zinc stearate, 3.2 wt % of a heat stabilizer, 2.4 wt % of di-n-butyl sebacate, 1 wt % of a phase change microcapsule, and the balance being PVC resin HANWHA P-1000. The heat stabilizer comprises 0.3 wt% of nano-silicon nitride with an average particle size of 20 nm, 0.3 wt% of nano-titanium nitride with an average particle size of 20 nm, 1.2 wt% of antioxidant 1010, 0.2 wt% of antioxidant 168, 0.3 wt% of UV-P, 0.3 wt% of UV-531, and 0.6 wt% of rare earth isooctanoate. The filler composition comprises 4.2 wt% of 500-mesh ammonium polyphosphate, 0.9 wt% of molybdenum disulfide nanosheets MoS2 with a particle size of 200 nm, 1.5 wt% of basic cerium carbonate sieved through an 800-mesh screen, 7.2 wt% of nano-aluminum hydroxide ZT-LA20, 3.3 wt% of nano-magnesium hydroxide with a particle size of 30-50 nm, 0.9 wt% of halloysite nanotubes, 10 wt% of nano-aluminum oxide VK-L04R, and 2 wt% of nano-aluminum nitride with a particle size of 50 nm.

[0204] The modified rubber composite material is made from 66 parts of Yanshan Petrochemical IIR1751, 6 parts of fluororubber FKM GBR6005, 35 parts of the TPU resin prepared in Example 9, 6 parts of maleic anhydride-modified polybutadiene, 3.6 parts of sulfur, 1.2 parts of nano-zinc oxide, 4 parts of accelerator D, 1 part of accelerator DM, 4 parts of antioxidant RD, 1 part of antioxidant 1098, 80 parts of functional filler, 4 parts of KH550 coupling agent, and 2 parts of titanate coupling agent KR 9S. The functional filler is composed of 35 parts of carbon nanotube-doped modified silica, 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of molybdenum disulfide nanosheets, and 15 parts of nano-alumina VK-L04R.

[0205] Control group: The formula of the antifreeze cable is as follows: the modified PVC resin consists of 3.6wt% ammonium polyphosphate, 2.4wt% zinc borate, 0.9wt% basic cerium carbonate, 7.5wt% nano aluminum hydroxide, 3.6wt% nano magnesium hydroxide, 12wt% nano alumina, 1wt% KH550 coupling agent, 0.8wt% zinc stearate, 1.6wt% antioxidant 1010, 0.2wt% antioxidant 168, 0.7wt% UV-P, 0.7wt% UV-531, 15.6wt% di-n-butyl sebacate, and the balance is PVC HANWHA P-1000.

[0206] The modified rubber composite material is made of 100 parts of Yanshan Petrochemical IIR1751, 3.6 parts of sulfur, 1.2 parts of nano zinc oxide, 4 parts of accelerator D, 1 part of accelerator DM, 4 parts of antioxidant RD, 1 part of antioxidant 1098, 35 parts of carbon black N550, 15 parts of ammonium polyphosphate, 5 parts of zinc borate, 10 parts of 1250 mesh molybdenum disulfide powder, 10 parts of 1250 mesh ultrafine alumina DCA-10S, and 5 parts of KH550 coupling agent.

[0207] Table 4: Test parameters of the antifreeze cables prepared with the best formula and the antifreeze cables in the control group

[0208]

[0209]

[0210] It can be seen from Examples 1-22 and Comparative Examples 1-16 and Tables 1-4 that the antifreeze cable in the present application has good low-temperature flexibility, impact toughness, wear resistance, shock absorption and damping protection performance, flame retardant performance, low-temperature toughness, tensile performance, and insulation and thermal conductivity. It can be used in the northern cold regions (-50°C to 80°C), and at the same time has good flame retardant and fire safety performance, weather resistance, and high-temperature resistance, which can improve the safety and stability of the cable.

[0211] To better cope with the severe cold and low temperature environment in high latitudes, a self-limiting temperature heating wire is spirally wound around the outer wall of the elastic filling layer of the conductive wire bundle of the antifreeze cable (the self-limiting temperature heating wire with a self-limiting temperature threshold of 60°C or 80°C can be selected). By adjusting the pitch of the self-limiting temperature heating wire, the power of the heating surface formed by the self-limiting temperature heating wire is controlled to adapt to antifreeze cable products of different specifications and sizes. The self-limiting temperature heating wire in the antifreeze cable is powered by an external power supply, which can be powered by a solar cell or an external charging station. The self-limiting temperature heating wire is selected from the 1K carbon fiber core self-limiting temperature heating wire provided by Zhejiang Danting. The resistance per unit length is 400-500Ω*m (10°C, 65% RH). Taking a 5m charging cable with a self-limiting temperature heating wire pitch of 5cm as an example, using an external charging station for power supply, the heating output power of the self-limiting temperature heating wire is 6-8W, which can be used to heat the rubber composite outer layer of the antifreeze cable (thermal conductivity (0.89-0.91W (m·K) -1 )、Elastic filling layer (thermal conductivity (0.6-0.7W (m·K) -1 ), modified PVC composite protective outer layer (thermal conductivity (0.65-0.70W (m·K) -1 ) for thermal compensation, and the released heat energy is transferred relatively quickly to the rubber composite outer layer, the elastic filling layer, and the modified PVC composite protective outer layer. Therefore, the cable in this application has good low-temperature flexibility and comfort performance even in severe cold environments, and can solve the problem of using charging cables in severe cold and low-temperature environments at high latitudes.

[0212] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A frost-proof cable, characterized in that: The invention comprises a rubber composite outer layer (1) and a conductive wire bundle (2) located in the rubber composite outer layer (1), wherein an elastic filling layer (3) is filled between the rubber composite outer layer (1) and the conductive wire bundle (2); the conductive wire bundle (2) comprises a plurality of conductive branch wires (20) and a plurality of high-elastic wires twisted together; a single conductive branch wire (20) comprises a multi-strand twisted copper wire core wire (201) and a modified PVC composite protective outer layer (202) coated on the outer wall of the multi-strand twisted copper wire core wire (201); The modified PVC composite protective outer layer (202) is made of modified PVC resin, and the modified PVC resin is made of the following raw materials in percentage by weight: 18-26 wt% of polyurethane resin, 0.05-0.25 wt% of cross-linking agent, 0.5-2 wt% of nanofiber, 28-36 wt% of filler composition, 0.5-2 wt% of surface modifier, 0.5-2 wt% of lubricant, 2-5 wt% of heat stabilizer, 1-5 wt% of plasticizer, 0.5-2 wt% of phase change microcapsule, and the balance is PVC resin with a polymerization degree of 900-1100; The polyurethane resin is a thermoplastic polyurethane elastomer with a Shore hardness of 40-65A and a Tg temperature below -60°C; The cross-linking agent is 3,3-dimethyl-4,4-diaminodicyclohexylmethane and / or 4,4-diaminodicyclohexylmethane; The nanofiber is at least one of nano-aramid fiber, nano-carbon fiber, carbon nanotube, and boron nitride whisker; The surface modifier is a siloxane coupling agent and / or a titanate coupling agent; The lubricant is at least one of stearate, PE wax, paraffin, stearyl alcohol, and butyl stearate; The heat stabilizer is composed of at least one of nano titanium nitride, nano silicon nitride, antioxidant, anti-ultraviolet agent, organic tin stabilizer, calcium zinc composite stabilizer, and isooctanoic acid rare earth; The plasticizer is at least one of tributyl 3-propanetricarboxylate and di-n-butyl sebacate; The filler composition is composed of a flame retardant filler and an insulating and thermally conductive filler in a mass ratio of (60-75):(25-40); The flame retardant filler comprises at least one of halloysite nanotubes and molybdenum disulfide nanosheets and at least one of zinc hydroxystannate, titanate nanotubes, ammonium polyphosphate, diammonium hydrogen phosphate, lithium phosphate, melamine, nano-bentonite, nano-kaolin, nano-montmorillonite, barium metaborate, ammonium metaborate, zinc borate, graphene, expandable graphene, basic cerium carbonate, nano-calcium carbonate, nano-magnesium hydroxide, nano-aluminum hydroxide, and nano-zinc oxide; The insulating thermal conductive filler includes at least one of nano-scale aluminum nitride, aluminum oxide, silicon nitride, and boron nitride.

2. The antifreeze cable according to claim 1, characterized in that: The modified PVC composite protective outer layer (202) is made of modified PVC resin, and the modified PVC resin is made of the following raw materials in percentage by weight: 21-22 wt% of polyurethane resin, 0.12-0.18 wt% of cross-linking agent, 1.2-1.6 wt% of nanofiber, 30-32 wt% of filler composition, 0.8-1.2 wt% of surface modifier, 0.8-1.2 wt% of lubricant, 3.6-4.2 wt% of heat stabilizer, 1.6-2.4 wt% of plasticizer, 1.6-2.0 wt% of phase change microcapsule, and the balance being PVC resin with a polymerization degree of 900-1100.

3. The antifreeze cable according to claim 1 or 2, characterized in that: The heat stabilizer consists of 5-10wt% of nano titanium nitride, 5-20wt% of nano silicon nitride, 25-40wt% of antioxidant 1010, 3-8wt% of antioxidant 168, 5-20wt% of anti-ultraviolet agent UV-P, 5-20wt% of anti-ultraviolet agent UV-531, and 5-20wt% of rare earth isooctanoate.

4. The antifreeze cable according to claim 1 or 2, characterized in that: The flame retardant filler consists of 15-30 wt% of ammonium polyphosphate, 5-20 wt% of halloysite nanotubes, 5-20 wt% of molybdenum disulfide nanosheets, 5-10 wt% of basic cerium carbonate, 10-25 wt% of nano magnesium hydroxide and the balance of nano aluminum hydroxide.

5. The antifreeze cable according to claim 1, characterized in that: The polyurethane resin is a thermoplastic polyurethane elastomer (TPU) with a hard segment content of 30-35wt%, an R value of 0.99-1.02, and a melting temperature of 160-180°C. The raw materials for preparing the TPU include polyols and reactive flame retardants. The polyols are composed of a polyether diol with a molecular weight of 2000-3000, a polycarbonate diol with a molecular weight of 2000-3000, a polyester diol with a molecular weight of 2000-3000, and at least one of hydroxy-terminated polybutadiene-acrylonitrile (HTBN) with a molecular weight of 2000-4500. The reactive flame retardant includes at least dibromoneopentyl glycol and / or Exolit OP550, and the reactive flame retardant accounts for 0.5-2.5wt% of the total mass of the TPU resin.

6. The antifreeze cable according to claim 1 or 2, characterized in that: The preparation method of the modified PVC resin is as follows: S1, preparation of polyurethane resin; S2, swelling the polyurethane resin and the PVC resin in an organic co-solvent to form a mixed swelling solution, wherein the organic co-solvent accounts for 60-75 wt% of the mass of the obtained mixed swelling solution; S3, adding accurately measured filler composition, surface modifier, lubricant, thermal stabilizer, and phase change microcapsules to the mixed swelling liquid, mechanically stirring for 30-60 minutes, then ultrasonically dispersing for 5-30 minutes, and distilling off the organic co-solvent at 0.06-0.08 MPa to obtain a mixed resin; S4, heating the obtained resin to 170-175°C, adding accurately measured plasticizer and cross-linking agent, and mixing for 300-320 seconds; S5, the obtained banburying mixture is placed in a screw extruder for melt extrusion, drawing, cooling, granulation, and drying. The melt extrusion temperature range is 150-175° C., and the finished modified PVC resin can be obtained.

7. The antifreeze cable according to claim 5, characterized in that: The rubber composite outer layer (1) is made of a modified rubber composite material, which comprises 64-72 parts of a rubber composition, 28-36 parts of a thermoplastic polyurethane elastomer (TPU), 4-8 parts of a maleic anhydride-modified polyolefin resin, 1-4 parts of a vulcanizing agent, 0.5-2 parts of a vulcanization activator, 1-5 parts of an accelerator, 2-4 parts of an anti-aging agent, 60-80 parts of a functional filler, and 2-6 parts of a dispersant. The rubber composition is composed of butyl rubber and / or bromobutyl rubber and fluororubber; The maleic anhydride modified polyolefin resin is maleic anhydride modified polyethylene and / or maleic anhydride modified polybutadiene; The vulcanizing agent is sulfur and / or colloidal vulcanization; the vulcanization activator is nano zinc oxide; The accelerator is at least one of accelerator DM, accelerator DZ, accelerator PZ, and accelerator D; The dispersant is a siloxane coupling agent and / or a titanate coupling agent; The anti-aging aid includes at least one of an alkylphenol antioxidant, a phenolic antioxidant, and a heterocyclic antioxidant; The functional filler is composed of at least one of white carbon black and carbon black doped with carbon nanotubes, flame retardant filler and nano-alumina; The flame retardant filler is at least one of ammonium polyphosphate, diammonium hydrogen phosphate, nano-montmorillonite, barium metaborate, ammonium metaborate, halloysite nanotubes, molybdenum disulfide nanosheets, nano-calcium carbonate, nano-magnesium hydroxide, and nano-aluminum hydroxide.

8. The antifreeze cable according to claim 7, characterized in that: The modified rubber composite material includes 65 parts of a rubber composition, 30 parts of a thermoplastic polyurethane elastomer (TPU), 5 parts of maleic anhydride-modified polybutadiene, 3-4 parts of a vulcanizing agent, 0.8-1.6 parts of a vulcanization activator, 3-4 parts of an accelerator, 3-4 parts of an anti-aging agent, 68-72 parts of a functional filler, and 3-5 parts of a dispersant.

9. The antifreeze cable according to claim 5, characterized in that: The high-elastic wire is made of 60-80 parts by mass of thermoplastic polyurethane elastomer TPU, 25-40 parts by mass of insulating and thermally conductive filler, and 1-3 parts by mass of a surface modifier; the insulating and thermally conductive filler includes at least one of nano-scale aluminum nitride, aluminum oxide, silicon nitride, and boron nitride; and the surface modifier is a siloxane coupling agent and / or a titanate coupling agent.

10. A method for preparing the antifreeze cable according to any one of claims 1 to 9, characterized in that: Here are the steps: Step 1: Preparation of modified PVC resin, modified rubber composite material, and high elastic wire; Step 2: melt-extrude the modified PVC resin prepared in step 1 and coat it on the outer wall of the multi-strand twisted copper wire core wire (201) to form a modified PVC composite protective outer layer (202) to obtain the conductive branch wire (20); Step 3, twisting the conductive branch wire (20) prepared in step 2 with the high elastic wire material, and melting them to form a conductive wire bundle (2) covered by the elastic filling layer (3); Step 4: using the modified rubber composite material to prepare an elastic rubber composite casing, i.e., a rubber composite outer layer (1); the obtained rubber composite outer layer (1) is sleeved on the outer wall of the elastic filling layer (3) to obtain a semi-finished antifreeze cable; Step 5: The semi-finished antifreeze cable wire is subjected to heat treatment to obtain a finished antifreeze cable wire.

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