An insulating and interference-resistant polyvinyl chloride cable material and its preparation method

Abstract

This invention discloses an insulating and anti-interference polyvinyl chloride (PVC) cable material and its preparation method, belonging to the field of insulating cable material processing technology. This invention addresses the technical problem that the flame retardant, insulation, and anti-electromagnetic interference properties of existing PVC cable materials need further improvement. The insulating and anti-interference PVC cable material comprises the following components by weight: 55-65 parts PVC, 20-30 parts activated PVC, 12-16 parts silicon-based reinforcing agent, 13-17 parts ammoniated loaded kaolin, 8-10 parts epoxidized flame retardant, and 6-8 parts auxiliary additives. This invention, by using activated PVC as a compatibilizer to promote the mixing of silicon-based reinforcing agent and PVC, and then modifying the flame retardant with epoxy resin and optimizing the composition of the flame retardant, not only effectively improves the insulation and tensile properties of the PVC cable material but also enhances its flame retardant and anti-electromagnetic interference properties.

Description

Technical Field

[0001] This invention relates to the field of insulating cable material processing technology, specifically to an insulating and interference-resistant polyvinyl chloride cable material and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) cables are widely used in power transmission, communication, and industrial equipment due to their excellent mechanical properties, chemical resistance, and cost advantages. However, traditional PVC cables are susceptible to interference in high-frequency electromagnetic fields or complex electromagnetic environments, leading to signal transmission distortion. Although some studies have improved interference resistance by adding a metal shielding layer (such as tinned copper wire), such structural designs are complex, costly, and prone to shielding effectiveness degradation due to mechanical deformation. Furthermore, the PVC matrix has high dielectric loss, and its insulation performance deteriorates significantly under high-temperature or high-frequency conditions, making it difficult to meet the needs of emerging fields such as 5G communication and new energy vehicles.

[0003] In the prior art, an invention patent with publication number CN116082741B discloses a cable shielding material, its preparation method, and its application. By weight, the raw materials of the cable shielding material include 65-85 parts of a matrix resin, 10-30 parts of conductive carbon black, 0.5-5 parts of a graphene-nano silver composite material, and 0.5-3 parts of a crosslinking agent. By adding the graphene-nano silver composite material, the amount of conductive carbon black used in the cable shielding material is reduced, which not only improves conductivity but also gives the cable material excellent mechanical and processing properties, and a high degree of surface smoothness.

[0004] Existing cable shielding materials achieve good electromagnetic shielding performance by introducing a large amount of conductive material into the matrix resin to reduce its resistivity. However, this modification method leads to a decrease in the insulation performance of the cable material, making it difficult to improve its electromagnetic shielding performance while ensuring the insulation performance. In existing technologies, the magnetic loss mechanism of magnetic materials can effectively absorb electromagnetic wave energy. However, magnetic materials with metal as the main component also have good conductivity, and their extensive use will also increase the insulation performance of the cable material. Moreover, the performance of a single magnetic material against electromagnetic interference needs further improvement. Furthermore, the flame retardancy rating of PVC is between B1 and B2, with a low burning rate and flame propagation speed. When used in cables, its flame retardancy needs further improvement.

[0005] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide an insulating and interference-resistant polyvinyl chloride cable material and its preparation method, which solves the technical problem that the flame retardant performance, insulation performance and electromagnetic interference resistance of existing PVC cable materials need to be further improved.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] An insulating and interference-resistant polyvinyl chloride cable material, comprising the following components by weight: 55-65 parts PVC, 20-30 parts activated PVC, 12-16 parts silicon-based reinforcing agent, 13-17 parts ammoniated loaded kaolin, 8-10 parts epoxidized flame retardant, and 6-8 parts auxiliary additives.

[0009] The activated PVC is obtained by the following steps:

[0010] A1. Mix polyvinyl chloride powder, sodium hydroxide and purified water. After sealing the reaction system, raise the temperature to 200-220℃ and the pressure to 2.8-3.2MPa. Keep it at this temperature for 2-3 hours. Then, perform post-treatment to obtain dechlorinated PVC.

[0011] A2. Stir and mix the dechlorinated PVC, formic acid and catalyst, raise the temperature of the reaction system to 60-70℃, add hydrogen peroxide solution dropwise to the reaction system, and after the addition is complete, keep the reaction at the temperature for 40-60 minutes, and then perform post-treatment to obtain activated PVC.

[0012] The synthesis reaction mechanism of activated PVC is as follows:

[0013] During the reaction, under the action of a strong base, it attacks the β-hydrogen on the polyvinyl chloride molecular chain. The chlorine atom in the polyvinyl chloride molecular chain acts as a leaving group and undergoes an E2 elimination reaction, removing HCl and forming a double bond on the polyvinyl chloride molecular chain to prepare dechlorinated PVC.

[0014] Sulfuric acid, as a strong acid catalyst, catalyzes the reaction of formic acid and hydrogen peroxide under acidic conditions to produce performic acid. Performic acid, as an electrophilic reagent, has its oxygen atoms attack the double bonds in dechlorinated PVC to form an epoxidized structure, thus preparing activated PVC.

[0015] Further, in step A1, the ratio of polyvinyl chloride powder, sodium hydroxide, and purified water is 8g:1.1-1.3g:30mL. The post-treatment includes: after the reaction is complete, the temperature of the reaction system is reduced to room temperature, the pressure is reduced to atmospheric pressure, the mixture is filtered, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a dryer at a temperature of 50-55℃ and vacuum dried to constant weight to obtain dechlorinated PVC.

[0016] Further, in step A2, the ratio of the amount of dechlorinated PVC, formic acid, catalyst, and hydrogen peroxide solution is 5g:20mL:0.1g:8mL, the catalyst is 90-95wt% sulfuric acid, and the mass concentration of the hydrogen peroxide solution is 30%. The post-treatment includes: after the reaction is completed, the temperature of the reaction system is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 50-55℃ and vacuum dried to constant weight to obtain activated PVC.

[0017] Furthermore, the preparation method of the silicon-based reinforcing agent is as follows: in an inert atmosphere, vinyl silicone oil, methyl methacrylate, isooctyl acrylate, 1,2-epoxy-7-octene and toluene are mixed, the temperature of the reaction system is raised to 70-80℃, an initiator solution is added dropwise to the reaction system, the reaction is kept at the temperature for 6-8 hours, and then post-processed to obtain the silicon-based reinforcing agent.

[0018] The synthesis reaction mechanism of silicon-based reinforcing agents is as follows:

[0019] During the reaction, under the action of a free radical initiator, the unsaturated olefin double bonds on vinyl silicone oil, methyl methacrylate, isooctyl acrylate, and 1,2-epoxy-7-octene molecules undergo a free radical addition reaction to form a polyolefin cross-linked structure reinforced with polysiloxane, thus preparing a silicon-based reinforcing agent.

[0020] Furthermore, the ratio of the vinyl silicone oil, methyl methacrylate, isooctyl acrylate, 1,2-epoxy-7-octene, toluene, and initiator solution is 7g:3g:2g:2g:50mL:5mL. The initiator solution is composed of azobisisobutyronitrile and toluene at a ratio of 1g:15mL. The post-treatment includes: after the reaction is complete, keeping the reaction system at 70-80℃, removing low-boiling substances under reduced pressure to obtain the silicon-based reinforcing agent.

[0021] Furthermore, the ammonified loaded kaolin is obtained by the following steps:

[0022] B1. Stir and mix calcined kaolin and activation liquid, keep the reaction system at 75-85℃ for 4-6 hours, and then perform post-treatment to obtain activated kaolin.

[0023] B2. Mix ferric chloride and ethylene glycol until the system is dissolved. Add activated kaolin to the reaction system and ultrasonically disperse for 60-80 min. While stirring, add trisodium citrate and ammonium acetate to the reaction system and stir at room temperature for 40-60 min. After post-treatment, load kaolin is obtained.

[0024] B3. Mix the loaded kaolin, anhydrous ethanol and 4-aminobutyltriethoxysilane, raise the temperature of the reaction system to 50-60℃, add 2-3 mol / L sodium hydroxide solution to the reaction system, keep the reaction at this temperature for 4-5 hours, and then perform post-treatment to obtain aminated loaded kaolin.

[0025] The synthesis reaction mechanism of loaded kaolin is as follows:

[0026] During the reaction, loose and porous calcined kaolin was selected as the raw material and activated to improve its reactivity, thus preparing activated kaolin. Ferric chloride dissolved in ethylene glycol to form Fe. 3+ ions, Fe 3+ It undergoes a coordination reaction with the hydroxyl groups on the surface of kaolin to form Fe-O bonds. Ethylene glycol acts as a reducing agent, and under high temperature conditions, some of the Fe... 3+ Reduced to Fe 2+ Magnetic iron oxide nanoparticles are formed and loaded onto the surface of kaolin. During the reaction, trisodium citrate and ammonium acetate act as stabilizers to prevent the nanoparticles from agglomerating, thus preparing iron oxide-loaded kaolin. 4-aminobutyltriethoxysilane is hydrolyzed in an alkaline environment to form silanol. The silanols undergo condensation reactions with each other or with the active sites on the surface of the loaded kaolin particles to form Si-O-Si bonds. Polysiloxane coating and amino modification are formed on the loaded kaolin particles, thus preparing aminated loaded kaolin.

[0027] Further, in step B1, the ratio of calcined kaolin to activation solution is 1g:5mL. The activation solution is composed of 2-3mol / L formic acid, sodium dodecyl sulfate, and 20-30wt% hydrogen peroxide in a ratio of 10mL:0.3g:2mL. The post-treatment includes: after the reaction is complete, the temperature of the reaction system is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral, dried, and the filter cake is transferred to a drying oven at a temperature of 70-80℃ and dried to constant weight to obtain activated kaolin.

[0028] Further, in step B2, the ratio of ferric chloride, ethylene glycol, activated kaolin, trisodium citrate, and ammonium acetate is 5g:50mL:9g:1g:1.3g. The post-treatment includes: after the reaction is complete, placing the reaction system in a heat exchange medium at 200℃ and keeping it at that temperature for 3-4 hours. After the temperature of the reaction system drops to room temperature, adding a 50 vol% ethanol aqueous solution to the reaction system, stirring and dispersing for 30-50 minutes, filtering, washing the filter cake three times with purified water and ethanol, drying it, transferring the filter cake to a drying oven at 70-80℃, and drying it to constant weight to obtain loaded kaolin.

[0029] Further, in step B3, the ratio of the loaded kaolin, anhydrous ethanol, 4-aminobutyltriethoxysilane, and 2-3 mol / L sodium hydroxide solution is 7 g:40 mL:3 g:10 mL. The post-treatment includes: after the reaction is complete, the temperature of the reaction system is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral, dried under vacuum, and the filter cake is transferred to a drying oven at a temperature of 65-75℃ and vacuum dried to constant weight to obtain aminated loaded kaolin.

[0030] Furthermore, the preparation method of the epoxidized flame retardant is as follows: epoxy resin and anhydrous ethanol are stirred and mixed, the temperature of the reaction system is raised to 70-80℃, and the system is kept warm and stirred until dissolved. Flame retardant is added to the reaction system, and the system is kept warm and stirred for 60-80 minutes. The temperature of the reaction system is lowered to room temperature, purified water is added to the reaction system, and the system is kept warm and stirred for 20-30 minutes. After post-treatment, the epoxidized flame retardant is obtained.

[0031] Furthermore, the ratio of epoxy resin, xylene, and flame retardant is 1g:10mL:3g. The flame retardant is composed of antimony trioxide, zinc stannate, ammonium octamolate, and graphene oxide in a weight ratio of 5:3:2:3. The post-treatment includes: after the reaction is complete, the reaction system temperature is lowered to room temperature, filtered, the filter cake is washed three times with purified water and then dried, the filter cake is transferred to a drying oven at a temperature of 60-70℃ and vacuum dried to constant weight to obtain epoxy flame retardant.

[0032] The synthesis reaction mechanism of epoxidized fuel inhibitors is as follows:

[0033] During the reaction, epoxy resin dissolves in anhydrous ethanol to form a homogeneous solution. Heating promotes the expansion of epoxy resin molecular chains. The surface of the fuel particles and the epoxy resin molecular chains are physically adsorbed and bonded to form a uniformly dispersed composite material. Purified water is added to reduce the solubility of epoxy resin, causing the composite material to precipitate from the solution and form a solid precipitate, thus preparing the epoxidized fuel.

[0034] The present invention also proposes a method for preparing an insulating and interference-resistant polyvinyl chloride cable material. The method for preparing the insulating and interference-resistant polyvinyl chloride cable material is as follows: PVC, activated PVC, silicon-based reinforcing agent, ammonified loaded kaolin, epoxidized flame retardant and auxiliary additives are mixed, melt-extruded by a twin-screw extruder and then pelletized to obtain polyvinyl chloride cable material.

[0035] Furthermore, the auxiliary additives are composed of plasticizer, dispersant, antioxidant and colorant in a weight ratio of 5:3:2:1:2. The plasticizer is phthalate, the dispersant is metal stearate, the antioxidant is antioxidant 1010, and the colorant is any one or more of chrome yellow, molybdenum chrome red, cobalt blue, chrome green and carbon black. The temperatures of the five temperature zones of the twin-screw extruder from the feed end to the discharge end are 180°C, 185°C, 190°C, 190°C and 195°C respectively.

[0036] The present invention has the following beneficial effects:

[0037] 1. The insulating and interference-resistant polyvinyl chloride (PVC) cable material of the present invention enhances the polarity of the PVC chain by introducing epoxy groups into activated PVC, thereby using activated PVC as a compatibilizer to promote the mixing of silicon-based reinforcing agents and PVC. Polar ester groups are introduced onto the polysiloxane molecules by methyl methacrylate and isooctyl acrylate, further enhancing the compatibility between the silicon-based reinforcing agent and PVC, thereby improving the mechanical strength of the PVC cable material. The amino groups modified on the surface of ammoniated kaolinite undergo ring-opening condensation with the epoxy groups on the activated PVC or silicon-based reinforcing agent molecules under high temperature conditions to form covalent bonds, constructing a three-dimensional network crosslinking in the PVC cable material. The flexible siloxane chains of the silicon-based reinforcing agent and the PVC molecular chains form a "rigid-flexible" structure through physical entanglement or chemical crosslinking, improving the tensile strength and elongation at break of the PVC cable material.

[0038] 2. The insulating and anti-interference polyvinyl chloride cable material of the present invention modifies the flame retardant with epoxy resin, coating the flame retardant with epoxy resin. The epoxy groups on the epoxy resin molecules are bonded to the polar groups of the activated PVC molecular chains through hydrogen bonds or covalent bonds, ensuring uniform dispersion of the flame retardant. In the flame retardant, antimony trioxide reacts with HCl released from the thermal decomposition of PVC to generate a gaseous free radical scavenger SbCl3, which inhibits flame propagation by quenching the active free radicals of the combustion chain reaction. The decomposition products of ammonium octamolate and zinc stannate at high temperatures can catalyze the formation of a char layer while diluting the concentration of combustible gas, inhibiting matrix decomposition. The sheet structure of graphene oxide migrates to the material surface during combustion, forming a continuous physical barrier to block the diffusion of combustible gas. Furthermore, the oxygen-containing functional groups of graphene oxide promote the dehydrogenation crosslinking of PVC, enhancing the density of the char layer and further improving the flame retardant performance of the cable material.

[0039] 3. The insulating and anti-interference polyvinyl chloride cable material of the present invention enhances the interfacial bonding force between kaolin and PVC matrix by loading iron oxide particles onto kaolin and modifying the kaolin particles with a large amount of amino groups, reducing filler agglomeration and ensuring uniform dispersion. The strong magnetism of the iron oxide particles can effectively absorb electromagnetic wave energy through eddy current loss and hysteresis loss, thus enhancing the electromagnetic shielding effect. Furthermore, the kaolin sheets and Fe3O4 nanoparticles form a "sheet-particle" composite structure, which enhances electromagnetic wave reflection and scattering, and extends the electromagnetic wave propagation path. The conductive network of graphene oxide attenuates electromagnetic waves through reflection and multiple reflections, further enhancing the electromagnetic shielding performance of the cable material. Detailed Implementation

[0040] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0041] In this application, the polyvinyl chloride powder is selected from Ningbo Senhong Plastics Co., Ltd., the manufacturer is Qilu Petrochemical, and the product specification is S-1300.

[0042] In this application, the vinyl silicone oil is selected from Jinan Xinglongda Chemical Co., Ltd., with a viscosity of 5000 cs and a vinyl content of 3%;

[0043] In this application, the epoxy resin is a bisphenol A type epoxy resin, model E-12;

[0044] In this application, the calcined kaolin selected is from Lingshou County Yongzhuo New Material Technology Co., Ltd., with a particle size of 200 mesh.

[0045] Example 1

[0046] This embodiment provides a method for preparing activated PVC for insulating and interference-resistant polyvinyl chloride cable materials, including the following steps:

[0047] A1. Preparation of dechlorinated PVC

[0048] Weigh out 800g of polyvinyl chloride powder, 110g of sodium hydroxide, and 3000mL of purified water and add them to a high-pressure reactor. Stir the mixture and seal the reactor. Raise the temperature of the heat exchange medium in the jacket of the high-pressure reactor to 200℃ and the pressure to 2.8MPa. Keep the reactor at this temperature for 2 hours. Then, lower the temperature of the high-pressure reactor to room temperature and the pressure to atmospheric pressure. Filter the mixture and wash the filter cake with purified water until it is neutral. Dry the filter cake and transfer it to a dryer at 50℃. Vacuum dry the filter cake to constant weight to obtain dechlorinated PVC.

[0049] A2. Preparation of activated PVC

[0050] Weigh out 800g of dechlorinated PVC, 3200mL of formic acid, and 16g of 90wt% sulfuric acid and add them to a 10L reactor. Mix the mixture and raise the reactor temperature to 60℃. Add 1280mL of 30wt% hydrogen peroxide solution dropwise to the reactor. After the addition is complete, keep the reactor at this temperature for 40min. Then, lower the reactor temperature to room temperature, filter the mixture, wash the filter cake with purified water until neutral, and then dry it. Transfer the filter cake to a drying oven at 50℃ and vacuum dry it to constant weight to obtain activated PVC.

[0051] Example 2

[0052] This embodiment provides a method for preparing activated PVC for insulating and interference-resistant polyvinyl chloride cable materials, including the following steps:

[0053] A1. Preparation of dechlorinated PVC

[0054] Weigh out 800g of polyvinyl chloride powder, 120g of sodium hydroxide, and 3000mL of purified water and add them to a high-pressure reactor. Stir the mixture. After sealing the high-pressure reactor, raise the temperature of the heat exchange medium in the jacket of the high-pressure reactor to 210℃ and the pressure to 3.0MPa. Keep the mixture at this temperature for 2.5h. Then, lower the temperature of the high-pressure reactor to room temperature and the pressure to atmospheric pressure. Filter the mixture and wash the filter cake with purified water until it is neutral. Then, dry the filter cake and transfer it to a dryer at 53℃. Vacuum dry the filter cake to constant weight to obtain dechlorinated PVC.

[0055] A2. Preparation of activated PVC

[0056] Weigh out 800g of dechlorinated PVC, 3200mL of formic acid, and 16g of 93wt% sulfuric acid and add them to a 10L reactor. Mix the mixture and raise the temperature of the reactor to 65℃. Add 1280mL of 30wt% hydrogen peroxide solution dropwise to the reactor. After the addition is complete, keep the reactor at this temperature for 50min. Then, lower the temperature of the reactor to room temperature, filter the mixture, wash the filter cake with purified water until neutral, and then dry it. Transfer the filter cake to a drying oven at 53℃ and vacuum dry it to constant weight to obtain activated PVC.

[0057] Example 3

[0058] This embodiment provides a method for preparing activated PVC for insulating and interference-resistant polyvinyl chloride cable materials, including the following steps:

[0059] A1. Preparation of dechlorinated PVC

[0060] Weigh out 800g of polyvinyl chloride powder, 130g of sodium hydroxide, and 3000mL of purified water and add them to a high-pressure reactor. Stir the mixture. After sealing the high-pressure reactor, raise the temperature of the heat exchange medium in the jacket of the high-pressure reactor to 220℃ and the pressure to 3.2MPa. Keep the mixture at this temperature for 3 hours. Then, lower the temperature of the high-pressure reactor to room temperature and the pressure to atmospheric pressure. Filter the mixture and wash the filter cake with purified water until it is neutral. Then, dry the filter cake and transfer it to a dryer at 55℃. Vacuum dry the filter cake to a constant weight to obtain dechlorinated PVC.

[0061] A2. Preparation of activated PVC

[0062] Weigh out 800g of dechlorinated PVC, 3200mL of formic acid, and 16g of 95wt% sulfuric acid and add them to a 10L reactor. Mix the mixture and raise the reactor temperature to 70℃. Add 1280mL of 30wt% hydrogen peroxide solution dropwise to the reactor. After the addition is complete, keep the reactor at this temperature for 60min. Then, lower the reactor temperature to room temperature, filter the mixture, wash the filter cake with purified water until neutral, and then dry it. Transfer the filter cake to a drying oven at 55℃ and vacuum dry it to constant weight to obtain activated PVC.

[0063] Example 4

[0064] This embodiment provides a method for preparing ammoniated loaded kaolin for insulating and interference-resistant polyvinyl chloride cable materials, including the following steps:

[0065] B1. Preparation of activated kaolin

[0066] Mix 2 mol / L formic acid, sodium dodecyl sulfate and 20 wt% hydrogen peroxide in a ratio of 10 mL: 0.3 g: 2 mL to obtain an activation solution for later use.

[0067] Weigh 1000g of calcined kaolin and 5000mL of activation solution and add them to a 5L reactor. Stir the reactor at 75℃ for 4 hours. After the reactor temperature is reduced to room temperature, filter the mixture. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 70℃ and dry it to constant weight to obtain activated kaolin.

[0068] B2. Preparation of Loaded Kaolin

[0069] Weigh 500g of ferric chloride and 5000mL of ethylene glycol and add them to a 10L beaker. Stir until the system is dissolved. Add 900g of activated kaolin to the beaker and sonicate for 60min. Transfer the sonicated solution to a 10L reactor and stir. Add 100g of trisodium citrate and 130g of ammonium acetate to the reactor and stir at room temperature for 40min. Pass a heat exchange medium at 200℃ through the jacket of the reactor and keep it at that temperature for 3h. After the temperature of the reaction system drops to room temperature, add 4L of 50vol% ethanol aqueous solution to the reaction system and stir for 30min. Filter the mixture and wash the filter cake three times with purified water and ethanol. Dry the filter cake and transfer it to a drying oven at 70℃. Dry the mixture to constant weight to obtain loaded kaolin.

[0070] B3. Preparation of ammoniated supported kaolin

[0071] Weigh out 700g of loaded kaolin, 4000mL of anhydrous ethanol and 300g of 4-aminobutyltriethoxysilane and add them to a 10L reactor. Stir the reactor and raise the temperature to 50℃. Add 1000mL of 2mol / L sodium hydroxide solution to the reactor and keep it at this temperature for 4h. Then lower the temperature of the reactor to room temperature, filter the mixture, wash the filter cake with purified water until neutral, and then dry it. Transfer the filter cake to a drying oven at 65℃ and vacuum dry it to constant weight to obtain aminated loaded kaolin.

[0072] Example 5

[0073] This embodiment provides a method for preparing ammoniated loaded kaolin for insulating and interference-resistant polyvinyl chloride cable materials, including the following steps:

[0074] B1. Preparation of activated kaolin

[0075] Mix 2.5 mol / L formic acid, sodium dodecyl sulfate, and 25 wt% hydrogen peroxide in a ratio of 10 mL: 0.3 g: 2 mL to obtain an activation solution for later use.

[0076] Weigh 1000g of calcined kaolin and 5000mL of activation solution and add them to a 5L reactor. Stir the reactor at 80℃ for 5 hours. After the reactor temperature is reduced to room temperature, filter the mixture. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 75℃ and dry it to constant weight to obtain activated kaolin.

[0077] B2. Preparation of Loaded Kaolin

[0078] Weigh 500g of ferric chloride and 5000mL of ethylene glycol and add them to a 10L beaker. Stir until the system is dissolved. Add 900g of activated kaolin to the beaker and sonicate for 70min. Transfer the sonicated solution to a 10L reactor and stir. Add 100g of trisodium citrate and 130g of ammonium acetate to the reactor and stir at room temperature for 50min. Pass a heat exchange medium at 200℃ through the jacket of the reactor and keep it at that temperature for 3.5h. After the temperature of the reaction system drops to room temperature, add 4L of 50vol% ethanol aqueous solution to the reaction system and stir for 40min. Filter the mixture and wash the filter cake three times with purified water and ethanol. Dry the filter cake and transfer it to a drying oven at 75℃. Dry the mixture to constant weight to obtain loaded kaolin.

[0079] B3. Preparation of ammoniated supported kaolin

[0080] Weigh out 700g of loaded kaolin, 4000mL of anhydrous ethanol and 300g of 4-aminobutyltriethoxysilane and add them to a 10L reactor. Stir the reactor and raise the temperature to 55℃. Add 1000mL of 2.5mol / L sodium hydroxide solution to the reactor and keep it at this temperature for 4.5h. Then lower the temperature of the reactor to room temperature, filter the mixture, wash the filter cake with purified water until neutral, and then dry it. Transfer the filter cake to a drying oven at 70℃ and vacuum dry it to constant weight to obtain aminated loaded kaolin.

[0081] Example 6

[0082] This embodiment provides a method for preparing ammoniated loaded kaolin for insulating and interference-resistant polyvinyl chloride cable materials, including the following steps:

[0083] B1. Preparation of activated kaolin

[0084] Mix 3 mol / L formic acid, sodium dodecyl sulfate and 30 wt% hydrogen peroxide in a ratio of 10 mL: 0.3 g: 2 mL to obtain an activation solution for later use.

[0085] Weigh 1000g of calcined kaolin and 5000mL of activation solution and add them to a 5L reactor. Stir the reactor at 85℃ for 6 hours. After the reactor temperature is reduced to room temperature, filter the mixture. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 80℃ and dry it to constant weight to obtain activated kaolin.

[0086] B2. Preparation of Loaded Kaolin

[0087] Weigh 500g of ferric chloride and 5000mL of ethylene glycol and add them to a 10L beaker. Stir until the system is dissolved. Add 900g of activated kaolin to the beaker and sonicate for 80min. Transfer the sonicated solution to a 10L reactor and stir. Add 100g of trisodium citrate and 130g of ammonium acetate to the reactor and stir at room temperature for 60min. Pass a heat exchange medium at 200℃ through the jacket of the reactor and keep it at that temperature for 4h. After the temperature of the reaction system drops to room temperature, add 4L of 50vol% ethanol aqueous solution to the reaction system and stir for 50min. Filter the mixture and wash the filter cake three times with purified water and ethanol. Dry the filter cake and transfer it to a drying oven at 80℃. Dry the cake to constant weight to obtain loaded kaolin.

[0088] B3. Preparation of ammoniated supported kaolin

[0089] Weigh out 700g of loaded kaolin, 4000mL of anhydrous ethanol and 300g of 4-aminobutyltriethoxysilane and add them to a 10L reactor. Stir the reactor and raise the temperature to 60℃. Add 1000mL of 3mol / L sodium hydroxide solution to the reactor and keep it at this temperature for 5h. Then lower the temperature of the reactor to room temperature, filter the mixture, wash the filter cake with purified water until neutral, and then dry it. Transfer the filter cake to a drying oven at 75℃ and vacuum dry it to constant weight to obtain aminated loaded kaolin.

[0090] Example 7

[0091] This embodiment provides a method for preparing an insulating and interference-resistant polyvinyl chloride cable material, including the following steps:

[0092] S1. Preparation of silicon-based reinforcing agents

[0093] Azobisisobutyronitrile and toluene were mixed evenly at a ratio of 1g:15mL to obtain an initiator solution for later use.

[0094] Weigh out 210g of vinyl silicone oil, 90g of methyl methacrylate, 60g of isooctyl acrylate, 60g of 1,2-epoxy-7-octene, and 1500mL of toluene, and add them to a 5L reactor under nitrogen protection. Stir the mixture and raise the reactor temperature to 70℃. Add 150mL of initiator solution dropwise to the reactor and maintain the temperature for 6 hours. Keep the reactor at 70℃ and remove low-boiling-point substances under reduced pressure to obtain the silicon-based reinforcing agent.

[0095] S2, Preparation of Epoxidized Retardant Fuel

[0096] Antimony trioxide, zinc stannate, ammonium octamolate, and graphene oxide were mixed evenly in a weight ratio of 5:3:2:3 to obtain a flame arrester for later use.

[0097] Weigh 300g of epoxy resin and 3000mL of anhydrous ethanol and add them to a 10L reactor. Stir and mix. Raise the reactor temperature to 70℃ and keep stirring until the system is dissolved. Add 900g of flame retardant to the reactor and keep stirring for 60min. Lower the reactor temperature to room temperature and add 5L of purified water. Keep stirring for 20min and lower the reactor temperature to room temperature. Filter the mixture. Wash the filter cake three times with purified water and dry it. Transfer the filter cake to a drying oven at 60℃ and vacuum dry it to constant weight to obtain the epoxy flame retardant.

[0098] S3, Preparation of polyvinyl chloride cable material

[0099] Dioctyl phthalate, sodium metal stearate, antioxidant 1010 and chrome yellow were mixed evenly in a weight ratio of 5:3:2:1:2 to obtain an auxiliary additive for later use.

[0100] Weigh out the following by weight: 55 parts of PVC, 20 parts of activated PVC prepared in Example 1, 12 parts of silicon-based reinforcing agent, 13 parts of ammoniated loaded kaolin prepared in Example 4, 8 parts of epoxidized flame retardant, and 6 parts of auxiliary additives, and add them to a twin-screw extruder. The temperatures of the five temperature zones of the twin-screw extruder from the feed end to the discharge end are 180°C, 185°C, 190°C, 190°C, and 195°C, respectively. After melt extrusion by the twin-screw extruder, the material is granulated to obtain polyvinyl chloride cable material.

[0101] Example 8

[0102] This embodiment provides a method for preparing an insulating and interference-resistant polyvinyl chloride cable material, including the following steps:

[0103] S1. Preparation of silicon-based reinforcing agents

[0104] Azobisisobutyronitrile and toluene were mixed evenly at a ratio of 1g:15mL to obtain an initiator solution for later use.

[0105] Weigh out 210g of vinyl silicone oil, 90g of methyl methacrylate, 60g of isooctyl acrylate, 60g of 1,2-epoxy-7-octene, and 1500mL of toluene, and add them to a 5L reactor under nitrogen protection. Stir the mixture and raise the reactor temperature to 75℃. Add 150mL of initiator solution dropwise to the reactor and maintain the temperature for 7 hours. Keep the reactor at 75℃ and remove low-boiling-point substances under reduced pressure to obtain the silicon-based reinforcing agent.

[0106] S2, Preparation of Epoxidized Retardant Fuel

[0107] Antimony trioxide, zinc stannate, ammonium octamolate, and graphene oxide were mixed evenly in a weight ratio of 5:3:2:3 to obtain a flame arrester for later use.

[0108] Weigh 300g of epoxy resin and 3000mL of anhydrous ethanol and add them to a 10L reactor. Stir and mix. Raise the reactor temperature to 75℃ and keep stirring until the system is dissolved. Add 900g of flame retardant to the reactor and keep stirring for 70min. Lower the reactor temperature to room temperature and add 5L of purified water. Keep stirring for 25min and lower the reactor temperature to room temperature. Filter the mixture. Wash the filter cake three times with purified water and dry it. Transfer the filter cake to a drying oven at 65℃ and vacuum dry it to constant weight to obtain the epoxy flame retardant.

[0109] S3, Preparation of polyvinyl chloride cable material

[0110] Diisooctyl phthalate, zinc stearate, antioxidant 1010 and molybdenum chromium red were mixed evenly in a weight ratio of 5:3:2:1:2 to obtain an auxiliary additive for later use.

[0111] Weigh out the following by weight: 60 parts of PVC, 25 parts of activated PVC prepared in Example 2, 14 parts of silicon-based reinforcing agent, 15 parts of ammoniated loaded kaolin prepared in Example 4, 9 parts of epoxidized flame retardant, and 7 parts of auxiliary additives, and add them to a twin-screw extruder. The temperatures of the five temperature zones of the twin-screw extruder from the feed end to the discharge end are 180°C, 185°C, 190°C, 190°C, and 195°C, respectively. After melt extrusion in the twin-screw extruder, the material is granulated to obtain polyvinyl chloride cable material.

[0112] Example 9

[0113] This embodiment provides a method for preparing an insulating and interference-resistant polyvinyl chloride cable material, including the following steps:

[0114] S1. Preparation of silicon-based reinforcing agents

[0115] Azobisisobutyronitrile and toluene were mixed evenly at a ratio of 1g:15mL to obtain an initiator solution for later use.

[0116] Weigh out 210g of vinyl silicone oil, 90g of methyl methacrylate, 60g of isooctyl acrylate, 60g of 1,2-epoxy-7-octene, and 1500mL of toluene, and add them to a 5L reactor under nitrogen protection. Stir the mixture and raise the reactor temperature to 80℃. Add 150mL of initiator solution dropwise to the reactor and maintain the temperature for 8 hours. Keep the reactor at 80℃ and remove low-boiling-point substances under reduced pressure to obtain the silicon-based reinforcing agent.

[0117] S2, Preparation of Epoxidized Retardant Fuel

[0118] Antimony trioxide, zinc stannate, ammonium octamolate, and graphene oxide were mixed evenly in a weight ratio of 5:3:2:3 to obtain a flame arrester for later use.

[0119] Weigh 300g of epoxy resin and 3000mL of anhydrous ethanol and add them to a 10L reactor. Stir and mix. Raise the reactor temperature to 80℃ and keep stirring until the system is dissolved. Add 900g of flame retardant to the reactor and keep stirring for 80min. Lower the reactor temperature to room temperature and add 5L of purified water. Keep stirring for 30min and lower the reactor temperature to room temperature. Filter the mixture. Wash the filter cake three times with purified water and dry it. Transfer the filter cake to a drying oven at 70℃ and vacuum dry it to constant weight to obtain the epoxy flame retardant.

[0120] S3, Preparation of polyvinyl chloride cable material

[0121] Diisopropyl phthalate, magnesium stearate, antioxidant 1010 and cobalt blue were mixed evenly in a weight ratio of 5:3:2:1:2 to obtain an auxiliary additive for later use.

[0122] Weigh out the following components by weight: 65 parts of PVC, 30 parts of activated PVC prepared in Example 3, 16 parts of silicon-based reinforcing agent, 17 parts of ammoniated loaded kaolin prepared in Example 6, 10 parts of epoxidized flame retardant, and 8 parts of auxiliary additives. Add these components to a twin-screw extruder. The temperatures of the five temperature zones in the twin-screw extruder from the feed end to the discharge end are 180°C, 185°C, 190°C, 190°C, and 195°C, respectively. After melt extrusion in the twin-screw extruder, the material is pelletized to obtain polyvinyl chloride cable material.

[0123] Comparative Example 1

[0124] The difference between this comparative example and Example 9 is that the epoxidized fuel in step S3 is replaced with the flame retardant fuel in step S2.

[0125] Comparative Example 2

[0126] The difference between this comparative example and Example 9 is that graphene oxide was not added to the flame retardant in step S2.

[0127] Comparative Example 3

[0128] The difference between this comparative example and Example 9 is that activated PVC was not added in step S3.

[0129] Comparative Example 4

[0130] The difference between this comparative example and Example 9 is that the ammonified loaded kaolin used is replaced by an equal amount of loaded kaolin.

[0131] Performance testing:

[0132] The flame retardancy rating, tensile strength, elongation at break and volume resistivity at 20°C of the polyvinyl chloride cable material samples prepared in Examples 7-9 and Comparative Examples 1-4 were determined in accordance with the standard T / SHPTA 016-2021 "Flame-retardant thermoplastic elastomer cable materials".

[0133] The shielding effectiveness of the polyvinyl chloride cable material samples prepared in Examples 7-9 and Comparative Examples 1-4 was determined in accordance with the standard GB / T 30142-2013 "Method for Measurement of Shielding Effectiveness of Planar Electromagnetic Shielding Materials".

[0134] The specific test results are shown in Table 1 below.

[0135] Table 1 - Performance Test Data of Samples

[0136]

[0137] Data Analysis:

[0138] Comparative analysis of the data in Table 1 shows that the polyvinyl chloride cable material prepared by this invention has a tensile strength of 28.9 MPa, an elongation at break of 354.5%, a flame retardant rating of V-0, and a volume resistivity of 8.73 × 10⁻⁶. 8 With a shielding effectiveness of 22.4 dB and all performance parameters superior to the comparative example, this invention demonstrates that by using activated PVC as a compatibilizer to promote the mixing of silicon-based reinforcing agents and PVC, and then modifying the flame retardant with epoxy resin and optimizing the composition of the flame retardant, it not only effectively improves the insulation and tensile properties of PVC cable material, but also enhances its flame retardant and electromagnetic interference resistance properties.

[0139] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0140] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0141] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A polyvinyl chloride (PVC) cable material for insulation and interference resistance, characterized in that, It includes the following components by weight: 55-65 parts PVC, 20-30 parts activated PVC, 12-16 parts silicone-based reinforcing agent, 13-17 parts ammoniated loaded kaolin, 8-10 parts epoxidized flame retardant and 6-8 parts auxiliary additives. The activated PVC is obtained by the following steps: A1. Mix polyvinyl chloride powder, sodium hydroxide and purified water. After sealing the reaction system, raise the temperature to 200-220℃ and the pressure to 2.8-3.2MPa. Keep it at this temperature for 2-3 hours. Then, perform post-treatment to obtain dechlorinated PVC. A2. Stir and mix dechlorinated PVC, formic acid and catalyst, raise the temperature of the reaction system to 60-70℃, add hydrogen peroxide solution dropwise to the reaction system, and after the addition is complete, keep the reaction at the temperature for 40-60 minutes, and then perform post-treatment to obtain activated PVC. The ammonified loaded kaolin is obtained by the following steps: B1. Stir and mix calcined kaolin and activation liquid, keep the reaction system at 75-85℃ for 4-6 hours, and then perform post-treatment to obtain activated kaolin. B2. Mix ferric chloride and ethylene glycol until the system is dissolved. Add activated kaolin to the reaction system and ultrasonically disperse for 60-80 min. While stirring, add trisodium citrate and ammonium acetate to the reaction system and stir at room temperature for 40-60 min. Place the reaction system in a heat exchange medium at 200℃ and keep it at that temperature for 3-4 h. After post-treatment, load kaolin is obtained. The ratio of ferric chloride, ethylene glycol, activated kaolin, trisodium citrate and ammonium acetate is 5g:50mL:9g:1g:1.3g. B3. Mix the loaded kaolin, anhydrous ethanol and 4-aminobutyltriethoxysilane, raise the temperature of the reaction system to 50-60℃, add 2-3 mol / L sodium hydroxide solution to the reaction system, keep the reaction at the temperature for 4-5 h, and then perform post-treatment to obtain aminated loaded kaolin. The preparation method of the epoxy flame retardant is as follows: epoxy resin and anhydrous ethanol are stirred and mixed, the temperature of the reaction system is raised to 70-80℃, and the system is kept warm and stirred until dissolved. The flame retardant is added to the reaction system, and the system is kept warm and stirred for 60-80 minutes. The temperature of the reaction system is lowered to room temperature, purified water is added to the reaction system, and the system is kept warm and stirred for 20-30 minutes. After post-treatment, the epoxy flame retardant is obtained. The flame retardant is composed of antimony trioxide, zinc stannate, ammonium octamolate, and graphene oxide in a weight ratio of 5:3:2:

3. The ratio of epoxy resin, anhydrous ethanol, and flame retardant is 1g:10mL:3g. The preparation method of the silicon-based reinforcing agent is as follows: In an inert atmosphere, vinyl silicone oil, methyl methacrylate, isooctyl acrylate, 1,2-epoxy-7-octene and toluene are mixed, the temperature of the reaction system is raised to 70-80℃, an initiator solution is added dropwise to the reaction system, the reaction is kept at the temperature for 6-8 hours, and then post-processed to obtain the silicon-based reinforcing agent.

2. The polyvinyl chloride cable material for insulation and interference resistance according to claim 1, characterized in that, In step A1, the ratio of polyvinyl chloride powder, sodium hydroxide, and purified water is 8g:1.1-1.3g:30mL; in step A2, the ratio of dechlorinated PVC, formic acid, catalyst, and hydrogen peroxide solution is 5g:20mL:0.1g:8mL, the catalyst is 90-95wt% sulfuric acid, and the mass concentration of the hydrogen peroxide solution is 30%.

3. The polyvinyl chloride cable material for insulation and interference resistance according to claim 1, characterized in that, The ratio of the amount of vinyl silicone oil, methyl methacrylate, isooctyl acrylate, 1,2-epoxy-7-octene, toluene, and initiator solution is 7g:3g:2g:2g:50mL:5mL, and the initiator solution is composed of azobisisobutyronitrile and toluene at a ratio of 1g:15mL.

4. The polyvinyl chloride cable material for insulation and interference resistance according to claim 1, characterized in that, In step B1, the ratio of calcined kaolin to activation solution is 1g:5mL, and the activation solution is composed of 2-3mol / L formic acid, sodium dodecyl sulfate, and 20-30wt% hydrogen peroxide in a ratio of 10mL:0.3g:2mL; in step B3, the ratio of loaded kaolin, anhydrous ethanol, 4-aminobutyltriethoxysilane, and 2-3mol / L sodium hydroxide solution is 7g:40mL:3g:10mL.

5. A method for preparing an insulating and interference-resistant polyvinyl chloride cable material as described in any one of claims 1-4, characterized in that, The preparation method of the insulating and anti-interference polyvinyl chloride cable material is as follows: PVC, activated PVC, silicon-based reinforcing agent, ammonified loaded kaolin, epoxidized flame retardant and auxiliary additives are mixed, melt-extruded by a twin-screw extruder and then pelletized to obtain polyvinyl chloride cable material.

6. The method for preparing an insulating and interference-resistant polyvinyl chloride cable material according to claim 5, characterized in that, The auxiliary additives are composed of plasticizer, dispersant, antioxidant and colorant in a weight ratio of 5:3:2:

1. The plasticizer is phthalate, the dispersant is metal stearate, the antioxidant is antioxidant 1010, and the colorant is any one or more of chrome yellow, molybdenum chrome red, cobalt blue, chrome green and carbon black. The temperatures of the five temperature zones of the twin-screw extruder from the feed end to the discharge end are 180℃, 185℃, 190℃, 190℃ and 195℃ respectively.

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