Insulated anti-interference polyvinyl chloride cable material and preparation method thereof

Abstract

The invention discloses an insulated anti-interference polyvinyl chloride cable material and a preparation method thereof, and belongs to the technical field of insulated cable material processing. The insulating anti-interference polyvinyl chloride cable material is used for solving the technical problem that the flame retardant property, the insulating property and the anti-electromagnetic interference property of a PVC cable material in the prior art need to be further improved. Comprising the following components in parts by weight: 55-65 parts of PVC, 20-30 parts of activated PVC, 12-16 parts of a silicon-based reinforcing agent, 13-17 parts of ammoniated supported kaolin, 8-10 parts of an epoxidized flame retardant and 6-8 parts of an auxiliary additive. Activated PVC is used as a compatilizer, mixing of a silicon-based reinforcing agent and PVC is promoted, the flame-retardant material is modified with epoxy resin, and the composition of the flame-retardant material is optimized, so that the insulation and tensile properties of the polyvinyl chloride cable material are effectively improved, and the flame-retardant and anti-electromagnetic interference properties of the polyvinyl chloride cable material are also improved.

Description

Technical Field

[0001] The present invention relates to the technical field of insulating cable material processing, and particularly relates to a polyvinyl chloride cable material with insulation and anti-interference properties and a preparation method thereof. Background Art

[0002] Due to its excellent mechanical properties, chemical corrosion resistance and cost advantages, polyvinyl chloride (PVC) cable materials are widely used in power transmission, communication and industrial equipment. However, traditional PVC cables are vulnerable to interference in high-frequency electromagnetic fields or complex electromagnetic environments, resulting in signal transmission distortion. Although some studies have improved anti-interference performance by adding metal shielding layers (such as tinned copper wires), such structural designs are complex, costly, and prone to a decrease in shielding efficiency due to mechanical deformation. In addition, the PVC matrix has a high dielectric loss, and its insulation performance deteriorates significantly under high-temperature or high-frequency conditions, making it difficult to meet the requirements of emerging fields such as 5G communication and new energy vehicles.

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

[0004] The cable shielding material of the prior art reduces its resistivity by introducing a large amount of conductive materials into the matrix resin, making it have good electromagnetic shielding performance. This modification method results in a reduction in the insulation performance of the cable material, and it is difficult to improve its anti-electromagnetic shielding performance while ensuring the insulation performance of the material. In the prior art, the magnetic loss mechanism of magnetic materials can effectively absorb electromagnetic wave energy. However, magnetic materials mainly composed of metals also have good electrical conductivity, and extensive use will also lead to an increase in the insulation performance of the cable material. Moreover, the anti-electromagnetic interference performance of a single magnetic material needs to be further improved. In addition, the flame retardancy rating of PVC is between B1 and B2, with a low burning rate and flame propagation rate. When applied in cables, its flame retardancy needs to be further improved.

[0005] In view of the technical deficiencies in this regard, a solution is proposed herein. Summary of the Invention

[0006] The purpose of the present invention is to provide a polyvinyl chloride cable material with insulation and anti-interference properties and a preparation method thereof, which are used to solve the technical problems that the flame retardancy, insulation performance and anti-electromagnetic interference performance of PVC cable materials in the prior art need to be further improved.

[0007] The object of the present invention can be achieved by the following technical solutions:

[0008] An insulating and anti-interference PVC cable material, comprising the following components by weight: 55-65 parts of PVC, 20-30 parts of activated PVC, 12-16 parts of a silicon-based reinforcing agent, 13-17 parts of ammoniated supported kaolin, 8-10 parts of an epoxy flame retardant, and 6-8 parts of an auxiliary additive;

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

[0010] A1. Stir and mix polyvinyl chloride powder, sodium hydroxide, and purified water. After the reaction system is sealed, the temperature is raised to 200-220 °C, the pressure is raised to 2.8-3.2 MPa, and heat preservation treatment is carried out for 2-3 h, followed by post-treatment to obtain dechlorinated PVC;

[0011] A2. Stir and mix dechlorinated PVC, formic acid, and a catalyst. Raise the temperature of the reaction system to 60-70 °C, and dropwise add hydrogen peroxide solution to the reaction system. After dropping, carry out heat preservation reaction for 40-60 min, followed by post-treatment to obtain activated PVC.

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

[0013] During the reaction process, 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 an E2 elimination reaction occurs, removing HCl while forming a double bond modification on the polyvinyl chloride molecular chain to prepare dechlorinated PVC;

[0014] Sulfuric acid acts as a strong acid catalyst to catalyze the reaction of formic acid and hydrogen peroxide under acidic conditions to generate performic acid. Performic acid acts as an electrophilic reagent, and its oxygen atom attacks the double bond in dechlorinated PVC to form an epoxy structure, thereby preparing activated PVC.

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

[0016] Further, in step A2, the dosage ratio of the dechlorinated PVC, formic acid, catalyst and hydrogen peroxide solution is 5 g: 20 mL: 0.1 g: 8 mL. The catalyst is 90 - 95 wt% 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 reduced to room temperature, and suction filtration is carried out. The filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to an oven at 50 - 55 °C and vacuum dried to constant weight to obtain activated PVC.

[0017] Further, the preparation method of the silicon-based reinforcing agent is as follows: in an inert atmosphere environment, 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 °C, and an initiator solution is added dropwise to the reaction system, and the reaction is carried out under heat preservation for 6 - 8 h, followed by post-treatment to obtain the silicon-based reinforcing agent.

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

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

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

[0021] Further, the ammoniated supported kaolin is processed by the following steps:

[0022] B1. Stir and mix the calcined kaolin and the activation solution, and keep the temperature of the reaction system at 75 - 85 °C for 4 - 6 h of heat preservation treatment, followed by post-treatment to obtain activated kaolin;

[0023] B2. Stir and dissolve ferric chloride and ethylene glycol until the system is dissolved. Add the activated kaolin to the reaction system and ultrasonically disperse for 60 - 80 min. Under stirring, add trisodium citrate and ammonium acetate to the reaction system, and stir at room temperature for 40 - 60 min, followed by post-treatment to obtain supported kaolin;

[0024] B3. Stir and mix the supported kaolin, absolute ethanol, and 4-aminobutyltriethoxysilane. Raise the temperature of the reaction system to 50 - 60 °C. Add a 2 - 3 mol / L sodium hydroxide solution to the reaction system, keep the temperature for reaction for 4 - 5 h, and perform post-treatment to obtain aminated supported kaolin.

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

[0026] During the reaction process, by selecting the fluffy and porous calcined kaolin as the raw material, activating it to improve its reaction activity, activated kaolin is prepared. Ferric chloride dissolves in ethylene glycol to form Fe 3+ ions, and Fe 3+ 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 reduces part of the Fe 3+ to Fe 2+ in a high-temperature environment, forming magnetic magnetite nanoparticles loaded on the surface of kaolin. During the reaction process, sodium citrate and ammonium acetate act as stabilizers to prevent nanoparticle aggregation, and supported kaolin loaded with iron tetroxide is prepared. 4-aminobutyltriethoxysilane hydrolyzes in an alkaline environment to form silanols, and condensation reactions occur between silanols or between silanols and the active sites on the upper surface of the supported kaolin particles to form Si - O - Si bonding, forming a polysiloxane coating and amino modification on the supported kaolin particles, and aminated supported kaolin is prepared.

[0027] Furthermore, in step B1, the dosage ratio of the calcined kaolin to the activating solution is 1 g:5 mL. The activating solution is composed of 2 - 3 mol / L formic acid, sodium dodecyl sulfate, and 20 - 30 wt% hydrogen peroxide in a dosage ratio of 10 mL:0.3 g:2 mL. The post-treatment includes: after the reaction is completed, lower the temperature of the reaction system to room temperature, perform suction filtration, wash the filter cake with purified water until neutral and then drain it, transfer the filter cake to an oven at 70 - 80 °C, and dry it to a constant weight to obtain activated kaolin.

[0028] Furthermore, in step B2, the dosage ratio of ferric chloride, ethylene glycol, activated kaolin, sodium citrate, and ammonium acetate is 5 g:50 mL:9 g:1 g:1.3 g. The post-treatment includes: after the reaction is completed, place the reaction system in a heat exchange medium at 200 °C, keep the temperature for 3 - 4 h, wait for the temperature of the reaction system to drop to room temperature, add a 50 vol% ethanol aqueous solution to the reaction system, stir and disperse for 30 - 50 min, perform suction filtration, wash the filter cake with purified water and ethanol three times and then drain it, transfer the filter cake to an oven at 70 - 80 °C, and dry it to a constant weight to obtain supported kaolin.

[0029] Further, in step B3, the dosage ratio of the loaded kaolin, absolute 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 completed, the temperature of the reaction system is reduced to room temperature, followed by suction filtration. The filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a drying oven at 65 - 75 °C and vacuum dried to constant weight to obtain the ammoniated loaded kaolin.

[0030] Further, the preparation method of the epoxy flame retardant is as follows: epoxy resin and absolute ethanol are stirred and mixed, and the temperature of the reaction system is raised to 70 - 80 °C. After holding and stirring until the system is dissolved, a flame retardant is added to the reaction system, and the mixture is held and stirred for 60 - 80 min. Then the temperature of the reaction system is reduced to room temperature, purified water is added to the reaction system, and the mixture is held and stirred for 20 - 30 min. After post-treatment, the epoxy flame retardant is obtained.

[0031] Further, the dosage ratio of the epoxy resin, xylene and flame retardant is 1 g:10 mL:3 g. The flame retardant is composed of antimony trioxide, zinc stannate, ammonium octamolybdate and graphene oxide in a weight ratio of 5:3:2:3. The post-treatment includes: after the reaction is completed, the temperature of the reaction system is reduced to room temperature, followed by suction filtration. The filter cake is washed 3 times with purified water and then dried by suction. The filter cake is transferred to a drying oven at 60 - 70 °C and vacuum dried to constant weight to obtain the epoxy flame retardant.

[0032] The synthesis reaction mechanism of the epoxy flame retardant is as follows:

[0033] During the reaction process, the epoxy resin dissolves in absolute ethanol to form a homogeneous solution. By heating treatment, the molecular chains of the epoxy resin are promoted to stretch. The surface of the flame retardant particles combines with the molecular chains of the epoxy resin through physical adsorption to form a uniformly dispersed composite material. Adding purified water reduces the solubility of the epoxy resin, causing the composite material to precipitate from the solution to form a solid precipitate, and the epoxy flame retardant is prepared.

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

[0035] Further, the auxiliary additive is composed of a plasticizer, a dispersant, an antioxidant, and a colorant in a weight ratio of 5:3:2:1:2. The plasticizer is phthalate, the dispersant is a metal salt of stearic acid, the antioxidant is antioxidant 1010, and the colorant is any one or more of chrome yellow, molybdate 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 in sequence.

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

[0037] 1. For the insulating and anti-interference PVC cable material of the present invention, by introducing epoxy groups into activated PVC, the polarity of the PVC chain is enhanced, so that activated PVC is used as a compatibilizer to promote the mixing of the silicon-based reinforcing agent and PVC. By introducing polar ester groups onto the polysiloxane molecule with methyl methacrylate and isooctyl acrylate, the compatibility between the silicon-based reinforcing agent and PVC is further enhanced, thereby improving the mechanical strength of the PVC cable material. The amino groups modified on the surface of ammoniated supported kaolin undergo ring-opening condensation with the epoxy groups on the molecules of activated PVC or the silicon-based reinforcing agent at high temperature to form covalent bond bonding, 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 combination" structure through physical entanglement or chemical crosslinking, improving the tensile strength and elongation at break of the PVC cable compound.

[0038] 2. For the insulating and anti-interference PVC cable material of the present invention, the flame retardant is modified with epoxy resin, and epoxy resin is coated on the outside of the flame retardant. The epoxy groups on the epoxy resin molecule are combined with the polar groups of the activated PVC molecular chain through hydrogen bonds or covalent bonds to ensure the uniform dispersion of the flame retardant. In the flame retardant, antimony trioxide reacts with HCl released by the thermal decomposition of PVC to generate a gas-phase free radical scavenger SbCl 3 , by quenching the active free radicals in the combustion chain reaction, inhibiting the flame propagation. The decomposition products of ammonium octamolybdate and zinc stannate at high temperature can catalyze the formation of a carbon layer while diluting the concentration of combustible gases, inhibiting the decomposition of the matrix. The lamellar structure of graphene oxide migrates to the surface of the material during combustion to form a continuous physical barrier, blocking the diffusion of combustible gases. Moreover, the oxygen-containing functional groups of graphene oxide promote the dehydrogenation crosslinking of PVC, enhancing the denseness of the carbon layer and further improving the flame retardant performance of the cable compound.

[0039] 3. The insulating and anti-interference polyvinyl chloride cable material of the present invention enhances the interfacial bonding force between kaolin and the PVC matrix by loading magnetite particles on kaolin and modifying a large number of amino groups on the outer surface of kaolin particles, reducing filler agglomeration and ensuring uniform dispersion. The strong magnetism of the magnetite particles can effectively absorb electromagnetic wave energy through eddy current loss and hysteresis loss, enhancing the electromagnetic shielding effect. Moreover, the kaolin lamellae and Fe 3 O 4 nanoparticles form a "lamella-particle" composite structure, enhancing the reflection and scattering of electromagnetic waves and prolonging the propagation path of electromagnetic waves. 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 manners

[0040] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0041] In this application, the polyvinyl chloride powder is selected from Ningbo Senhong Plastic 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., the viscosity is 5000 cs, and the vinyl content is 3%;

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

[0044] In this application, the calcined kaolin is selected from LingShou YongZhuo New Materials Technology Co., Ltd., and the particle size is 200 mesh.

[0045] Example 1

[0046] This example provides a preparation method of activated PVC for an insulating and anti-interference polyvinyl chloride cable material, including the following steps:

[0047] A1. Preparation of dechlorinated PVC

[0048] Weigh: 800 g of polyvinyl chloride powder, 110 g of sodium hydroxide and 3000 mL of purified water, add them to a high-pressure reaction kettle and stir. After the high-pressure reaction kettle is sealed, the temperature of the heat exchange medium in the jacket of the high-pressure reaction kettle is raised to 200 °C, the pressure is raised to 2.8 MPa, and heat preservation treatment is carried out for 2 h. Then the temperature of the high-pressure reaction kettle is lowered to room temperature, the pressure is lowered to atmospheric pressure, and filtration is carried out. The filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a dryer at 50 °C and vacuum dried to constant weight to obtain dechlorinated PVC.

[0049] A2. Preparation of Activated PVC

[0050] Weigh and add: 800 g of dechlorinated PVC, 3200 mL of formic acid, and 16 g of 90 wt% sulfuric acid into a 10 L reaction kettle and mix. Raise the temperature of the reaction kettle to 60 °C, and add dropwise 1280 mL of 30 wt% hydrogen peroxide solution into the reaction kettle. After the addition is completed, keep the temperature for reaction for 40 min. Lower the temperature of the reaction kettle to room temperature, carry out suction filtration, wash the filter cake with purified water until it is neutral and then drain it. Transfer the filter cake to a drying oven at 50 °C and dry it under vacuum until it reaches a constant weight to obtain activated PVC.

[0051] Example 2

[0052] This example provides a preparation method of activated PVC for an insulating and anti-interference polyvinyl chloride cable material, including the following steps:

[0053] A1. Preparation of Dechlorinated PVC

[0054] Weigh and add: 800 g of polyvinyl chloride powder, 120 g of sodium hydroxide, and 3000 mL of purified water into a high-pressure reaction kettle and stir. After the high-pressure reaction kettle is sealed, raise the temperature of the heat exchange medium in the jacket of the high-pressure reaction kettle to 210 °C and the pressure to 3.0 MPa, and keep the temperature for 2.5 h. Lower the temperature of the high-pressure reaction kettle to room temperature and the pressure to atmospheric pressure, carry out suction filtration, wash the filter cake with purified water until it is neutral and then drain it. Transfer the filter cake to a dryer at 53 °C and dry it under vacuum until it reaches a constant weight to obtain dechlorinated PVC.

[0055] A2. Preparation of Activated PVC

[0056] Weigh and add: 800 g of dechlorinated PVC, 3200 mL of formic acid, and 16 g of 93 wt% sulfuric acid into a 10 L reaction kettle and mix. Raise the temperature of the reaction kettle to 65 °C, and add dropwise 1280 mL of 30 wt% hydrogen peroxide solution into the reaction kettle. After the addition is completed, keep the temperature for reaction for 50 min. Lower the temperature of the reaction kettle to room temperature, carry out suction filtration, wash the filter cake with purified water until it is neutral and then drain it. Transfer the filter cake to a drying oven at 53 °C and dry it under vacuum until it reaches a constant weight to obtain activated PVC.

[0057] Example 3

[0058] This example provides a preparation method of activated PVC for an insulating and anti-interference polyvinyl chloride cable material, including the following steps:

[0059] A1. Preparation of Dechlorinated PVC

[0060] Weigh: 800 g of polyvinyl chloride powder, 130 g of sodium hydroxide and 3000 mL of purified water are added to a high-pressure reactor and stirred. After the high-pressure reactor is sealed, the temperature of the heat exchange medium in the jacket of the high-pressure reactor is raised to 220 °C, and the pressure is raised to 3.2 MPa. After heat preservation for 3 h, the temperature of the high-pressure reactor is lowered to room temperature, and the pressure is lowered to atmospheric pressure. Then, filtration is carried out. The filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a dryer at 55 °C and vacuum dried to constant weight to obtain dechlorinated PVC.

[0061] A2. Preparation of activated PVC

[0062] Weigh: 800 g of dechlorinated PVC, 3200 mL of formic acid and 16 g of 95 wt% sulfuric acid are added to a 10 L reactor and mixed. The temperature of the reactor is raised to 70 °C, and 1280 mL of 30 wt% hydrogen peroxide solution is added dropwise to the reactor. After the addition is completed, the reaction is carried out under heat preservation for 60 min. The temperature of the reactor is lowered to room temperature, and filtration is carried out. The filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a drying oven at 55 °C and vacuum dried to constant weight to obtain activated PVC.

[0063] Example 4

[0064] This example provides a preparation method of ammonia-loaded kaolin for an insulating and anti-interference polyvinyl chloride cable material, which includes the following steps:

[0065] B1. Preparation of activated kaolin

[0066] Mix 2 mol / L formic acid, sodium dodecyl sulfate and 20 wt% hydrogen peroxide uniformly according to the dosage ratio of 10 mL: 0.3 g: 2 mL to obtain an activation solution for standby;

[0067] Weigh: 1000 g of calcined kaolin and 5000 mL of the activation solution are added to a 5 L reactor and stirred. The temperature of the reactor is 75 °C, and after heat preservation for 4 h, the temperature of the reactor is lowered to room temperature, and filtration is carried out. The filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a drying oven at 70 °C and dried to constant weight to obtain activated kaolin.

[0068] B2. Preparation of loaded kaolin

[0069] Weigh: 500 g of ferric chloride and 5000 mL of ethylene glycol are added to a 10 L beaker and stirred until the system is dissolved. 900 g of activated kaolin is added to the beaker, and ultrasonic dispersion is carried out for 60 min. The ultrasonic solution is transferred to a 10 L reactor and stirred. 100 g of trisodium citrate and 130 g of ammonium acetate are added to the reactor, and stirring is carried out at room temperature for 40 min. A heat exchange medium with a temperature of 200 °C is introduced into the jacket of the reactor, and heat preservation treatment is carried out for 3 h. After the temperature of the reaction system drops to room temperature, 4 L of 50 vol% ethanol aqueous solution is added to the reaction system, and stirring and dispersion are carried out for 30 min. Filtration is carried out, and the filter cake is washed three times with purified water and ethanol and then dried by suction. The filter cake is transferred to a drying oven at 70 °C and dried to constant weight to obtain supported kaolin.

[0070] B3. Preparation of ammoniated supported kaolin

[0071] Weigh: 700 g of supported kaolin, 4000 mL of absolute ethanol and 300 g of 4-aminobutyltriethoxysilane are added to a 10 L reactor and stirred. The temperature of the reactor is raised to 50 °C. 1000 mL of 2 mol / L sodium hydroxide solution is added to the reactor, and heat preservation reaction is carried out for 4 h. The temperature of the reactor is lowered to room temperature, filtration is carried out, and the filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a drying oven at 65 °C and vacuum dried to constant weight to obtain ammoniated supported kaolin.

[0072] Example 5

[0073] This example provides a preparation method of ammoniated supported kaolin for an insulating and anti-interference polyvinyl chloride cable material, 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 evenly according to the dosage ratio of 10 mL: 0.3 g: 2 mL to obtain an activation solution for standby;

[0076] Weigh: 1000 g of calcined kaolin and 5000 mL of the activation solution are added to a 5 L reactor and stirred. The temperature of the reactor is 80 °C, and heat preservation treatment is carried out for 5 h. The temperature of the reactor is lowered to room temperature, filtration is carried out, and the filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a drying oven at 75 °C and dried to constant weight to obtain activated kaolin.

[0077] B2. Preparation of supported kaolin

[0078] Weigh: 500 g of ferric chloride and 5000 mL of ethylene glycol are added to a 10 L beaker and stirred until the system is dissolved. 900 g of activated kaolin is added to the beaker, and ultrasonic dispersion is carried out for 70 min. The ultrasonic solution is transferred to a 10 L reactor and stirred. 100 g of trisodium citrate and 130 g of ammonium acetate are added to the reactor, and stirring is carried out at room temperature for 50 min. A heat exchange medium at 200 °C is introduced into the jacket of the reactor, and heat preservation treatment is carried out for 3.5 h. After the temperature of the reaction system drops to room temperature, 4 L of 50 vol% ethanol aqueous solution is added to the reaction system, and stirring and dispersion are carried out for 40 min. Filtration is carried out, and the filter cake is washed three times with purified water and ethanol and then dried by suction. The filter cake is transferred to a drying oven at 75 °C and dried to constant weight to obtain loaded kaolin.

[0079] B3. Preparation of ammoniated loaded kaolin

[0080] Weigh: 700 g of loaded kaolin, 4000 mL of absolute ethanol and 300 g of 4-aminobutyltriethoxysilane are added to a 10 L reactor and stirred. The temperature of the reactor is raised to 55 °C. 1000 mL of 2.5 mol / L sodium hydroxide solution is added to the reactor, and heat preservation reaction is carried out for 4.5 h. The temperature of the reactor is lowered to room temperature, filtration is carried out, and the filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a drying oven at 70 °C and vacuum dried to constant weight to obtain ammoniated loaded kaolin.

[0081] Example 6

[0082] This example provides a preparation method of ammoniated loaded kaolin for an insulating and anti-interference polyvinyl chloride cable material, including the following steps:

[0083] B1. Preparation of activated kaolin

[0084] 3 mol / L formic acid, sodium dodecyl sulfate and 30 wt% hydrogen peroxide are mixed evenly according to the dosage ratio of 10 mL: 0.3 g: 2 mL to obtain an activation solution for standby;

[0085] Weigh: 1000 g of calcined kaolin and 5000 mL of the activation solution are added to a 5 L reactor and stirred. The temperature of the reactor is 85 °C, and heat preservation treatment is carried out for 6 h. The temperature of the reactor is lowered to room temperature, filtration is carried out, and the filter cake is washed with purified water until neutral and then dried by suction. The filter cake is transferred to a drying oven at 80 °C and dried to constant weight to obtain activated kaolin.

[0086] B2. Preparation of loaded kaolin

[0087] Weigh: 500 g of ferric chloride and 5000 mL of ethylene glycol, add them to a 10 L beaker, stir until the system dissolves, add 900 g of activated kaolin to the beaker, disperse ultrasonically for 80 min, transfer the ultrasonic solution to a 10 L reaction kettle and stir, add 100 g of trisodium citrate and 130 g of ammonium acetate to the reaction kettle, stir at room temperature for 60 min, introduce a heat exchange medium with a temperature of 200 °C into the jacket of the reaction kettle, keep warm for 4 h, wait for the temperature of the reaction system to drop to room temperature, add 4 L of 50 vol% ethanol aqueous solution to the reaction system, stir and disperse for 50 min, filter by suction, wash the filter cake three times with purified water and ethanol and then drain by suction, transfer the filter cake to a drying oven at 80 °C, dry to constant weight to obtain supported kaolin.

[0088] B3. Preparation of aminated supported kaolin

[0089] Weigh: 700 g of supported kaolin, 4000 mL of absolute ethanol and 300 g of 4-aminobutyltriethoxysilane, add them to a 10 L reaction kettle and stir, raise the temperature of the reaction kettle to 60 °C, add 1000 mL of 3 mol / L sodium hydroxide solution to the reaction kettle, keep warm and react for 5 h, lower the temperature of the reaction kettle to room temperature, filter by suction, wash the filter cake with purified water until neutral and then drain by suction, transfer the filter cake to a drying oven at 75 °C, dry under vacuum to constant weight to obtain aminated supported kaolin.

[0090] Example 7

[0091] This example provides a preparation method of an insulating and anti-interference polyvinyl chloride cable material, which includes the following steps:

[0092] S1. Preparation of a silicon-based reinforcing agent

[0093] Mix azobisisobutyronitrile and toluene evenly at a ratio of 1 g:15 mL to obtain an initiator solution for standby;

[0094] Weigh: 210 g of vinyl silicone oil, 90 g of methyl methacrylate, 60 g of isooctyl acrylate, 60 g of 1,2-epoxy-7-octene and 1500 mL of toluene, add them to a 5 L reaction kettle under nitrogen protection and stir, raise the temperature of the reaction kettle to 70 °C, drop 150 mL of the initiator solution into the reaction kettle, keep warm and react for 6 h, keep the reaction kettle at 70 °C, reduce pressure to remove low-boiling substances to obtain a silicon-based reinforcing agent.

[0095] S2. Preparation of an epoxy flame retardant

[0096] Mix antimony trioxide, zinc stannate, ammonium octamolybdate and graphene oxide evenly at a weight ratio of 5:3:2:3 to obtain a flame retardant for standby;

[0097] Weigh: 300 g of epoxy resin and 3000 mL of absolute ethanol are added to a 10 L reaction kettle and stirred and mixed. The temperature of the reaction kettle is raised to 70 °C, and it is kept warm and stirred until the system is dissolved. 900 g of flame retardant is added to the reaction kettle, and it is kept warm and stirred for 60 min. The temperature of the reaction kettle is lowered to room temperature. 5 L of purified water is added to the reaction kettle, and it is kept warm and stirred for 20 min. The temperature of the reaction kettle is lowered to room temperature. It is filtered by suction. The filter cake is washed 3 times with purified water and then dried by suction. The filter cake is transferred to a drying oven at 60 °C and dried in vacuum until constant weight to obtain an epoxy flame retardant.

[0098] S3. Prepare polyvinyl chloride cable material

[0099] Mix dioctyl phthalate, sodium metal stearate, antioxidant 1010 and chrome yellow evenly according to the weight ratio of 5:3:2:1:2 to obtain an auxiliary additive for standby;

[0100] Weigh by weight: 55 parts of PVC, 20 parts of activated PVC prepared in Example 1, 12 parts of a silicon-based reinforcing agent, 13 parts of ammoniated supported kaolin prepared in Example 4, 8 parts of an epoxy flame retardant and 6 parts of an auxiliary additive are added to a twin-screw extruder. The temperatures of the 5 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 in sequence. After melting and extruding through the twin-screw extruder, it is pelletized to obtain a polyvinyl chloride cable material.

[0101] Example 8

[0102] This example provides a preparation method of an insulating and anti-interference polyvinyl chloride cable material, including the following steps:

[0103] S1. Prepare a silicon-based reinforcing agent

[0104] Mix azodiisobutyronitrile and toluene evenly according to 1 g:15 mL to obtain an initiator solution for standby;

[0105] Weigh: 210 g of vinyl silicone oil, 90 g of methyl methacrylate, 60 g of isooctyl acrylate, 60 g of 1,2-epoxy-7-octene and 1500 mL of toluene are added to a 5 L reaction kettle under nitrogen protection and stirred. The temperature of the reaction kettle is raised to 75 °C. 150 mL of the initiator solution is added dropwise to the reaction kettle, and it is kept warm and reacted for 7 h. The reaction kettle is kept warm at 75 °C, and low-boiling substances are removed under reduced pressure to obtain a silicon-based reinforcing agent.

[0106] S2. Prepare an epoxy flame retardant

[0107] Mix antimony trioxide, zinc stannate, ammonium octamolybdate and graphene oxide evenly according to the weight ratio of 5:3:2:3 to obtain a flame retardant for standby;

[0108] Weigh: 300 g of epoxy resin and 3000 mL of absolute ethanol, add them to a 10 L reaction kettle and stir to mix. Raise the temperature of the reaction kettle to 75 °C, keep stirring while heating until the system dissolves. Add 900 g of flame retardant to the reaction kettle, keep stirring while heating for 70 min. Lower the temperature of the reaction kettle to room temperature. Add 5 L of purified water to the reaction kettle, keep stirring while heating for 25 min. Lower the temperature of the reaction kettle to room temperature. Filter by suction. Wash the filter cake with purified water three times and then drain it by suction. Transfer the filter cake to a drying oven at 65 °C and dry it under vacuum until constant weight to obtain the epoxy flame retardant.

[0109] S3. Prepare polyvinyl chloride cable compound

[0110] Mix diisooctyl phthalate, zinc stearate, antioxidant 1010 and molybdenum chromate red evenly according to the weight ratio of 5:3:2:1:2 to obtain auxiliary additives for standby.

[0111] Weigh by parts 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 supported kaolin prepared in Example 4, 9 parts of epoxy flame retardant and 7 parts of auxiliary additives, 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 in sequence. After melting and extruding through the twin-screw extruder, pelletize to obtain the polyvinyl chloride cable compound.

[0112] Example 9

[0113] This example provides a preparation method of an insulating and anti-interference polyvinyl chloride cable material, which includes the following steps:

[0114] S1. Prepare silicon-based reinforcing agent

[0115] Mix azobisisobutyronitrile and toluene evenly according to 1 g:15 mL to obtain an initiator solution for standby.

[0116] Weigh: 210 g of vinyl silicone oil, 90 g of methyl methacrylate, 60 g of isooctyl acrylate, 60 g of 1,2-epoxy-7-octene and 1500 mL of toluene, add them to a 5 L reaction kettle under nitrogen protection and stir. Raise the temperature of the reaction kettle to 80 °C, dropwise add 150 mL of the initiator solution to the reaction kettle, keep the reaction at 80 °C for 8 h while heating. Keep the reaction kettle at 80 °C and reduce the pressure to remove low-boiling substances to obtain the silicon-based reinforcing agent.

[0117] S2. Prepare epoxy flame retardant

[0118] Mix antimony trioxide, zinc stannate, ammonium octamolybdate and graphene oxide evenly according to the weight ratio of 5:3:2:3 to obtain a flame retardant for standby.

[0119] Weigh: 300 g of epoxy resin and 3000 mL of absolute ethanol are added to a 10 L reactor and stirred and mixed. The temperature of the reactor is raised to 80 °C, and it is kept warm and stirred until the system is dissolved. 900 g of flame retardant is added to the reactor, and it is kept warm and stirred for 80 min. The temperature of the reactor is lowered to room temperature. 5 L of purified water is added to the reactor, and it is kept warm and stirred for 30 min. The temperature of the reactor is lowered to room temperature. It is filtered by suction. The filter cake is washed 3 times with purified water and then dried by suction. The filter cake is transferred to a drying oven at 70 °C and vacuum dried to constant weight to obtain the epoxy flame retardant.

[0120] S3. Preparation of polyvinyl chloride cable compound

[0121] Diisopropyl phthalate, magnesium stearate, antioxidant 1010 and cobalt blue are mixed evenly according to the weight ratio of 5:3:2:1:2 to obtain an auxiliary additive for standby;

[0122] Weigh by weight: 65 parts of PVC, 30 parts of activated PVC prepared in Example 3, 16 parts of a silicon-based reinforcing agent, 17 parts of ammoniated supported kaolin prepared in Example 6, 10 parts of the epoxy flame retardant and 8 parts of the auxiliary additive are added to a twin-screw extruder. The temperatures of the 5 temperature zones of the twin-screw extruder from the feeding end to the discharging end are 180 °C, 185 °C, 190 °C, 190 °C and 195 °C in sequence. After melting and extruding through the twin-screw extruder, it is pelletized to obtain the polyvinyl chloride cable compound.

[0123] Comparative Example 1

[0124] The difference between this comparative example and Example 9 is that the flame retardant in Step S2 is used to replace the epoxy flame retardant in Step S3.

[0125] Comparative Example 2

[0126] The difference between this comparative example and Example 9 is that graphene oxide is 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 is not added in Step S3.

[0129] Comparative Example 4

[0130] The difference between this comparative example and Example 9 is that the used ammoniated supported kaolin is replaced by supported kaolin in equal amount.

[0131] Performance test:

[0132] Referring to the standard T / SHPTA 016-2021 "Flame Retardant Thermoplastic Elastomer Cable Compound", the flame retardant grade, tensile strength, elongation at break and volume resistivity at 20 °C of the polyvinyl chloride cable compound specimens prepared in Examples 7-9 and Comparative Examples 1-4 are measured;

[0133] The shielding effectiveness of the PVC cable material specimens prepared in Examples 7-9 and Comparative Examples 1-4 was measured with reference to the standard GB / T 30142-2013 "Measurement Method for Shielding Effectiveness of Flat Electromagnetic Shielding Materials".

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

[0135] Table 1 - Performance Test Data Sheet of Specimens

[0136]

[0137] Data Analysis:

[0138] By comparing and analyzing the data in Table 1 above, the tensile strength of the PVC cable material prepared in the present invention reached 28.9 MPa, the elongation at break reached 354.5%, the flame retardant grade reached V-0, the volume resistivity reached 8.73×10 8 Ω·m, and the shielding effectiveness reached 22.4 dB. All performance parameters are superior to those of the comparative examples, indicating that by using activated PVC as a compatibilizer, promoting the mixing of the silicon-based reinforcing agent and PVC, modifying the flame retardant with epoxy resin, and optimizing the composition of the flame retardant, the present invention not only effectively improves the insulation and tensile properties of the PVC cable material, but also improves its flame retardant and electromagnetic interference resistance properties.

[0139] The above content is only an example and illustration of the structure of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the structure of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

[0140] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0141] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only the specific embodiments. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. An insulated anti-interference polyvinyl chloride cable material, characterized in that: The invention comprises the following components by weight: 55-65 parts of PVC, 20-30 parts of activated PVC, 12-16 parts of silicon-based reinforcing agent, 13-17 parts of aminated loaded kaolin, 8-10 parts of epoxidized flame retardant and 6-8 parts of auxiliary additives; The activated PVC is processed by the following steps: A1. Stir and mix polyvinyl chloride powder, sodium hydroxide and purified water. After the reaction system is sealed, the temperature is increased to 200-220°C, the pressure is increased to 2.8-3.2MPa, and the heat treatment is carried out for 2-3h. After post-treatment, dechlorinated PVC is obtained; A2. Stir and mix the dechlorinated PVC, formic acid and catalyst, raise the temperature of the reaction system to 60-70°C, dropwise add hydrogen peroxide solution to the reaction system, and after the dropwise addition is complete, heat-retain the reaction for 40-60 minutes, and post-treat to obtain activated PVC.

2. The insulated anti-interference polyvinyl chloride cable material according to claim 1, characterized in that: In step A1, the amount ratio of the polyvinyl chloride powder, sodium hydroxide and purified water is 8g:1.1-1.3g:30mL; in step A2, the amount ratio of the 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 insulated anti-interference polyvinyl chloride cable material according to claim 1, characterized in that: 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 increased to 70-80° C., an initiator solution is added dropwise to the reaction system, the reaction is kept warm for 6-8 hours, and post-processed to obtain the silicon-based reinforcing agent.

4. The insulated anti-interference polyvinyl chloride cable material according to claim 3, characterized in that: The usage 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, and the initiator solution is composed of azobisisobutyronitrile and toluene in a ratio of 1g:15mL.

5. The insulated anti-interference polyvinyl chloride cable material according to claim 1, characterized in that: The ammoniation-loaded kaolin is obtained by processing the following steps: B1, calcined kaolin and activation solution are stirred and mixed, the reaction system temperature is 75-85°C, the temperature is kept at 4-6h, and post-processed to obtain activated kaolin; B2, ferric chloride and ethylene glycol were mixed and stirred until the system was dissolved, activated kaolin was added to the reaction system, ultrasonically dispersed for 60-80 min, trisodium citrate and ammonium acetate were added to the reaction system under stirring, stirred at room temperature for 40-60 min, and post-treated to obtain loaded kaolin; B3. Stir and mix the loaded kaolin, anhydrous ethanol and 4-aminobutyltriethoxysilane, raise the temperature of the reaction system to 50-60° C., add 2-3 mol / L sodium hydroxide solution to the reaction system, keep the temperature for 4-5 hours, and post-treat to obtain aminated loaded kaolin.

6. The insulated anti-interference polyvinyl chloride cable material according to claim 5, characterized in that: In step B1, the calcined kaolin and the activation solution are used in a ratio of 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 B2, the ferric chloride, ethylene glycol, activated kaolin, trisodium citrate and ammonium acetate are used in a ratio of 5g:50mL:9g:1g:1.3g; in step B3, the loaded kaolin, anhydrous ethanol, 4-aminobutyltriethoxysilane and 2-3mol / L sodium hydroxide solution are used in a ratio of 7g:40mL:3g:10mL.

7. The insulated anti-interference polyvinyl chloride cable material according to claim 1, characterized in that: 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 increased to 70-80° C., the system is stirred and kept warm until the system is dissolved, the flame retardant is added to the reaction system, the system is stirred and kept warm for 60-80 minutes, the temperature of the reaction system is reduced to room temperature, purified water is added to the reaction system, the system is stirred and kept warm for 20-30 minutes, and post-processed to obtain the epoxidized flame retardant.

8. The insulated anti-interference polyvinyl chloride cable material according to claim 7, characterized in that: The epoxy resin, xylene and flame retardant are used in a ratio of 1 g:10 mL:3 g, and the flame retardant is composed of antimony trioxide, zinc stannate, ammonium octamolybdate and graphene oxide in a weight ratio of 5:3:2:

3.

9. A method for preparing an insulated and anti-interference polyvinyl chloride cable material as claimed in any one of claims 1 to 8, characterized in that: The preparation method of the insulated and anti-interference polyvinyl chloride cable material comprises the following steps: mixing PVC, activated PVC, silicon-based reinforcing agent, aminated loaded kaolin, epoxidized flame retardant and auxiliary additives, and then pelletizing after melt extrusion through a twin-screw extruder to obtain the polyvinyl chloride cable material.

10. The method for preparing an insulated and anti-interference polyvinyl chloride cable material according to claim 9, characterized in that: The auxiliary additives are composed of a plasticizer, a dispersant, an antioxidant and a colorant in a weight ratio of 5:3:2:1:2, the plasticizer is a phthalate, the dispersant is a 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 sections 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.

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