CN116836476A - Electromagnetic shielding composite material for high-voltage cable and preparation process thereof - Google Patents

Electromagnetic shielding composite material for high-voltage cable and preparation process thereof Download PDF

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CN116836476A
CN116836476A CN202310835741.0A CN202310835741A CN116836476A CN 116836476 A CN116836476 A CN 116836476A CN 202310835741 A CN202310835741 A CN 202310835741A CN 116836476 A CN116836476 A CN 116836476A
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composite material
parts
mixing
electromagnetic shielding
voltage cable
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CN116836476B (en
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张人尹
任伟强
梁勇
邱丹彪
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Jiangyin Haijiang Polymer Material Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/001Conductive additives
    • CCHEMISTRY; METALLURGY
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

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Abstract

The application relates to the technical field of shielding materials, in particular to a high-voltage cable electromagnetic shielding composite material and a preparation process thereof, comprising the following processes: mixing conductive filler and dispersing agent to obtain modified filler; mixing the base material, the modified filler, the modifier and the processing aid, mixing, extruding, granulating and drying to obtain a composite material; wherein the dispersing agent is prepared by the following process: taking 2-propenyl-4, 6-biphenyl formylresorcinol alcohol, and reacting with 3-mercaptopropyl trimethoxy silane under the protection of nitrogen atmosphere to obtain the dispersing agent. According to the application, the polar groups such as carbonyl are introduced by using the dispersing agent, so that a shell layer with a high dielectric constant is formed on the surface of the conductive filler, and the conductivity of the composite material is improved; and a high-density trap is formed at the interface, so that the breakdown field intensity of the composite material is improved, and the improvement of the temperature resistance, the conductivity and the electric resistance of the shielding material made of the composite material is realized.

Description

Electromagnetic shielding composite material for high-voltage cable and preparation process thereof
Technical Field
The application relates to the technical field of shielding materials, in particular to a high-voltage cable electromagnetic shielding composite material and a preparation process thereof.
Background
With the flight of China and the expansion of urban scale, the current cables mainly develop towards the large-capacity, long-distance and high-efficiency power transmission direction. And from the economic and technical aspects, the advantages of low loss, low cost, high stability and the like of direct current transmission are realized, so that the direct current transmission has great advantages. At present, XLPE is generally used for insulation of the high-voltage direct-current cable, but XLPE insulation is greatly affected by space charges. The semiconductive shielding layer is used as an important component in XLPE insulated cables, and can prevent partial discharge from occurring in gaps between the conductive wire cores and the insulating layer. Because of lower economic cost, the conventional semiconductive shielding layer is usually used as a conductive filler, but if the addition amount of the conductive carbon black is excessive, the toughness and the smoothness of the manufactured shielding layer can be reduced. Therefore, we propose a high-voltage cable electromagnetic shielding composite material and a preparation process thereof.
Disclosure of Invention
The application aims to provide a high-voltage cable electromagnetic shielding composite material and a preparation process thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the application provides the following technical scheme: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
s1, treating conductive filler: heating the conductive filler to 90-110 ℃, adding a dispersing agent, and mixing at a high speed for 5-10 min to obtain a modified filler;
s2: preparation of composite material: mixing the base material, the modified filler, the modifier and the processing aid, mixing, extruding, granulating and drying to obtain the composite material.
Further, the mixing process conditions are as follows: the mixing temperature is 110-120 ℃, and the mixing time is 10-25 min.
Further, the extrusion process conditions were: the temperature of each zone is 145-150 ℃, 155-160 ℃, 165-170 ℃, 175-180 ℃, 165-170 ℃ and 155-160 ℃; the rotating speed of the host machine is 90-120 r/min.
Further, the drying process conditions are as follows: the drying temperature is 60-80 ℃ and the drying time is 12-24 h.
Further, the composite comprises the following components in parts by mass: 79 to 87 parts of base material, 15 to 23 parts of modified filler, 0.75 to 2.0 parts of dispersing agent, 1.0 to 5.0 parts of modifier and 4.6 to 6.9 parts of processing aid.
Further, the base material comprises 23.7 to 26.1 parts of Low Density Polyethylene (LDPE) and 55.3 to 60.9 parts of ethylene-butyl acrylate copolymer (EBA);
ethylene-butyl acrylate copolymer: EBA REPSOL E1770, melt flow rate 7g/10min, butyl acrylate content 17%, from Spanish Replotel;
low density polyethylene: LD100BW, melt flow rate 2.1g/10min, derived from China petrochemical groups.
Further, the conductive filler comprises 15-24 parts of conductive carbon black and 1-5 parts of graphite;
conductive carbon black: n220 is from Tianjin Chi Rui Shengtai chemical industry Co., ltd;
graphite: flake graphite with average particle size of 325 meshes and density of 2.1g/cm 3 The purity is more than or equal to 99 percent, and the graphite is sourced from the Tokay graphite Co.Ltd;
zinc oxide: the tablets had an average particle size of 10. Mu.m, and were obtained from Exxon Mobil.
Further, the processing aid comprises 2.0 to 3.0 parts of cross-linking agent, 0.05 to 0.15 part of cross-linking catalyst, 2 to 3 parts of lubricant and 0.50 to 0.75 part of antioxidant;
the cross-linking agent is selected from one of dicumyl peroxide DCP and di-tert-butyl cumene peroxide BIBP;
the crosslinking catalyst is selected from one of dibutyl tin dilaurate, di-n-octyl tin dilaurate and dodecylbenzene sulfonic acid;
the lubricant is stearic acid and zinc oxide with the mass ratio of 1:1; zinc oxide: the tablets had an average particle size of 10. Mu.m, and were obtained from Exxon Mobil. The addition of fillers and processing aids can lead to poor melt fluidity during processing, rapidly increased internal friction force of the melt, poor dispersibility of the conductive fillers, even agglomeration phenomenon, and influence the smoothness and conductivity of the composite. In the mixing process of the composite material, the melt is easy to flow unstably, so that the materials are mixed unevenly. The lubricant is added to reduce the internal friction force during material processing and enhance the flow force of the melt.
The antioxidant is prepared from antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1. The addition of the antioxidant can improve the service life of the prepared shielding layer and effectively inhibit the oxidative degradation of the base material; has good compatibility with the base material, is not easy to separate out, plays a synergistic effect with the cross-linking agent, and improves the performances of oxidation resistance, temperature resistance, weather resistance and the like of the composite material.
In the technical scheme, the conductive carbon black can reduce the resistivity of the composite material, has lower economic cost, and is used as a main conductive filler to be added into the electromagnetic shielding composite material of the high-voltage cable. However, if the addition amount of the conductive carbon black is too large, the toughness and the smoothness of the prepared shielding layer can be reduced; if the content is small, the conductivity of the shielding layer cannot be ensured. And the conductive carbon black is uniformly distributed in the base material, so that a stable conductive network structure can be formed, the resistivity is reduced, but the base material is heated to expand along with the increase of the temperature of the prepared shielding layer, so that the conductive network of the carbon black is destroyed, and the phenomenon of resistivity increase is shown.
Therefore, the graphite with the lamellar structure is added as the second conductive filler, so that the conductive performance of the composite material can be greatly improved, more conductive networks are formed, the conductive carbon black dispersed in the base material is connected, the resistivity of the prepared shielding material is reduced, and the insulating layer is prevented from being damaged by electric field distortion. The introduction of the second filler enables a good maintenance of the conductive network even if the binder expands under the influence of temperature. Meanwhile, the smoothness of the semiconductive shielding layer is guaranteed by adding the second filler, the viscosity and the shearing strength of the composite material are improved, and the mechanical properties of the manufactured shielding material are improved. Meanwhile, zinc oxide in the lubricant can also exert certain conductivity, so that the electrical property and mechanical property of the prepared composite material are further enhanced.
The application uses the conductive carbon black, the graphite and the zinc oxide in a compounding way, and reduces the total usage amount of the conductive filler through the synergistic enhancement effect of the conductive network, thereby realizing the required resistivity and reducing the damage of the conductive filler to the performance of the base material.
Further, the dispersing agent is aromatic siloxane, and is specifically prepared by the following process:
mixing 2-propenyl-4, 6-dibenzoyl resorcinol alcohol and methylene dichloride, slowly adding 3-mercaptopropyl trimethoxy silane and triethylamine under the protection of nitrogen atmosphere at the temperature of 0-5 ℃, dropwise adding for 60min, reacting at constant temperature for 28-30 h, and performing rotary evaporation to obtain the aromatic siloxane.
Further, the mass ratio of the 2-propenyl-4, 6-biphenyl formylresorcinol alcohol, 3-mercaptopropyl trimethoxy silane and triethylamine is (24.4-25.0): 11.6-12.0): 1;
the proportion of the 2-propenyl-4, 6-biphenyl formylresorcinol alcohol and methylene dichloride is 20-30 g/100mL;
3-mercaptopropyl trimethoxy silane and triethylamine in the system are mixed and added into a reaction system of the dispersing agent in the form of solution, the solvent is methylene dichloride, and the concentration of the solution is 40wt%.
In the technical scheme, the aromatic siloxane is used as the dispersing agent, after the surface of the conductive filler is modified, the compatibility between the conductive filler and the polymer base stock can be enhanced, the dispersibility of the conductive filler in the base stock is improved, and the stacking of the conductive filler is reduced, so that the electrical property of the composite material is improved, and the stability of a conductive network formed by the conductive filler is enhanced.
The aromatic siloxane is obtained by reacting 2-propenyl-4, 6-dibenzoyl resorcinol alcohol and 3-mercaptopropyl trimethoxy silane, and is obtained by reacting an olefinic bond with a mercapto group, and the prepared aromatic siloxane reacts with hydroxyl groups on the surface of a conductive filler under the high-temperature shearing action to obtain the functionalized modified filler.
The introduction of carbonyl and other polar groups forms a shell layer with high dielectric constant on the surface of the conductive filler, and under the action of an external electric field, the polar shell layer undergoes inductive polarization, so that carriers migrate at the interface of the filler and the base material to form a conductive sheath, the number of movable carriers at the interface is increased, and the conductivity of the prepared composite material is improved. The introduction of the dibenzoyl resorcinol alcohol structure enables the conductive sheath to utilize the high electron affinity of the conductive sheath as a charge trap, form a high-density trap at an interface, capture movable carriers, inhibit charge injection, form coulomb shielding, weaken the damage of carriers to a base material molecular chain, and enable the breakdown field strength of the composite material to be improved. And with the increase of temperature, carriers are easier to migrate, interface effect is improved, the energy level of traps is increased, the influence of temperature on the relative dielectric constant of the shielding layer prepared from the composite material can be reduced, and the improvement of the temperature resistance, the conductivity and the electric resistance of the shielding material prepared from the composite material is realized.
Further, the modifier is prepared by the following process:
mixing 2-propenyl-4, 6-diphenyl formylresorcinol alcohol, methyl dichlorosilane and a platinum catalyst, heating to 75-100 ℃, and carrying out reflux reaction for 7-10 h; distilling to obtain chlorosilane;
adding butenyl dichloromethylsilane into chlorosilane, heating to 75-85 ℃, and carrying out reflux reaction for 1-2 h; adding methanol, and continuing the reaction for 60-90 min; and (5) distilling under reduced pressure to obtain the modifier.
Further, the molar ratio of the 2-propenyl-4, 6-biphenyl formylresorcinol alcohol to the methyldichlorosilane (CAS 75-54-7) is 1 (1.1-1.3);
platinum catalyst: the mass concentration of the solution is 2 percent of chloroplatinic acid isopropanol solution, and the dosage of the solution is 0.5 to 1.5X10 of methyldichlorosilane -4( Calculated as platinum).
Further, the mass ratio of chlorosilane, butenyl dichloromethylsilane and methanol is (14.7-15.2): 33.8-35.5): 2.
Further, step S2 includes the following processes:
mixing a crosslinking catalyst, an antioxidant and 30-50% of base materials by mass to obtain a catalyst master batch;
drying the modifier, the cross-linking agent, the base materials of the rest mass components and the lubricant to constant weight, and mixing to obtain a cross-linked master batch;
mixing the catalyst master batch, the crosslinking master batch and the modified filler, extruding, granulating and drying to obtain the composite material.
In the technical scheme, under the action of a platinum catalyst, 2-propenyl-4, 6-dibenzoyl resorcinol alcohol and methyl dichlorosilane undergo an addition reaction to obtain chlorosilane, hydroxyl of the 2-propenyl-4, 6-dibenzoyl resorcinol alcohol in the chlorosilane is substituted with chloro in butenyl dichloromethyl silane, and the reactive chlorosilane in the product is converted into siloxane by utilizing methanol to obtain a stable modifier. In the preparation process of the composite material, firstly, a modifier and a cross-linking agent are mixed and mixed with a base material, so that the butenyl in the modifier and the base material are cross-linked and grafted; and then co-extruding the obtained catalyst master batch and the cross-linked master batch, and cross-linking the silicon-oxygen bonds in the modifier structure under the action of the cross-linked catalyst in the water producing agent and the catalyst master batch, so as to realize the preparation of the composite material and improve the thermal stability and mechanical property of the composite material. Meanwhile, the introduction of the 2-propenyl-4, 6-biphenyl formylresorcinol alcohol structure can also improve the breakdown strength and the electrical resistance of the composite material.
In the technical scheme, zinc oxide in the conductive filler can be cooperated with stearic acid in the lubricant to serve as a water generating agent, so that the crosslinking reaction of siloxane in the modifier is not required to be carried out in water/water vapor, the crosslinking between the modifier and polyethylene is promoted, the crosslinking effect of chemical bonds between molecules occurs, a three-dimensional network molecular structure is established, the crosslinking degree in a composite material system is improved, and the mechanical property and the thermal stability of the prepared shielding material are further improved; meanwhile, the melt processing can be lubricated, a lubricating effect is exerted, and the smoothness of the composite material is improved.
Through the crosslinking of the modifier, the low-density polyethylene and the ethylene-butyl acrylate copolymer, the compatibility between the base material and the conductive filler can be effectively improved, and the compactness of the composite material is improved, so that the mechanical property of the composite material is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the following examples, the "parts" numbers are mass parts;
ethylene-butyl acrylate copolymer: EBA REPSOL E1770, melt flow rate 7g/10min, butyl acrylate content 17%, from Spanish Replotel;
low density polyethylene: LD100BW, melt flow rate 2.1g/10min, derived from China petrochemical group;
conductive carbon black: n220 is from Tianjin Chi Rui Shengtai chemical industry Co., ltd;
graphite: flake graphite with average particle size of 325 meshes and density of 2.1g/cm 3 The purity is more than or equal to 99 percent, and the graphite is sourced from the Tokay graphite Co.Ltd;
zinc oxide: the tablets had an average particle size of 10. Mu.m, and were obtained from Exxon Mobil.
Example 1: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
s1, treating conductive filler:
1.1. mixing 24.4 parts of 2-propenyl-4, 6-dibenzoyl resorcinol alcohol and 100mL of dichloromethane, slowly adding 11.6 parts of 3-mercaptopropyl trimethoxy silane and 1 part of triethylamine under the protection of nitrogen atmosphere at the temperature of 5 ℃, dropwise adding for 60min, reacting at constant temperature for 28h, and performing rotary evaporation to obtain a dispersing agent; wherein, 3-mercaptopropyl trimethoxy silane and triethylamine are mixed and added into a reaction system of a dispersing agent in the form of solution, the solvent is methylene dichloride, and the concentration of the solution is 40wt%;
1.2. heating the conductive filler to 90 ℃, adding a dispersing agent, and mixing at a high speed for 10min to obtain a modified filler;
s2: preparation of composite material:
2.1. mixing 35.8 parts of 2-propenyl-4, 6-biphenyl formylresorcinol alcohol, 12.7 parts of methyl dichlorosilane and a platinum catalyst, heating to 75 ℃, and carrying out reflux reaction for 10 hours; distilling to obtain chlorosilane; wherein platinum catalyzesThe preparation method comprises the following steps: solution of chloroplatinic acid isopropyl alcohol with mass concentration of 2% and dosage of 0.5X10 of methyldichlorosilane -4( Calculated as platinum);
14.7 parts of chlorosilane is taken, 33.8 parts of butenyl dichloromethylsilane is added, the temperature is raised to 75 ℃, and the reflux reaction is carried out for 2 hours; adding 2 parts of methanol, and continuing to react for 90min; vacuum distilling to obtain modifier;
2.2. mixing a crosslinking catalyst, an antioxidant and 50% of base materials by mass to obtain a catalyst master batch; drying the modifier, the cross-linking agent, the base materials of the rest mass components and the lubricant to constant weight, and mixing to obtain a cross-linked master batch; the mixing process conditions are as follows: mixing temperature is 110 ℃, and mixing time is 10min;
mixing the catalyst master batch, the crosslinking master batch and the modified filler, extruding, granulating and drying to obtain a composite material; the extrusion process conditions are as follows: the temperature of each zone is 145 ℃, 155 ℃, 165 ℃, 175 ℃, 165 ℃ and 155 ℃; the rotating speed of the host machine is 90r/min; the drying process conditions are as follows: drying at 60 ℃ for 24 hours;
wherein the base material is 23.7 parts of low-density polyethylene and 55.3 parts of ethylene-butyl acrylate copolymer; the conductive filler is 15 parts of conductive carbon black and 1 part of graphite;
the processing aid comprises 2.0 parts of cross-linking agent (dicumyl peroxide DCP), 0.05 part of cross-linking catalyst (dodecylbenzene sulfonic acid), 2 parts of lubricant (the combination of stearic acid and zinc oxide with the mass ratio of 1:1) and 0.50 part of antioxidant (the combination of antioxidant 1010 and antioxidant 168 with the mass ratio of 2:1);
the composite was 79 parts base, 15 parts modified filler, 0.75 parts dispersant, 1.0 part modifier and 4.6 parts processing aid.
Example 2: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
s1, treating conductive filler:
1.1. mixing 24.7 parts of 2-propenyl-4, 6-dibenzoyl resorcinol alcohol and 100mL of dichloromethane, slowly adding 11.8 parts of 3-mercaptopropyl trimethoxy silane and 1 part of triethylamine under the protection of nitrogen atmosphere at the temperature of 2 ℃, dropwise adding for 60min, reacting at constant temperature for 29h, and performing rotary evaporation to obtain a dispersing agent; wherein, 3-mercaptopropyl trimethoxy silane and triethylamine are mixed and added into a reaction system of a dispersing agent in the form of solution, the solvent is methylene dichloride, and the concentration of the solution is 40wt%;
1.2. heating the conductive filler to 100 ℃, adding a dispersing agent, and mixing at a high speed for 8min to obtain a modified filler;
s2: preparation of composite material:
2.1. mixing 35.8 parts of 2-propenyl-4, 6-biphenyl formylresorcinol alcohol, 13.8 parts of methyl dichlorosilane and a platinum catalyst, heating to 85 ℃, and carrying out reflux reaction for 8 hours; distilling to obtain chlorosilane; wherein the platinum catalyst: chloroplatinic acid isopropyl alcohol solution with mass concentration of 2 percent and using 1.0X10 of methyldichlorosilane -4( Calculated as platinum);
15 parts of chlorosilane is taken, 34.6 parts of butenyl dichloromethylsilane is added, the temperature is raised to 80 ℃, and the reflux reaction is carried out for 1.5 hours; adding 2 parts of methanol, and continuing to react for 75min; vacuum distilling to obtain modifier;
2.2. mixing a crosslinking catalyst, an antioxidant and a base material with 40 mass percent to obtain a catalyst master batch; drying the modifier, the cross-linking agent, the base materials of the rest mass components and the lubricant to constant weight, and mixing to obtain a cross-linked master batch; the mixing process conditions are as follows: the mixing temperature is 115 ℃ and the mixing time is 18min;
mixing the catalyst master batch, the crosslinking master batch and the modified filler, extruding, granulating and drying to obtain a composite material; the extrusion process conditions are as follows: the temperature of each zone is 148 ℃, 158 ℃, 168 ℃, 178 ℃, 168 ℃ and 158 ℃; the rotating speed of the host machine is 90-120 r/min; the drying process conditions are as follows: drying at 70 ℃ for 18 hours;
wherein the base material is 25.0 parts of low-density polyethylene and 58.1 parts of ethylene-butyl acrylate copolymer; the conductive filler is 20 parts of conductive carbon black and 3 parts of graphite;
the processing aid comprises 2.5 parts of cross-linking agent (di-tert-butyl isopropyl benzene peroxide), 0.1 part of cross-linking catalyst (dibutyl tin dilaurate), 2.5 parts of lubricant (the combination of stearic acid and zinc oxide in a mass ratio of 1:1) and 0.62 part of antioxidant (the combination of antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1);
the composite material comprises 73 parts of base material, 19 parts of modified filler, 1.4 parts of dispersing agent, 3 parts of modifier and 5.8 parts of processing aid.
Example 3: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
s1, treating conductive filler:
1.1. mixing 25.0 parts of 2-propenyl-4, 6-dibenzoyl resorcinol alcohol and methylene dichloride, slowly adding 12.0 parts of 3-mercaptopropyl trimethoxy silane and 1 part of triethylamine under the protection of nitrogen atmosphere at the temperature of 0 ℃ for 60min, reacting for 30h at constant temperature, and performing rotary evaporation to obtain a dispersing agent; wherein, 3-mercaptopropyl trimethoxy silane and triethylamine are mixed and added into a reaction system of a dispersing agent in the form of solution, the solvent is methylene dichloride, and the concentration of the solution is 40wt%;
1.2. heating the conductive filler to 110 ℃, adding a dispersing agent, and mixing at a high speed for 5min to obtain a modified filler;
s2: preparation of composite material:
2.1. mixing 35.8 parts of 2-propenyl-4, 6-biphenyl formylresorcinol alcohol, 14.9 parts of methyl dichlorosilane and a platinum catalyst, heating to 100 ℃, and carrying out reflux reaction for 7h; distilling to obtain chlorosilane; wherein the platinum catalyst: chloroplatinic acid isopropyl alcohol solution with mass concentration of 2% and dosage of 1.5X10 of methyldichlorosilane -4( Calculated as platinum);
15.2 parts of chlorosilane is taken, 35.5 parts of butenyl dichloromethylsilane is added, the temperature is raised to 85 ℃, and the reflux reaction is carried out for 1 hour; adding 2 parts of methanol, and continuing to react for 90min; vacuum distilling to obtain modifier;
2.2. mixing a crosslinking catalyst, an antioxidant and a base material with 30 mass percent to obtain a catalyst master batch; drying the modifier, the cross-linking agent, the base materials of the rest mass components and the lubricant to constant weight, and mixing to obtain a cross-linked master batch; the mixing process conditions are as follows: mixing temperature is 120 ℃, and mixing time is 25min;
mixing the catalyst master batch, the crosslinking master batch and the modified filler, extruding, granulating and drying to obtain a composite material; the extrusion process conditions are as follows: the temperature of each zone is 150 ℃, 160 ℃, 170 ℃, 180 ℃, 170 ℃ and 160 ℃; the rotating speed of the host machine is 120r/min; the drying process conditions are as follows: drying at 80 ℃ for 12 hours;
wherein the base material is 26.1 parts of low-density polyethylene and 60.9 parts of ethylene-butyl acrylate copolymer; the conductive filler is 24 parts of conductive carbon black and 5 parts of graphite;
the processing aid comprises 3.0 parts of crosslinking agent dicumyl peroxide, 0.15 parts of crosslinking catalyst (di-n-octyl tin dilaurate), 3 parts of lubricant (the combination of stearic acid and zinc oxide with the mass ratio of 1:1) and 0.75 part of antioxidant (the combination of antioxidant 1010 and antioxidant 168 with the mass ratio of 2:1);
the composite material comprises 87 parts of base material, 23 parts of modified filler, 2.0 parts of dispersing agent, 5.0 parts of modifier and 6.9 parts of processing aid.
Comparative example 1: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
s1, treating conductive filler: heating the conductive filler to 90 ℃, adding a dispersing agent KH-560, and mixing at a high speed for 10min to obtain a modified filler;
step S2 was the same as in example 1 to obtain a composite material.
Comparative example 2: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
s1, treating conductive filler: heating the conductive filler to 90 ℃, adding a dispersing agent KH-560, and mixing at a high speed for 10min to obtain a modified filler;
s2: preparation of composite material:
2.1. 10.2 parts of allyl hydroxyethyl ether, 12.7 parts of methyl dichlorosilane and a platinum catalyst are mixed, the temperature is raised to 75 ℃, and the mixture is subjected to reflux reaction for 10 hours; distilling to obtain chlorosilane; wherein the platinum catalyst: solution of chloroplatinic acid isopropyl alcohol with mass concentration of 2% and dosage of 0.5X10 of methyldichlorosilane -4( Calculated as platinum);
14.7 parts of chlorosilane is taken, 33.8 parts of butenyl dichloromethylsilane is added, the temperature is raised to 75 ℃, and the reflux reaction is carried out for 2 hours; adding 2 parts of methanol, and continuing to react for 90min; vacuum distilling to obtain modifier;
step 2.2 was the same as in example 1 to obtain a composite material.
Comparative example 3: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
s1, treating conductive filler: heating the conductive filler to 90 ℃, adding a dispersing agent KH-560, and mixing at a high speed for 10min to obtain a modified filler;
s2: preparation of composite material: taking allyl dimethoxy silane as a modifier;
step 2.2 was the same as in example 1 to obtain a composite material.
Comparative example 4: the preparation process of the electromagnetic shielding composite material of the high-voltage cable comprises the following steps:
the conductive filler is conductive carbon black, the lubricant is stearic acid, and other processes and parameters are the same as those of comparative example 3, so that the composite material is obtained.
Experiment
Placing the composite materials obtained in the examples 1-3 and the comparative examples 1-4 into a tabletting mould with the thickness of 1.0mm, carrying out hot-pressing pre-plasticizing and heat preservation for 10min at the temperature of 200 ℃ and the temperature of 5MPa, and pressurizing to 15MPa and carrying out hot-pressing plasticizing and heat preservation for 5min; rapidly water-cooling, cooling to room temperature under 15MPa to obtain samples, detecting the performances of the samples and recording the detection results:
detecting the number of the protrusions: taking a sample with the size of 1.0cm multiplied by 1.0cm, observing and recording the number of the projections with the surface size of more than or equal to 10 mu m;
mechanical property test: using GB/T1040.3 as a reference standard, adopting an electronic universal testing machine to test the tensile strength and elongation at break of a sample, wherein the tensile rate is 250mm/min, and the gauge length is 20mm;
heat resistance test: placing the sample at 135 ℃ for thermal aging for 168 hours, taking out and cooling, detecting the mechanical properties of the sample again, and calculating the change rate of the tensile strength and the elongation at break of the sample before and after aging;
volume resistivity test: using GB/T3048.3 as a reference standard, adopting a resistivity tester to test the volume resistance of a sample in an oil bath at the experimental temperature of 20 ℃ and at the experimental temperature of 90 ℃, and calculating the volume resistivity of the sample according to the formula rho=RWD/L, wherein the size of the sample is 3cm multiplied by 0.5cm multiplied by 0.1cm;
breakdown field strength test: adopting a cylindrical electrode structure, immersing a sample and an electrode in silicone oil, and raising the DC voltage at the rate of 0.3kV/s until the sample breaks down, wherein the size of the sample is 1cm multiplied by 0.15cm, and the test temperature is 25 ℃;
from the data in the above table, the following conclusions can be clearly drawn:
the composites obtained in examples 1 to 3 were compared with the composites obtained in comparative examples 1 to 4, and it was found that the results of the detection,
the composites obtained in examples 1-3 have lower volume resistivity, higher tensile strength, elongation at break, breakdown field strength data, and fewer protrusions detected, as compared to the comparative examples, which fully demonstrates that the present application achieves improved conductivity, heat resistance, breakdown resistance, and smoothness properties for the resulting composites.
The conductive filler of comparative example 1 was different in surface-modifying substance from example 1; the modifier components in comparative examples 2-3 were different based on comparative example 1; in contrast to comparative example 3, the inorganic filler in comparative example 4 is only conductive carbon black; from the data, the composites obtained in comparative examples 1 to 4 were deteriorated in volume resistivity, tensile strength, elongation at break, breakdown field strength data, and the number of projections detected in comparative examples 3 to 4 was increased. It is known that the preparation process of the composite material and the arrangement of the required components can promote the improvement of the comprehensive performance of the composite material.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. A preparation process of a high-voltage cable electromagnetic shielding composite material is characterized by comprising the following steps of: the method comprises the following steps:
s1, treating conductive filler: heating the conductive filler to 90-110 ℃, adding a dispersing agent, and mixing at a high speed for 5-10 min to obtain a modified filler;
s2: preparation of composite material: mixing the base material, the modified filler, the modifier and the processing aid, mixing, extruding, granulating and drying to obtain a composite material;
the dispersing agent is prepared by the following process:
mixing 2-propenyl-4, 6-dibenzoyl resorcinol alcohol and methylene dichloride, slowly adding 3-mercaptopropyl trimethoxy silane and triethylamine under the protection of nitrogen atmosphere at the temperature of 0-5 ℃, dropwise adding for 60min, reacting at constant temperature for 28-30 h, and performing rotary evaporation to obtain the dispersing agent.
2. The process for preparing the electromagnetic shielding composite material for the high-voltage cable according to claim 1, wherein the process comprises the following steps of: the composite material comprises the following components in parts by mass: 79 to 87 parts of base material, 15 to 23 parts of modified filler, 0.75 to 2.0 parts of dispersing agent, 1.0 to 5.0 parts of modifier and 4.6 to 6.9 parts of processing aid.
3. The process for preparing the electromagnetic shielding composite material for the high-voltage cable according to claim 1, wherein the process comprises the following steps of: the base material comprises 23.7-26.1 parts of low-density polyethylene and 55.3-60.9 parts of ethylene-butyl acrylate copolymer.
4. The process for preparing the electromagnetic shielding composite material for the high-voltage cable according to claim 1, wherein the process comprises the following steps of: the conductive filler comprises 15-24 parts of conductive carbon black and 1-5 parts of graphite.
5. The process for preparing the electromagnetic shielding composite material for the high-voltage cable according to claim 1, wherein the process comprises the following steps of: the processing aid comprises 2.0 to 3.0 parts of cross-linking agent, 0.05 to 0.15 part of cross-linking catalyst, 2 to 3 parts of lubricant and 0.50 to 0.75 part of antioxidant;
the cross-linking agent is selected from one of dicumyl peroxide and di-tert-butyl isopropyl peroxide;
the crosslinking catalyst is selected from one of dibutyl tin dilaurate, di-n-octyl tin dilaurate and dodecylbenzene sulfonic acid.
6. The process for preparing the electromagnetic shielding composite material for the high-voltage cable according to claim 1, wherein the process comprises the following steps of: the mixing process conditions are as follows: the mixing temperature is 110-120 ℃, and the mixing time is 10-25 min.
7. The process for preparing the electromagnetic shielding composite material for the high-voltage cable according to claim 1, wherein the process comprises the following steps of: the extrusion process conditions are as follows: the temperature of each zone is 145-150 ℃, 155-160 ℃, 165-170 ℃, 175-180 ℃, 165-170 ℃ and 155-160 ℃; the rotating speed of the host machine is 90-120 r/min.
8. The process for preparing the electromagnetic shielding composite material for the high-voltage cable according to claim 1, wherein the process comprises the following steps of: the modifier is prepared by the following process:
mixing 2-propenyl-4, 6-diphenyl formylresorcinol alcohol, methyl dichlorosilane and a platinum catalyst, heating to 75-100 ℃, and carrying out reflux reaction for 7-10 h; distilling to obtain chlorosilane;
adding butenyl dichloromethylsilane into chlorosilane, heating to 75-85 ℃, and carrying out reflux reaction for 1-2 h; adding methanol, and continuing the reaction for 60-90 min; and (5) distilling under reduced pressure to obtain the modifier.
9. The process for preparing the electromagnetic shielding composite material for the high-voltage cable, which is disclosed in claim 5, is characterized in that: the step S2 specifically comprises the following processes:
mixing a crosslinking catalyst, an antioxidant and 30-50% of base materials by mass to obtain a catalyst master batch;
drying the modifier, the cross-linking agent, the base materials of the rest mass components and the lubricant to constant weight, and mixing to obtain a cross-linked master batch;
mixing the catalyst master batch, the crosslinking master batch and the modified filler, extruding, granulating and drying to obtain the composite material.
10. A high voltage cable electromagnetic shielding composite made according to any one of claims 1-9.
CN202310835741.0A 2023-07-10 2023-07-10 Electromagnetic shielding composite material for high-voltage cable and preparation process thereof Active CN116836476B (en)

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