CN113801385A - Crosslinkable polyethylene insulating material for high-voltage cable and preparation method thereof - Google Patents
Crosslinkable polyethylene insulating material for high-voltage cable and preparation method thereof Download PDFInfo
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- 239000011810 insulating material Substances 0.000 title claims abstract description 37
- -1 polyethylene Polymers 0.000 title claims abstract description 36
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 29
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 35
- 239000004971 Cross linker Substances 0.000 claims abstract description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 229920001684 low density polyethylene Polymers 0.000 claims description 15
- 239000004702 low-density polyethylene Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- 229920003020 cross-linked polyethylene Polymers 0.000 claims description 7
- 239000004703 cross-linked polyethylene Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 6
- 239000012774 insulation material Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 3
- 150000002978 peroxides Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 7
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- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000005684 electric field Effects 0.000 abstract description 4
- 230000009022 nonlinear effect Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08L2203/00—Applications
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- C08L2207/064—VLDPE
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Abstract
The invention relates to a crosslinkable polyethylene insulating material for a high-voltage cable and a preparation method thereof, wherein the material comprises the following components in percentage by mass: 97.5 to 99.3 percent of non-polar base material, 0.5 to 2 percent of cross linker and 0.1 to 0.5 percent of antioxidant. The traditional insulating material is modified by introducing a material without impurities and polar molecules, so that polar impurities causing nonlinear change of conductivity and crosslinking decomposition byproducts in the insulating material are reduced, the generation and migration of charges under a direct-current electric field are effectively inhibited, and the nonlinear effect of conductivity in a high-voltage cable is further inhibited; meanwhile, the preparation method of the material is simple and feasible, and the industrial applicability is strong.
Description
Technical Field
The invention relates to the field of insulating materials, in particular to a crosslinkable polyethylene insulating material for a high-voltage cable and a preparation method thereof.
Background
With the rapid development of electric power construction, the insulating material cable is widely applied to the aspects of production, transportation, installation, recovery and the like due to the advantages of small volume, light weight, high working temperature, low maintenance cost and environmental protection. However, the nonlinear change effect of the electrical conductivity of the insulating material along with the temperature and the field intensity is too large, so that the existing polyethylene cable insulating material can only be used for transmitting direct current energy in a low-voltage distribution system, but cannot be directly applied to a high-voltage direct current system.
At present, the local electric field intensity is far higher than the operation intensity of a cable, so that the cable material can be directly broken down, and meanwhile, the additives and crosslinking byproducts in the insulating material are ionized and polarized under a direct-current electric field to aggravate the nonlinear change phenomenon of the conductivity in the polyethylene insulating cable, so that the accumulation of the nonlinear excessive increase effect of the conductivity in the high-voltage direct-current cable needs to be inhibited.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a crosslinkable polyethylene insulation material for high voltage cables, which suppresses the non-linear effect of conductivity in high voltage cables, and a method for preparing the same.
The purpose of the invention is realized by adopting the following technical scheme:
the invention provides a crosslinkable polyethylene insulating material for a high-voltage cable, which is improved in that the material comprises the following components in percentage by mass:
97.5 to 99.3 percent of non-polar base material, 0.5 to 2 percent of cross linker and 0.1 to 0.5 percent of antioxidant.
Preferably, the material is prepared from the following components in percentage by mass:
97.5 to 98.5 percent of non-polar base material, 1.5 to 2 percent of cross linker and 0.1 to 0.2 percent of antioxidant.
Preferably, the non-polar base material is low-density polyethylene or a mixture of low-density polyethylene and ultra-low-density polyethylene with the mass fraction being more than or equal to 80%, the melt flow rate is 0.15-0.25g/min, the density is 910-3。
Preferably, the molecular weight distribution of the nonpolar base material is 5.2-6.3, and the ash content of the nonpolar base material is less than or equal to 100 ppm.
Preferably, the crosslinking agent is a peroxide compound.
Preferably, the antioxidant is a thiobisphenol compound.
Further, the crosslinking agent includes: dicumyl peroxide.
Further, the antioxidant comprises: a bis-sulfide.
The invention provides a process for the preparation of a crosslinkable polyethylene insulation for high voltage cables according to claim 1, the improvement comprising:
1) melting and mixing: mixing the non-polar base material and the antioxidant at 120-125 deg.c;
2) absorption: cooling the mixture of step 1) to 80 ℃ and incorporating the cross-linking agent into the mixture by a spray absorption method;
3) drying: drying the product obtained in the step 2), and then cooling to room temperature to obtain the crosslinked polyethylene insulating material.
Compared with the closest prior art, the invention has the following beneficial effects:
(1) according to the technical scheme provided by the invention, the traditional insulating material is modified by introducing the material without impurities and polar molecules, so that polar impurities causing nonlinear change of conductivity in the insulating material and crosslinking decomposition byproducts are reduced, the generation and migration of charges in a direct-current electric field are effectively inhibited, the nonlinear change of the conductivity of the insulating material is reduced to 200-500 times from 1000-2000 times of that of the conventional common material at the conditions of 30 ℃, 10kV/mm, 70 ℃ and 50kV/mm, and the nonlinear effect of the conductivity in a high-voltage cable is inhibited;
(2) according to the technical scheme provided by the invention, the ultra-clean low-density polyethylene material is adopted, so that the introduction of polar impurities is reduced, and the resistivity level of the material is improved;
(3) according to the technical scheme provided by the invention, the moisture content is not more than 200ppm (Karl Fischer method) after the formula compounding and batch production is completed, and the influence of water content on the conductivity is reduced;
(4) according to the technical scheme provided by the invention, the adopted cross-linking agent is a peroxide type cross-linking agent with the purity of more than 99.5%, impurities in the cross-linking agent are controlled, and the purity of the crosslinkable polyethylene insulating material is also improved;
(5) according to the technical scheme provided by the invention, the adopted antioxidant is a hindered phenol antioxidant, the purity of the antioxidant reaches more than 99.5 percent, and the purity of the crosslinkable polyethylene insulating material is improved by controlling impurities in the antioxidant;
(6) the technical scheme provided by the invention comprises the following steps: melting, mixing, absorbing and drying, the method is simple and feasible, and the industrial applicability is strong.
Drawings
Fig. 1 is a measured value and a fitted curve of the conductivity of a crosslinkable polyethylene insulation material for a high voltage cable according to the present invention as a function of temperature and field strength;
FIG. 2 is a measured value and a fitted curve of the conductivity of a cross-linkable polyethylene of a commercial high-voltage cable as a function of temperature and field strength;
fig. 3 is a process flow diagram of a method for preparing a crosslinkable polyethylene insulation material for a high voltage cable according to the present invention.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The invention provides a crosslinkable polyethylene insulating material for a high-voltage cable, which comprises the following components in percentage by mass:
97.5 percent of non-polar base stock, 2 percent of cross-linking agent and 0.5 percent of antioxidant.
In this example, the non-polar base material is low density polyethylene or a mixture of low density polyethylene and ultra-low density polyethylene with a mass fraction of 80% or more, and has a melt flow rate of 0.15-0.25g/min and a density of 910-3。
In the embodiment, the nonpolar base material has a molecular weight distribution of 5.2-6.3, and the ash content of the nonpolar base material is less than or equal to 100 ppm.
In this embodiment, the crosslinking agent is a peroxide compound.
In this example, the antioxidant is a thiobis phenolic compound.
Specifically, the crosslinking agent includes: dicumyl peroxide.
Specifically, the antioxidant comprises: a bis-sulfide.
The preparation method of the crosslinkable polyethylene insulating material for the high-voltage cable comprises the following steps:
1) melting and mixing: blending the non-polar base material with an antioxidant at 120 ℃;
2) absorption: cooling the mixture of step 1) to 80 ℃ and incorporating the cross-linking agent into the mixture by a spray absorption method;
3) drying: drying the product obtained in the step 2), and then cooling to room temperature to obtain the crosslinked polyethylene insulating material.
Example 2
The invention provides a crosslinkable polyethylene insulating material for a high-voltage cable, which is prepared from the following components in percentage by mass:
98.1 percent of non-polar base stock, 1.8 percent of cross-linking agent and 0.1 percent of antioxidant.
In this example, the non-polar base material is low density polyethylene or a mixture of low density polyethylene and ultra-low density polyethylene with a mass fraction of 80% or more, and has a melt flow rate of 0.15-0.25g/min and a density of 910-3。
In the embodiment, the nonpolar base material has a molecular weight distribution of 5.2-6.3, and the ash content of the nonpolar base material is less than or equal to 100 ppm.
In this embodiment, the crosslinking agent is a peroxide compound.
In this example, the antioxidant is a thiobis phenolic compound.
Specifically, the crosslinking agent includes: dicumyl peroxide.
Specifically, the antioxidant comprises: a bis-sulfide.
The preparation method of the crosslinkable polyethylene insulating material for the high-voltage cable comprises the following steps:
1) melting and mixing: blending the non-polar base material with an antioxidant at 122 ℃;
2) absorption: cooling the mixture of step 1) to 80 ℃ and incorporating the cross-linking agent into the mixture by a spray absorption method;
3) drying: drying the product obtained in the step 2), and then cooling to room temperature to obtain the crosslinked polyethylene insulating material.
Example 3
The invention provides a crosslinkable polyethylene insulating material for a high-voltage cable, which is prepared from the following components in percentage by mass:
98.2 percent of non-polar base stock, 1.5 percent of cross-linking agent and 0.3 percent of antioxidant.
In this example, the non-polar base material is low density polyethylene or a mixture of low density polyethylene and ultra-low density polyethylene with a mass fraction of 80% or more, and has a melt flow rate of 0.15-0.25g/min and a density of 910-3。
In the embodiment, the nonpolar base material has a molecular weight distribution of 5.2-6.3, and the ash content of the nonpolar base material is less than or equal to 100 ppm.
In this embodiment, the crosslinking agent is a peroxide compound.
In this example, the antioxidant is a thiobis phenolic compound.
Specifically, the crosslinking agent includes: dicumyl peroxide.
Specifically, the antioxidant comprises: a bis-sulfide.
The preparation method of the crosslinkable polyethylene insulating material for the high-voltage cable comprises the following steps:
1) melting and mixing: blending the non-polar base material with an antioxidant at 123 ℃;
2) absorption: cooling the mixture of step 1) to 80 ℃ and incorporating the cross-linking agent into the mixture by a spray absorption method;
3) drying: drying the product obtained in the step 2), and then cooling to room temperature to obtain the crosslinked polyethylene insulating material.
Example 4
The invention provides a crosslinkable polyethylene insulating material for a high-voltage cable, which is prepared from the following components in percentage by mass:
98.8 percent of non-polar base stock, 1.0 percent of cross-linking agent and 0.2 percent of antioxidant.
In this example, the non-polar base material is low density polyethylene or a mixture of low density polyethylene and ultra-low density polyethylene with a mass fraction of 80% or more, and has a melt flow rate of 0.15-0.25g/min and a density of 910-3。
In the embodiment, the nonpolar base material has a molecular weight distribution of 5.2-6.3, and the ash content of the nonpolar base material is less than or equal to 100 ppm.
In this embodiment, the crosslinking agent is a peroxide compound.
In this example, the antioxidant is a thiobis phenolic compound.
Specifically, the crosslinking agent includes: dicumyl peroxide.
Specifically, the antioxidant comprises: a bis-sulfide.
The preparation method of the crosslinkable polyethylene insulating material for the high-voltage cable comprises the following steps:
1) melting and mixing: blending the non-polar base material with an antioxidant at 124 ℃;
2) absorption: cooling the mixture of step 1) to 80 ℃ and incorporating the cross-linking agent into the mixture by a spray absorption method;
3) drying: drying the product obtained in the step 2), and then cooling to room temperature to obtain the crosslinked polyethylene insulating material.
Example 5
The invention provides a crosslinkable polyethylene insulating material for a high-voltage cable, which is prepared from the following components in percentage by mass:
99.3 percent of non-polar base material, 0.5 percent of cross-linking agent and 0.2 percent of antioxidant.
In this example, the non-polar base material is low density polyethylene or a mixture of low density polyethylene and ultra-low density polyethylene with a mass fraction of 80% or more, and has a melt flow rate of 0.15-0.25g/min and a density of 910-3。
In the embodiment, the nonpolar base material has a molecular weight distribution of 5.2-6.3, and the ash content of the nonpolar base material is less than or equal to 100 ppm.
In this embodiment, the crosslinking agent is a peroxide compound.
In this example, the antioxidant is a thiobis phenolic compound.
Specifically, the crosslinking agent includes: dicumyl peroxide.
Specifically, the antioxidant comprises: a bis-sulfide.
The preparation method of the crosslinkable polyethylene insulating material for the high-voltage cable comprises the following steps:
1) melting and mixing: blending the non-polar base material with an antioxidant at 125 deg.C;
2) absorption: cooling the mixture of step 1) to 80 ℃ and incorporating the cross-linking agent into the mixture by a spray absorption method;
3) drying: drying the product obtained in the step 2), and then cooling to room temperature to obtain the crosslinked polyethylene insulating material.
The crosslinkable polyethylene insulation for high voltage cables obtained in the above 5 examples and the commercially available samples a and B were subjected to the following tests:
and preserving the heat of the material at 120 ℃ for 5min, melting and pre-pressing the crosslinkable polyethylene insulating material into a film sample by using a hot vulcanizing machine at 5-10 MPa, heating to 180 ℃ for crosslinking reaction, keeping the pressure at 5-10 MPa for 10min after reaching the temperature. After the crosslinking reaction is completed, the sample is gradually cooled to room temperature, and degassing is carried out in a high-temperature environment of 70 ℃ to remove crosslinking byproducts as much as possible. Then, the volume resistivity of the insulating material test piece is tested, and a Keithley 6517 high-resistance meter (the thickness of a sample in a minimum theoretical measurement precision volume conductivity measurement test reaches 10-15A level) and a three-electrode system are adopted according to the test method of GB/T1410, and the test method is shown in the following table 1:
TABLE 1 volume resistivity Change, ρ, for examples of the invention70℃、50kV/mm/ρ30℃、10kV/mm
As can be seen from Table 1, the fact that the nonlinear change of the conductivity of the crosslinkable polyethylene insulating material for the high-voltage cable is reduced to 200-500 times from 1000-2000 times of the existing material under the conditions of 30 ℃, 10kV/mm to 70 ℃ and 50kV/mm shows that the technical scheme provided by the invention effectively inhibits the nonlinear effect of the conductivity in the high-voltage cable.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A crosslinkable polyethylene insulation material for high voltage cables, characterized in that it comprises the following components in mass percent:
97.5 to 99.3 percent of non-polar base material, 0.5 to 2 percent of cross linker and 0.1 to 0.5 percent of antioxidant.
2. The material according to claim 1, wherein the material is prepared from the following components in percentage by mass:
97.5 to 98.5 percent of non-polar base material, 1.5 to 2 percent of cross linker and 0.1 to 0.2 percent of antioxidant.
3. The material of claim 1, wherein saidThe non-polar base material is low-density polyethylene or a mixture of low-density polyethylene with the mass fraction being more than or equal to 80% and ultra-low-density polyethylene, the melt flow rate is 0.15-0.25g/min, the density is 910-3。
4. The material of claim 1, wherein the nonpolar base material has a molecular weight distribution of 5.2 to 6.3 and an ash content of the nonpolar base material of less than or equal to 100 ppm.
5. A material according to claim 1, wherein the cross-linking agent is a peroxide-based compound.
6. The material of claim 1, wherein the antioxidant is a thiobis phenolic compound.
7. A material as claimed in claim 5, wherein the cross-linking agent comprises: dicumyl peroxide.
8. The material of claim 6, wherein the antioxidant comprises: a bis-sulfide.
9. A method for preparing a crosslinkable polyethylene insulation for high voltage cables according to claim 1, characterized in that it comprises:
1) melting and mixing: mixing the non-polar base material and the antioxidant at 120-125 deg.c;
2) absorption: cooling the mixture of step 1) to 80 ℃ and incorporating the cross-linking agent into the mixture by a spray absorption method;
3) drying: drying the product obtained in the step 2), and then cooling to room temperature to obtain the crosslinked polyethylene insulating material.
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| CN (1) | CN113801385A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965543A (en) * | 2014-05-21 | 2014-08-06 | 哈尔滨理工大学 | Crosslinkable polyethylene insulation material for high-voltage direct-current cable |
| CN109942932A (en) * | 2019-02-22 | 2019-06-28 | 全球能源互联网研究院有限公司 | A kind of heatproof high-voltage cable insulating material and preparation method thereof |
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2020
- 2020-06-11 CN CN202010531953.6A patent/CN113801385A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965543A (en) * | 2014-05-21 | 2014-08-06 | 哈尔滨理工大学 | Crosslinkable polyethylene insulation material for high-voltage direct-current cable |
| CN109942932A (en) * | 2019-02-22 | 2019-06-28 | 全球能源互联网研究院有限公司 | A kind of heatproof high-voltage cable insulating material and preparation method thereof |
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