CN113248832A - High-voltage direct-current polypropylene cable material - Google Patents
High-voltage direct-current polypropylene cable material Download PDFInfo
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- CN113248832A CN113248832A CN202110147115.3A CN202110147115A CN113248832A CN 113248832 A CN113248832 A CN 113248832A CN 202110147115 A CN202110147115 A CN 202110147115A CN 113248832 A CN113248832 A CN 113248832A
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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Abstract
The invention provides a high-voltage direct-current polypropylene cable material which comprises the following components in parts by weight: 100 parts of copolymerization modified polypropylene material and 0.5-1 part of antioxidant. The high-voltage direct-current polypropylene cable material disclosed by the invention adopts the copolymerized polypropylene directly produced by a petrochemical device as an insulating material, and the antioxidant is added, so that the high-voltage direct-current polypropylene cable material has excellent mechanical property and electrical property, can replace crosslinked polyethylene to be used as the insulating material of a high-voltage cable, is environment-friendly as the copolymerized polypropylene is a thermoplastic material, can be recycled after the cable is retired, and reduces the use cost of the cable material.
Description
Technical Field
The invention relates to the technical field of power systems, in particular to a high-voltage direct-current polypropylene cable material and a preparation method thereof.
Background
XLPE (crosslinked polyethylene cable) has excellent mechanical property and electrical property, and is the main insulating material of the current extrusion-coated cable. But the byproducts generated in the cross-linking process of the cross-linked polyethylene are not easy to remove, the control difficulty of the purity of the cable is high, and the breakdown performance and the space charge performance of the cable are greatly influenced. Meanwhile, the cross-linking and degassing processes are high in energy consumption and low in production efficiency, the retired insulating part is difficult to recycle, and the environmental pollution is great due to incineration or landfill. Therefore, it is very important to develop an environmentally friendly cable satisfying mechanical and electrical properties. Polypropylene is a thermoplastic material with good electrical properties and can be recycled after its lifetime has ended. However, the isotactic polypropylene has some disadvantages, such as high brittleness, poor low-temperature performance, etc., which make it impossible to be directly applied to cable materials.
Disclosure of Invention
In view of the above, the invention provides a high-voltage direct-current polypropylene cable material, and aims to solve the problem that the existing polypropylene cable material cannot be popularized and used in cable materials due to poor low-temperature performance.
In one aspect, the invention provides a high-voltage direct-current polypropylene cable material, which comprises the following components in parts by weight: 100 parts of copolymerization modified polypropylene material and 0.5-1 part of antioxidant.
Further, in the high-voltage direct-current polypropylene cable material, the antioxidant is selected from one or more of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
Further, in the high-voltage direct-current polypropylene cable material, in the antioxidant, the mass fraction of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine in the total mass of the antioxidant is more than or equal to 50%.
Further, in the high-voltage direct-current polypropylene cable material, in the antioxidant, the mass fractions of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite ester and 4,4' -thiobis (6-tert-butyl-3-methylphenol) in the total mass of the antioxidant are respectively greater than or equal to 10% and less than or equal to 20%.
Further, in the high-voltage direct-current polypropylene cable material, the copolymerization modified polypropylene is isotactic polypropylene or atactic polypropylene.
Further, in the high-voltage direct-current polypropylene cable material, the melt index of the copolymerization modified polypropylene is 2 +/-0.5 g/10 min.
Further, in the high-voltage direct-current polypropylene cable material, the copolymerization modified polypropylene is prepared by adding propylene, a main catalyst, a cocatalyst or an external electron donor, hydrogen and ethylene into an industrial petrochemical device for catalytic reaction.
Further, in the high-voltage direct-current polypropylene cable material, the ethylene content in the prepared copolymerization modified polypropylene is 10wt% -40 wt%.
The high-voltage direct-current polypropylene cable material disclosed by the invention adopts the co-polypropylene as an insulating material, and the antioxidant is added, so that the high-voltage direct-current polypropylene cable material has excellent mechanical property and electrical property, can replace the cross-linked polyethylene to be used as an insulating material of a high-voltage cable, is environment-friendly because the co-polypropylene is a thermoplastic material, can be recycled after the cable is retired, and reduces the use cost of the cable material.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1a is a typical polarization microscope image of a polypropylene cable material prepared in comparative example 1 according to the present invention;
FIG. 1b is a typical polarization microscope image of the polypropylene cable material prepared in example 1 of the present invention;
FIG. 2a is a typical polarization microscope image of the polypropylene cable material prepared in comparative example 2 of the present invention;
fig. 2b is a typical polarization microscope image of the polypropylene cable material prepared in example 2 of the present invention.
Detailed Description
While the preferred embodiments of the present invention are described below, it should be understood that various changes and modifications can be made by one skilled in the art without departing from the principles of the invention, and such changes and modifications are also considered to be within the scope of the invention.
The high-voltage direct-current polypropylene cable material provided by the invention comprises the following components in parts by weight: 100 parts of copolymerization modified polypropylene material and 0.5-1 part of antioxidant. Namely: taking a copolymerization modified polypropylene material as a matrix, and adding 0.5-1 part of antioxidant into 100 parts of the copolymerization modified polypropylene material. The copolymerization modified polypropylene material is directly produced by a petrochemical device, and specifically, the copolymerization modified polypropylene is prepared by adding propylene, a main catalyst, a cocatalyst or an external electron donor, hydrogen and ethylene into an industrial petrochemical device for catalytic reaction. In the raw materials for preparing the copolymerization modified polypropylene, the content of ethylene is 10-40 wt%.
Wherein: the melt index of the copolymerization modified polypropylene is 2 +/-0.5 g/10min, and the determination conditions of the melt index are as follows: the 2.16kg force test was applied at 230 ℃.
The antioxidant is selected from one or more of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy phenyl) propionic acid ] pentaerythritol ester, tri (2, 4-di-tert-butylphenyl) phosphite and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
In the antioxidant, 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine accounts for more than or equal to 50% of the total mass of the antioxidant, and has the functions of oxidation resistance and copper resistance.
That is, in the antioxidant, only 1, 2-bis (3, 5-di-t-butyl-4-hydroxy-phenylpropionic acid) hydrazine may be added without adding tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-t-butylphenyl) phosphite and 4,4' -thiobis (6-t-butyl-3-methylphenol).
When the antioxidant is added with tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 4,4' -thiobis (6-tert-butyl-3-methylphenol), the mass fraction of each of the three antioxidants accounts for more than or equal to 10% and less than or equal to 20% of the total mass of the antioxidant. Of course, the mass fractions of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite and 4,4' -thiobis (6-tert-butyl-3-methylphenol) based on the total mass of the antioxidant may be the same or different.
In the embodiment of the invention, the copolymerization modified cable insulating material is produced by directly carrying out catalytic copolymerization modification granulation by a petrochemical device, and meanwhile, the antioxidant is added into the petrochemical device in the material copolymerization modification process. The modified insulating material can be directly used for producing novel environment-friendly high-voltage polypropylene cables. Compared with the prior art, the preparation method of the invention, which is used for modifying the high-voltage direct-current cable by using double screws in a laboratory and a cable plant, can avoid the introduction of impurities such as dust and the like caused by secondary processing, and ensure the purity of the insulating material to the greatest extent from the source.
The invention is described in detail below in terms of several specific examples.
Example 1
100 parts of isotactic polypropylene obtained by modifying isotactic polypropylene, 0.8 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine and 0.15 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ] pentaerythritol ester are respectively added into a granulating device to be directly granulated to obtain the polypropylene cable material.
Example 2
Respectively adding 100 parts of random copolymerization polypropylene obtained by modifying random polypropylene, 0.6 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ] pentaerythritol ester, 0.1 part of tris (2.4-di-tert-butylphenyl) phosphite and 0.1 part of 4,4' -thiobis (6-tert-butyl-3-methylphenol) into a granulating device for direct granulation to obtain the polypropylene cable material.
Example 3
100 parts of isotactic polypropylene obtained by modifying isotactic polypropylene, 0.4 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine and 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ] pentaerythritol ester are respectively added into a granulating device to be directly granulated to obtain the polypropylene cable material.
Example 4
100 parts of random copolymer polypropylene obtained by modifying random polypropylene, 0.55 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, 0.15 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ] pentaerythritol ester, 0.15 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.15 part of 4,4' -thiobis (6-tert-butyl-3-methylphenol) are added into a granulating device to be directly granulated to obtain the polypropylene cable material.
Comparative example 1
100 parts of isotactic polypropylene and 0.9 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine are respectively added into a granulating device to be directly granulated to obtain the polypropylene cable material.
Comparative example 2
Respectively adding 100 parts of atactic polypropylene, 0.5 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ] pentaerythritol ester, 0.1 part of tris (2.4-di-tert-butylphenyl) phosphite and 0.1 part of 4,4' -thiobis (6-tert-butyl-3-methylphenol) into a granulating device for direct granulation to obtain the polypropylene cable material.
The polypropylene cable materials prepared in examples 1 and 2 and comparative examples 1 and 2 were subjected to performance tests, and the test results are shown in the following table:
it can be seen that the elongation at break of the polypropylene cable materials prepared in examples 1 and 2 of the present invention is greatly improved compared with the unmodified polypropylene insulation materials in comparative examples 1 and 2, and the polypropylene after copolymerization modification has a greatly reduced elastic modulus, and the materials have better flexibility, and the copolymerized polypropylene has more excellent mechanical properties. Meanwhile, as can be seen from the volume resistivity at normal temperature and high temperature, the temperature-dependent change after copolymerization modification is smaller; the polypropylene material modified by copolymerization has great advantages in the aspects of tensile property and temperature volume resistivity.
Further, the polypropylene cable materials prepared in example 1, comparative example 1, example 2 and comparative example 2 of the present invention were scanned by a polarization microscope, and the morphology structure of the obtained polypropylene insulation material shows that: in the appearance diagram of the polypropylene insulating material in the comparative example 1, the spherical crystal surface is smooth, and the cross extinction phenomenon is obvious; the morphology of the polypropylene insulating material in example 1 can see a complete spherulite structure, the spherulite outline is obvious, the surface structure of the spherulite is rough, and certain impurities seem to exist on the spherulite structure; in the morphology chart of the polypropylene insulating material in the comparative example 2, stray crystals are not formed, an obvious spherulite structure cannot be observed, and a large number of crystal nuclei are generated in the visual field range of the two materials in the crystallization process; in the morphology chart of the polypropylene insulating material in the example 2, a complete spherulite structure is difficult to find, and most of crystals exist in a crushed crystal form.
Because higher crystallinity and bigger crystal size are favorable for breakdown strength, breakdown type faults possibly occurring in the operation process of the cable are prevented, but the high crystallinity also can increase the mechanical strength of the material, increase the brittleness and is not favorable for the construction and installation of the cable. A balance between mechanical and electrical properties needs to be adjusted according to the copolymerization modification. The typical core-shell structure observed in fig. 1b and fig. 2b is a specific structure in the co-modified PP, and the structure can balance the mechanical properties of the material with the mechanical properties.
In conclusion, the high-voltage direct-current polypropylene cable material provided by the invention mainly comprises the copolymerization modified polypropylene material and the antioxidant, the elongation at break of the polypropylene cable material prepared from the components is greatly improved and exceeds that of XLPE (about 500%), the elastic modulus is greatly reduced, the flexibility of the material is better, the cable is favorably laid, and the copolymerization polypropylene has excellent mechanical properties. Meanwhile, the cable material after copolymerization modification has smaller temperature change.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The high-voltage direct-current polypropylene cable material is characterized by comprising the following components in parts by weight: 100 parts of copolymerization modified polypropylene material and 0.5-1 part of antioxidant.
2. The high-voltage direct current polypropylene cable material according to claim 1, wherein the antioxidant is selected from one or more of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
3. The high-voltage direct current polypropylene cable material according to claim 3, wherein the mass fraction of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine in the antioxidant in the total mass of the antioxidant is greater than or equal to 50%.
4. The high-voltage direct current polypropylene cable material according to claim 3, wherein in the antioxidant, the mass fractions of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 4,4' -thiobis (6-tert-butyl-3-methylphenol) in the total mass of the antioxidant are respectively greater than or equal to 10% and less than or equal to 20%.
5. The high-voltage direct current polypropylene cable material according to claim 1, wherein the co-modified polypropylene is isotactic polypropylene or atactic polypropylene.
6. The high-voltage direct current polypropylene cable material according to claim 1, wherein the melt index of the co-polymerized modified polypropylene is 2 ± 0.5g/10 min.
7. The high-voltage direct-current polypropylene cable material as claimed in claim 1, wherein the co-polymerized modified polypropylene is prepared by adding propylene, a main catalyst, a cocatalyst or an external electron donor, hydrogen and ethylene into an industrial petrochemical device to perform a catalytic reaction.
8. The high-voltage direct current polypropylene cable material according to claim 7, wherein the ethylene content in the prepared copolymerization modified polypropylene is 10wt% to 40 wt%.
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| CN202110147115.3A CN113248832A (en) | 2021-02-03 | 2021-02-03 | High-voltage direct-current polypropylene cable material |
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| CN202110147115.3A CN113248832A (en) | 2021-02-03 | 2021-02-03 | High-voltage direct-current polypropylene cable material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114015154A (en) * | 2021-11-09 | 2022-02-08 | 南方电网科学研究院有限责任公司 | Preparation method of environment-friendly high-voltage cable polypropylene insulating material |
| CN114106504A (en) * | 2021-09-06 | 2022-03-01 | 中国电力科学研究院有限公司 | Thermoplastic medium-voltage cable insulating material and preparation method thereof |
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2021
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| CN114106504A (en) * | 2021-09-06 | 2022-03-01 | 中国电力科学研究院有限公司 | Thermoplastic medium-voltage cable insulating material and preparation method thereof |
| CN114015154A (en) * | 2021-11-09 | 2022-02-08 | 南方电网科学研究院有限责任公司 | Preparation method of environment-friendly high-voltage cable polypropylene insulating material |
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