CN109337263B - Irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature and production method thereof - Google Patents
Irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature and production method thereof Download PDFInfo
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- CN109337263B CN109337263B CN201811169797.2A CN201811169797A CN109337263B CN 109337263 B CN109337263 B CN 109337263B CN 201811169797 A CN201811169797 A CN 201811169797A CN 109337263 B CN109337263 B CN 109337263B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Abstract
The invention discloses a low-temperature-processable irradiation crosslinking high-temperature-resistant cable accessory and a production method thereof, wherein the preparation material of the cable accessory comprises the following components by weight: 100 parts of ethylene-tetrafluoroethylene copolymer, wherein the molar ratio of C-F groups to C-H groups of the crosslinked ethylene-tetrafluoroethylene copolymer is 1: 2-9; 0.3-3 parts of a crosslinking agent; 0.3-4 parts of a heat-resistant agent; 0.3-3 parts of an antioxidant; 1-10 parts of antimony trioxide; 0.1-3 parts of pentaerythritol stearate; 0.1-2 parts of N' N-ethylene bis stearamide; 0.1-3 parts of white oil. The invention not only has low processing temperature and can process at the temperature of 200-238 ℃, but also can lead the cross-linking agent to be difficult to volatilize and self-polymerize, thus improving the cross-linking effect and stability of the material, and the cross-linked material has higher elongation at break and can keep the elongation at break above 200 percent.
Description
Technical Field
The invention relates to the technical field of cable accessories, in particular to an irradiation crosslinking high-temperature-resistant cable accessory and a production method thereof.
Background
Ethylene-tetrafluoroethylene copolymer (ETFE), also known as F40, is the toughest and lightest fluoroplastic, a clear crystalline material. The ETFE has excellent dielectric property, insulating property and mechanical property, and has the advantages of irradiation resistance, cracking resistance, aging resistance, various chemical solvents resistance, high and low temperature resistance and long-term working temperature of between 65 ℃ below zero and 150 ℃. After the ETFE resin is subjected to crosslinking irradiation, the radiation resistance, the tensile strength and the ageing resistance are greatly improved, the long-term working temperature is increased to 200 ℃, and the ETFE resin is widely applied to special cable insulation, such as the insulation of various cables and communication cables in transportation, aviation, chemical and nuclear plants, oil wells and underground.
The cross-linking agent of the prior X-ETFE material is easy to self-polymerize in the production process, has strict requirements on the processing temperature, has poor thermal stability in the processing process, is easy to yellow, and further deepens the color after irradiation. Chinese patent publication No. 105061876A discloses a performance-adjustable irradiation crosslinking ethylene-tetrafluoroethylene copolymer insulating material, and the problems of large smoke generation, poor thermal stability and yellowing of a crosslinking agent in the production process are improved and solved by introducing a technology of a composite crosslinking agent containing a crosslinking agent prepolymer.
Disclosure of Invention
The invention aims to solve the problems and provides a radiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature.
In order to achieve the purpose, the invention provides a radiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature, which is prepared from the following components in parts by weight: 100 parts of ethylene-tetrafluoroethylene copolymer, wherein the molar ratio of C-F groups to C-H groups of the crosslinked ethylene-tetrafluoroethylene copolymer is 1: 2-9; 0.3-3 parts of a crosslinking agent; 0.3-4 parts of a heat-resistant agent; 0.3-3 parts of an antioxidant; 1-10 parts of antimony trioxide; 0.1-3 parts of pentaerythritol stearate; 0.1-2 parts of N' N-ethylene bis stearamide; 0.1-3 parts of white oil.
Preferably, the crosslinking agent is a complex of trihydroxymethylpropane trimethacrylate and triallyl isocyanurate.
Preferably, the heat-resistant agent is cerium oxide or a composite of cerium oxide and titanium dioxide.
Preferably, the antioxidant is a complex of 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) 2, 4, 6-trimethylbenzene and N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propane ] hydrazine.
Preferably, the weight ratio of the 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) 2, 4, 6-trimethylbenzene to the N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propane ] hydrazine in the antioxidant is 1: 0.2.
The invention also provides a production method of the irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature, which comprises the following steps:
(1) and (3) processing the master batch: firstly, banburying and granulating the preparation material of the irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature by a banbury mixer or extruding the preparation material by a double-screw extruder, drawing wires and air cooling and granulating the preparation material to form master batch particles, wherein the temperature for banburying and granulating the preparation material or extruding the preparation material by the double-screw extruder is 200-238 ℃;
(2) an extrusion step: extruding the master batch particles to obtain a semi-finished product of the cable accessory through an extruder, wherein the processing temperature of the extruder is 200-238 ℃;
(3) an irradiation step: irradiating the semi-finished product of the cable accessory by an electron accelerator or a cobalt source or an ultraviolet light source;
(4) expanding and cooling: expanding the irradiated cable accessory semi-finished product by 2-6 times by using expansion equipment; and then cooling and shaping are carried out, thus obtaining the irradiation crosslinking high temperature resistant cable accessory capable of being processed at low temperature.
Compared with the prior art, the invention has the following beneficial technical effects:
the irradiation crosslinking high-temperature-resistant cable preparation material capable of being processed at low temperature is prepared by adjusting the molar ratio of C-F groups to C-H groups of a crosslinked ethylene-tetrafluoroethylene copolymer to 1: 2-9, adding a heat-resistant agent, and using a common crosslinking agent to realize the temperature resistance of 200 ℃, so that the processing temperature is low, the cable can be processed at the temperature of 200-238 ℃, the crosslinking agent is not easy to volatilize and self-polymerize, the crosslinking effect and stability of the material are improved, the elongation at break of the crosslinked material is high, and the elongation at break can be kept above 200%.
Detailed Description
In order to explain the technical contents, formulation ratios, and objects and effects of the present invention in detail, the following description will be given in conjunction with the embodiments.
The invention relates to a low-temperature-processable irradiation crosslinking high-temperature-resistant cable accessory, which is prepared from the following components in parts by weight: 100 parts of ethylene-tetrafluoroethylene copolymer, wherein the molar ratio of C-F groups to C-H groups of the crosslinked ethylene-tetrafluoroethylene copolymer is 1: 2-9; 0.3-3 parts of a crosslinking agent; 0.3-4 parts of a heat-resistant agent; 0.3-3 parts of an antioxidant; 1-10 parts of antimony trioxide; 0.1-3 parts of pentaerythritol stearate; 0.1-2 parts of N' N-ethylene bis stearamide; 0.1-3 parts of white oil.
Preferably, the crosslinking agent is a complex of trihydroxymethylpropane trimethacrylate and triallyl isocyanurate.
Preferably, the heat-resistant agent is cerium oxide or a compound of cerium oxide and titanium dioxide;
preferably, the antioxidant is a complex of 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) 2, 4, 6-trimethylbenzene and N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propane ] hydrazine.
Preferably, the weight ratio of the 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) 2, 4, 6-trimethylbenzene to the N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propane ] hydrazine in the antioxidant is 1: 0.2.
The invention also provides a production method of the irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature, which comprises the following steps:
(1) and (3) processing the master batch: firstly, banburying and granulating the preparation material of the irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature by a banbury mixer or extruding the preparation material by a double-screw extruder, drawing wires and air cooling and granulating the preparation material to form master batch particles, wherein the temperature for banburying and granulating the preparation material or extruding the preparation material by the double-screw extruder is 200-238 ℃;
(2) an extrusion step: extruding the master batch particles to obtain a semi-finished product of the cable accessory through an extruder, wherein the processing temperature of the extruder is 200-238 ℃;
(3) an irradiation step: irradiating the semi-finished product of the cable accessory by an electron accelerator or a cobalt source or an ultraviolet light source;
(4) expanding and cooling: expanding the irradiated cable accessory semi-finished product by 2-6 times by using expansion equipment; and then cooling and shaping are carried out, thus obtaining the irradiation crosslinking high temperature resistant cable accessory capable of being processed at low temperature.
Several specific examples of this embodiment of the invention are set forth below, all parts being by weight unless otherwise indicated:
example 1
The material composition of example 1 was: 100 parts of ETFE, wherein the molar ratio of C-F groups to C-H groups is 1: 2, 0.5 part of TMPTMA, 1 part of TAIC, 1 part of cerium oxide, 1 part of titanium dioxide, 13302 parts of antioxidant, 10240.4 parts of antioxidant,
5 parts of antimony trioxide, 1 part of pentaerythritol stearate, 0.5 part of N' N-ethylene bis stearamide and 1.5 parts of white oil.
Example 2
The preparation material of the embodiment 2 comprises the following components: 100 parts of ETFE, wherein the molar ratio of C-F groups to C-H groups is 1: 4, 1 part of TMPTMA, 1 part of TAIC, 1 part of cerium oxide, 2 parts of titanium dioxide, 13302 parts of antioxidant, 10240.4 parts of antioxidant, 5 parts of antimony trioxide, 1 part of pentaerythritol stearate, 0.5 part of N' N-ethylene bis stearamide and 1.5 parts of white oil.
Example 3
The preparation material of example 3 comprises the following components:
100 parts of ETFE, wherein the molar ratio of C-F groups to C-H groups is 1: 7, 1.5 parts of TMPTMA, 1 part of TAIC, 2 parts of cerium oxide, 4 parts of titanium dioxide, 13302 parts of antioxidant, 10240.4 parts of antioxidant, 5 parts of antimony trioxide, 1 part of pentaerythritol stearate, 0.5 part of N' N-ethylene bis stearamide and 1.5 parts of white oil.
Example 4
The preparation material of example 4 comprises the following components: 100 parts of ETFE, wherein the molar ratio of C-F groups to C-H groups is 1: 9, 2.5 parts of TMPTMA, 0.5 part of TAIC, 5 parts of cerium oxide, 13302 parts of antioxidant, 10240.4 parts of antioxidant, 5 parts of antimony trioxide, 1 part of pentaerythritol stearate, 0.5 part of N' N-ethylene bis stearamide and 1.5 parts of white oil.
The prepared materials of the above examples 1 to 4 are respectively used for producing the cable accessories according to the production method of the irradiation crosslinking high temperature resistant cable accessories which can be processed at low temperature.
The comparative results of the tests on the samples produced in the above examples 1 to 4 according to the above method are as follows:
the test results in the table show that the invention can effectively improve the elongation at break before aging of the insulation, the absolute value of the elongation at break after the aging test is carried out for 200 ℃ and 260 hours is more than 150%, and the insulation can be processed at the temperature of 200-238 ℃, the lower processing temperature reduces the requirements of processing equipment, so that the cross-linking agent is not easy to volatilize and self-polymerize, the cross-linking effect and the stability of the material are improved, and meanwhile, the irradiation cross-linking high-temperature resistant cable accessory can resist the temperature of 200 ℃. The elongation at break of the cross-linked material is high, and the elongation at break can be kept above 200%.
The present invention is not limited to the above-described embodiments, and various changes may be made by those skilled in the art, which changes are equivalent or similar to the present invention and are intended to be included within the scope of the appended claims.
Claims (3)
1. The utility model provides a but high temperature resistant cable accessories of irradiation crosslinking of low temperature processing which characterized in that: the preparation material comprises the following components by weight: 100 parts of ethylene-tetrafluoroethylene copolymer, wherein the molar ratio of C-F groups to C-H groups of the crosslinked ethylene-tetrafluoroethylene copolymer is 1: 2-7; 0.3-3 parts of a crosslinking agent; 0.3-4 parts of a heat-resistant agent; 0.3-3 parts of an antioxidant; 1-10 parts of antimony trioxide; 0.1-3 parts of pentaerythritol stearate; 0.1-2 parts of N' N-ethylene bis stearamide; 0.1-3 parts of white oil;
wherein the cross-linking agent is a compound of trihydroxy methyl propane trimethacrylate and triallyl isocyanurate;
the heat-resistant agent is a compound of cerium oxide and titanium dioxide;
the antioxidant is a compound of 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) 2, 4, 6-trimethylbenzene and N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propane ] hydrazine.
2. The cryogenically-processable radiation-crosslinked, high temperature-resistant cable accessory of claim 1, wherein: in the antioxidant, the weight ratio of 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) 2, 4, 6-trimethylbenzene to N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propane ] hydrazine is 1: 0.2.
3. A method for producing a low temperature processable radiation cross-linked high temperature resistant cable accessory according to claim 1 or 2, characterized by the steps of:
(1) and (3) processing the master batch: firstly, banburying and granulating the preparation material of the low-temperature-processable irradiation crosslinking high-temperature-resistant cable accessory in the claim 1 or 2 by using a banbury mixer or extruding, drawing and air-cooling and granulating the preparation material by using a double-screw extruder to form master batch particles, wherein the banburying and granulating temperature of the banbury mixer or the extruding temperature of the master batch particles by using the double-screw extruder is 200-238 ℃;
(2) an extrusion step: extruding the master batch particles to obtain a semi-finished product of the cable accessory through an extruder, wherein the processing temperature of the extruder is 200-238 ℃;
(3) an irradiation step: irradiating the semi-finished product of the cable accessory by an electron accelerator or a cobalt source or an ultraviolet light source;
(4) expanding and cooling: expanding the irradiated cable accessory semi-finished product by 2-6 times by using expansion equipment; and then cooling and shaping are carried out, thus obtaining the irradiation crosslinking high temperature resistant cable accessory capable of being processed at low temperature.
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| CN201811169797.2A CN109337263B (en) | 2018-10-08 | 2018-10-08 | Irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature and production method thereof |
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| CN201811169797.2A CN109337263B (en) | 2018-10-08 | 2018-10-08 | Irradiation crosslinking high-temperature-resistant cable accessory capable of being processed at low temperature and production method thereof |
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| CN109337263B true CN109337263B (en) | 2022-04-15 |
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| JPH07292199A (en) * | 1994-04-28 | 1995-11-07 | Asahi Glass Co Ltd | Fluoropolymer composition and method for crosslinking the same |
| CN103059382A (en) * | 2013-01-16 | 2013-04-24 | 上海伟星新型建材有限公司 | Method for preparing high-performance irradiation cross-linking ultrahigh polyethylene extrusion plate |
| CN106188815B (en) * | 2015-02-05 | 2018-11-27 | 中广核三角洲（江苏）塑化有限公司 | The crosslinked ethene-tetrafluoroethylene copolymer material of heat resistant |
| CN104710794B (en) * | 2015-04-09 | 2017-09-22 | 深圳科创新源新材料股份有限公司 | Automatic solidification insulating protection material and its method of manufacturing technology |
| CN105061876A (en) * | 2015-08-06 | 2015-11-18 | 中广核三角洲（江苏）塑化有限公司 | Adjustable performance irradiation crosslinking ethylene-tetrafluoroethene copolymer insulation material |
| CN106317598B (en) * | 2016-08-30 | 2019-04-30 | 上海电缆研究所有限公司 | A kind of crosslinking fluoroplastics heat-shrinkable T bush and preparation method thereof |
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