CN109337263A - Can low temperature process cross-linking radiation high temperature-resistant cable attachment and production method - Google Patents
Can low temperature process cross-linking radiation high temperature-resistant cable attachment and production method Download PDFInfo
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- CN109337263A CN109337263A CN201811169797.2A CN201811169797A CN109337263A CN 109337263 A CN109337263 A CN 109337263A CN 201811169797 A CN201811169797 A CN 201811169797A CN 109337263 A CN109337263 A CN 109337263A
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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
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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
- H01B3/443—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
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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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- 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
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- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention disclose it is a kind of can low temperature process cross-linking radiation high temperature-resistant cable attachment and production method, by weight, the material for preparing of cable accessory includes following component: 100 parts of ethylene-tetrafluoroethylene copolymer, the C-F group of the crosslinked ethene-tetrafluoroethylene copolymer and the molar ratio of C-H group are 1: (2-9)；0.3~3 part of crosslinking agent；0.3~4 part of heat-resistant agent；0.3~3 part of antioxidant；1~10 part of antimony oxide；0.1~3 part of pentaerythritol stearate；0.1~2 part of N ' N- ethylene bis stearamide；0.1~3 part of white oil.Not only processing temperature is low by the present invention, can 200 DEG C~238 DEG C at a temperature of process, and crosslinking agent can be made not volatile, it is not easy autohemagglutination, the cross-linking effect and stability of material are improved, the elongation at break of material is higher after crosslinking, and elongation at break is positively retained at 200% or more.
Description
Technical field
The present invention relates to cable accessory technical field more particularly to cross-linking radiation high temperature-resistant cable attachment and production methods.
Background technique
Ethylene-tetrafluoroethylene copolymer (ETFE) is also known as F40, and clear crystals material is most tough and most light fluoroplastics.
ETFE has excellent dielectricity, insulation performance and mechanical property, and radiation resistance, resistance to cracking is ageing-resistant, resistance to various chemical solution
Agent, high-low temperature resistant, long-term operating temperature is between -65 DEG C~150 DEG C.After the crosslinked irradiation of ETFE resin, radiation resistance, tension
Intensity and anti-aging property greatly promote, and long-term operating temperature is increased to 200 DEG C, are widely used in special cable insulation, such as
The insulation of transport, aviation, chemistry and nuclear plant, oil well and underground various cables and communication cable.
The current X-ETFE material easy autohemagglutination of crosslinking agent in process of production, processing temperature is required it is harsh, processed
Thermal stability is poor in journey, easily turns to be yellow, and color is further deepened after irradiation.Chinese patent publication No. 105061876A is disclosed
A kind of adjustable cross-linking radiation ethylene-tetrafluoroethylene copolymer Insulation Material of performance, by introducing a kind of pre-polymerization containing crosslinking agent
The technology of the multiple crosslinking agent of body, improves and solves that above-mentioned production process smoke amount is big, and crosslinking agent thermal stability is poor, and jaundice is asked
Topic, however, crosslinking agent performed polymer is difficult to produce, and volatile, stability is to be improved.
Summary of the invention
It is an object of the invention in view of the above-mentioned problems, provide it is a kind of can low temperature process cross-linking radiation high temperature-resistant cable it is attached
Part.
To reach above-mentioned purpose, the present invention provide it is a kind of can low temperature process cross-linking radiation high temperature-resistant cable attachment, by weight
Meter, preparing material includes following component: 100 parts of ethylene-tetrafluoroethylene copolymer, the cross-linked ethylene-tetrafluoroethene is total
The C-F group of polymers and the molar ratio of C-H group are 1: (2-9)；0.3~3 part of crosslinking agent；0.3~4 part of heat-resistant agent；Antioxidant
0.3~3 part；1~10 part of antimony oxide；0.1~3 part of pentaerythritol stearate；N ' N- ethylene bis stearamide 0.1~2
Part；0.1~3 part of white oil.
Preferably, the crosslinking agent is trihydroxy methyl propane trimethyl acrylic ester and triallyl isocyanurate
Compound.
Preferably, the heat-resistant agent is the compound of cerium oxide or cerium oxide, titanium dioxide.
Preferably, the antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) 2,4,6- trimethylbenzenes with
The compound of bis- [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propane] hydrazines of N, N '-.
Preferably, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) 2,4,6- trimethylbenzenes in the antioxidant
With N, the weight ratio of bis- [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propane] hydrazines of N '-is 1: 0.2.
The present invention also provides it is a kind of can low temperature process cross-linking radiation high temperature-resistant cable attachment production method, including it is as follows
Step:
(1) masterbatch procedure of processing: first by it is above-mentioned can low temperature process cross-linking radiation high temperature-resistant cable attachment preparation
Material is granulated through mixer mixing or forms masterbatch pellet through double screw extruder extrusion, wire drawing, air-cooled pelletizing shape again, wherein
The temperature that mixer mixing is granulated or squeezes out again through double screw extruder is 200 DEG C~238 DEG C；
(2) extrusion step: by above-mentioned masterbatch pellet by extruder squeeze out cable accessory semi-finished product, wherein extruder plus
Work temperature is 200 DEG C~238 DEG C；
(3) irradiation steps: above-mentioned cable accessory semi-finished product are irradiated by electron accelerator or cobalt source or ultraviolet source；
(4) the cable accessory semi-finished product after irradiation expansion, cooling step: are subjected to 2-6 times of expansion with expansion device；Then
Carry out it is cooling, be formed to get to can low temperature process cross-linking radiation high temperature-resistant cable attachment.
The present invention has following advantageous effects compared with prior art:
The present invention can low temperature process cross-linking radiation high temperature resistant cable prepare material pass through cross-linked ethylene-tetrafluoroethene is total
The C-F group of polymers and the molar ratio of C-H group are adjusted to 1: (2-9), while heat-resistant agent is added, and it is using common crosslinking agent
Can reach 200 DEG C of heatproof, not only processing temperature is low, can 200 DEG C~238 DEG C at a temperature of process, and crosslinking agent can be made
It is not volatile, it is not easy autohemagglutination, improves the cross-linking effect and stability of material, the elongation at break of material is higher after crosslinking, fracture
Elongation is positively retained at 200% or more.
Specific embodiment
For the technology contents, formula rate, the objects and the effects that the present invention will be described in detail, below in conjunction with embodiment
It is explained in detail.
The present invention can low temperature process cross-linking radiation high temperature-resistant cable attachment, by weight, prepare material include it is following
Component: 100 parts of ethylene-tetrafluoroethylene copolymer, C-F group and the C-H group of the crosslinked ethene-tetrafluoroethylene copolymer
Molar ratio is 1: (2-9)；0.3~3 part of crosslinking agent；0.3~4 part of heat-resistant agent；0.3~3 part of antioxidant；Antimony oxide 1~10
Part；0.1~3 part of pentaerythritol stearate；0.1~2 part of N ' N- ethylene bis stearamide；0.1~3 part of white oil.
Preferably, the crosslinking agent is trihydroxy methyl propane trimethyl acrylic ester and triallyl isocyanurate
Compound.
Preferably, the heat-resistant agent is the compound of cerium oxide or cerium oxide, titanium dioxide；
Preferably, the antioxidant be 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) 2,4,6- trimethylbenzenes with
The compound of bis- [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propane] hydrazines of N, N '-.
Preferably, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) 2,4,6- trimethylbenzenes in the antioxidant
With N, the weight ratio of bis- [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propane] hydrazines of N '-is 1: 0.2.
The present invention also provides it is a kind of can low temperature process cross-linking radiation high temperature-resistant cable attachment production method, including it is as follows
Step:
(1) masterbatch procedure of processing: first by it is above-mentioned can low temperature process cross-linking radiation high temperature-resistant cable attachment preparation
Material is granulated through mixer mixing or forms masterbatch pellet through double screw extruder extrusion, wire drawing, air-cooled pelletizing shape again, wherein
The temperature that mixer mixing is granulated or squeezes out again through double screw extruder is 200 DEG C~238 DEG C；
(2) extrusion step: by above-mentioned masterbatch pellet by extruder squeeze out cable accessory semi-finished product, wherein extruder plus
Work temperature is 200 DEG C~238 DEG C；
(3) irradiation steps: above-mentioned cable accessory semi-finished product are irradiated by electron accelerator or cobalt source or ultraviolet source；
(4) the cable accessory semi-finished product after irradiation expansion, cooling step: are subjected to 2-6 times of expansion with expansion device；Then
Carry out it is cooling, be formed to get to can low temperature process cross-linking radiation high temperature-resistant cable attachment.
Present embodiment several specific embodiments of the invention are described below, and unless otherwise indicated, all numbers are with weight
Meter:
Embodiment 1
The material component of embodiment 1 are as follows: 100 parts of ETFE, wherein the molar ratio of C-F group and C-H group is 1: 2,
0.5 part of TMPTMA, 1 part of TAIC, 1 part of cerium oxide, 1 part of titanium dioxide, 1,330 2 parts of antioxidant, 1,024 0.4 parts of antioxidant,
5 parts of antimony oxide, 1 part of pentaerythritol stearate, 0.5 part of N ' N- ethylene bis stearamide, 1.5 parts of white oil.
Embodiment 2
Embodiment 2 prepares material component are as follows: and 100 parts of ETFE, wherein the molar ratio of C-F group and C-H group is 1: 4,
1 part of TMPTMA, 1 part of TAIC, 1 part of cerium oxide, 2 parts of titanium dioxide, 1,330 2 parts of antioxidant, 1,024 0.4 parts of antioxidant, three
Aoxidize 5 parts of two antimony, 1 part of pentaerythritol stearate, 0.5 part of N ' N- ethylene bis stearamide, 1.5 parts of white oil.
Embodiment 3
Embodiment 3 prepares material component are as follows:
100 parts of ETFE, wherein the molar ratio of C-F group and C-H group is 1.5 parts of 1: 7, TMPTMA, 1 part of TAIC, oxygen
Change 2 parts of cerium, 4 parts of titanium dioxide, 1,330 2 parts of antioxidant, 1,024 0.4 parts of antioxidant, 5 parts of antimony oxide, pentaerythrite is hard
1 part of resin acid ester, 0.5 part of N ' N- ethylene bis stearamide, 1.5 parts of white oil.
Embodiment 4
Embodiment 4 prepares material component are as follows: and 100 parts of ETFE, wherein the molar ratio of C-F group and C-H group is 1: 9,
2.5 parts of TMPTMA, 0.5 part of TAIC, 5 parts of cerium oxide, 1,330 2 parts of antioxidant, 1,024 0.4 parts of antioxidant, antimony oxide 5
Part, 1 part of pentaerythritol stearate, 0.5 part of N ' N- ethylene bis stearamide, 1.5 parts of white oil.
By above-described embodiment 1 to embodiment 4 prepare material respectively according to it is above-mentioned can low temperature process the resistance to height of cross-linking radiation
The production method of warm cable accessory produces cable accessory.
The sample test comparing result that above embodiments 1 to embodiment 4 is produced according to the method described above is as follows:
From the test result in table can be seen that the present invention can effectively improve the aging of insulation before elongation at break,
200 DEG C, 150% or more elongation at break absolute value after 260 hours degradations, and can be in 200 DEG C~238 DEG C of temperature
The lower processing of degree, lower processing temperature reduce the requirement of process equipment, this can make crosslinking agent not volatile, be not easy autohemagglutination, improve
The cross-linking effect and stability of material, while cross-linking radiation high temperature-resistant cable attachment heatproof of the present invention reaches 200 DEG C.Material after crosslinking
The elongation at break of material is higher, and elongation at break is positively retained at 200% or more.
The invention is not limited to above-mentioned specific embodiment, those skilled in the art can also make a variety of accordingly
Variation, but any be equal or similar variation should all be covered within the scope of the claims with of the invention.
Claims (6)
1. one kind can low temperature process cross-linking radiation high temperature-resistant cable attachment, it is characterised in that: by weight, prepare material packet
Containing following component: 100 parts of ethylene-tetrafluoroethylene copolymer, the C-F group and C-H of the crosslinked ethene-tetrafluoroethylene copolymer
The molar ratio of group is 1: (2-9)；0.3~3 part of crosslinking agent；0.3~4 part of heat-resistant agent；0.3~3 part of antioxidant；Antimony oxide
1~10 part；0.1~3 part of pentaerythritol stearate；0.1~2 part of N ' N- ethylene bis stearamide；0.1~3 part of white oil.
2. it is according to claim 1 can low temperature process cross-linking radiation high temperature-resistant cable attachment, it is characterised in that: the friendship
Join the compound that agent is trihydroxy methyl propane trimethyl acrylic ester and triallyl isocyanurate.
3. it is according to claim 1 can low temperature process cross-linking radiation high temperature-resistant cable attachment, it is characterised in that: it is described resistance to
Thermit powder is the compound of cerium oxide or cerium oxide, titanium dioxide.
4. it is according to claim 1 can low temperature process cross-linking radiation high temperature-resistant cable attachment, it is characterised in that: it is described anti-
Oxygen agent is 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) 2,4,6- trimethylbenzenes and bis- [β-(3, the 5- bis- tertiary fourths of N, N '-
Base -4- hydroxy phenyl) propane] hydrazine compound.
5. it is according to claim 4 can low temperature process cross-linking radiation high temperature-resistant cable attachment, it is characterised in that: it is described anti-
1 in oxygen agent, 3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) 2,4,6- trimethylbenzenes and bis- [β-(3,5- bis- uncles of N, N '-
Butyl -4- hydroxy phenyl) propane] hydrazine weight ratio be 1: 0.2.
6. it is a kind of it is according to any one of claims 1 to 5 can low temperature process cross-linking radiation high temperature-resistant cable attachment life
Production method, it is characterised in that include the following steps:
(1) masterbatch procedure of processing: first by it is described in any one of claim 1 to 5 can low temperature process cross-linking radiation high temperature resistant
The material for preparing of cable accessory is granulated through mixer mixing or is formed again through double screw extruder extrusion, wire drawing, air-cooled pelletizing shape
Masterbatch pellet, wherein the temperature that mixer mixing is granulated or squeezes out again through double screw extruder is 200 DEG C~238 DEG C；
(2) extrusion step: above-mentioned masterbatch pellet is squeezed out into cable accessory semi-finished product by extruder, wherein the processing temperature of extruder
Degree is 200 DEG C~238 DEG C；
(3) irradiation steps: above-mentioned cable accessory semi-finished product are irradiated by electron accelerator or cobalt source or ultraviolet source；
(4) the cable accessory semi-finished product after irradiation expansion, cooling step: are subjected to 2-6 times of expansion with expansion device；Then it carries out
It is cooling, be formed to get to can low temperature process cross-linking radiation high temperature-resistant cable attachment.
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| Application Number | Priority Date | Filing Date | Title |
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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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| Application Number | Priority Date | Filing Date | Title |
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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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| CN109337263A true CN109337263A (en) | 2019-02-15 |
| CN109337263B CN109337263B (en) | 2022-04-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724503A (en) * | 2020-12-31 | 2021-04-30 | 深圳市沃尔核材股份有限公司 | Heat-shrinkable sleeve and manufacturing method thereof |
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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 |
| CN104629159A (en) * | 2015-02-05 | 2015-05-20 | 中广核三角洲（江苏）塑化有限公司 | Crosslinked ethylene-tetrafluoroethylene copolymer insulating material |
| CN104710794A (en) * | 2015-04-09 | 2015-06-17 | 深圳科创新源工业材料有限公司 | Automatic-curing insulation protective material and manufacturing technique thereof |
| 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 |
| CN106317598A (en) * | 2016-08-30 | 2017-01-11 | 上海电缆研究所 | Cross-linked fluoroplastic heat-shrinkable tube and preparation method thereof |
-
2018
- 2018-10-08 CN CN201811169797.2A patent/CN109337263B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104629159A (en) * | 2015-02-05 | 2015-05-20 | 中广核三角洲（江苏）塑化有限公司 | Crosslinked ethylene-tetrafluoroethylene copolymer insulating material |
| CN104710794A (en) * | 2015-04-09 | 2015-06-17 | 深圳科创新源工业材料有限公司 | Automatic-curing insulation protective material and manufacturing technique thereof |
| 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 |
| CN106317598A (en) * | 2016-08-30 | 2017-01-11 | 上海电缆研究所 | Cross-linked fluoroplastic heat-shrinkable tube and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724503A (en) * | 2020-12-31 | 2021-04-30 | 深圳市沃尔核材股份有限公司 | Heat-shrinkable sleeve and manufacturing method thereof |
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