CN105295190A - Functionalized high polymer composite material with carbon black and graphene as conductive mediums - Google Patents
Functionalized high polymer composite material with carbon black and graphene as conductive mediums Download PDFInfo
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- CN105295190A CN105295190A CN201510922025.1A CN201510922025A CN105295190A CN 105295190 A CN105295190 A CN 105295190A CN 201510922025 A CN201510922025 A CN 201510922025A CN 105295190 A CN105295190 A CN 105295190A
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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
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
Abstract
The invention relates to a high polymer composite material for the semiconductive shielding inside and outside 6kV-220kV cross-linked polyethylene insulated high-voltage cables and particularly relates to a functionalized high polymer composite material with carbon black and graphene as conductive media. The functionalized high polymer composite material comprises the following components in percentage by weight: 55%-62% of ethylene-vinyl acetate copolymer or polyethylene, 23%-30% of conductive carbon black, 1%-5% of graphene powder, 8%-12% of white oil, 0.5%-1% of an antioxidant, 0.3%-1% of zinc stearate and 0.6%-1.2% of a cross-linking agent DCP. According to the functionalized high polymer composite material, the conductivity of a semiconductive shielding material product can be remarkably improved, and furthermore, the thermal stability of the semiconductive shielding material product is substantially improved.
Description
Technical field
The present invention relates to a kind of polymer composite, particularly relate to a kind of carbon black, functionalized macromolecular matrix material that Graphene is conducting medium.
Background technology
Crosslinked polyetylene insulated high-tension cable (crosslinked cable) is a kind of power cable that in power transmission and distribution field, usage quantity is very large.The semiconductive shieldin material of current crosslinked cable mainly adopts the dispersed mode adding carbon black in ethylene-vinyl acetate copolymer EVA to make, but because and factor that thermostability not good undesirable by carbon black conductive affects, cause the volume specific resistance index of current material undesirable, the standard of execution also can only be relaxed in index of correlation requirement.Be for the volume specific resistance of the semiconductive shieldin material of conductor shielding and insulation shielding when requiring 20 DEG C in current standard (JB/T10738-2007) and be not more than 100 Ω cm, the volume specific resistance being used for the semiconductive shieldin material of conductor shielding when 90 DEG C is not more than 5000 Ω cm, and the volume specific resistance being used for the semiconductive shieldin material of insulation shielding when 90 DEG C is and is not more than 2500 Ω cm.Its volume specific resistance visible is bigger than normal and thermostability is quite bad (20 DEG C with 90 DEG C of lower volume change in resistance more than 20 times).Thus not ideal enough to cable shield homogenizing electric field effect, easily cause cable to run discharge fault and life-span decline, particularly evident on the impact of 110kV and above extra-high-tension cable.
Summary of the invention
The present invention is intended to address the aforementioned drawbacks, and provides a kind of carbon black, Graphene to be the functionalized macromolecular matrix material of conducting medium.
In order to overcome the defect existed in background technology, the technical solution adopted for the present invention to solve the technical problems is: this carbon black, Graphene are that the functionalized macromolecular matrix material of conducting medium comprises following mass percentage composition: ethylene-vinyl acetate copolymer or polyethylene 55% ~ 62%, graphitized carbon black 23% ~ 30%, Graphene powder 1% ~ 5%, white oil 8% ~ 12%, oxidation inhibitor 0.5% ~ 1%, Zinic stearas 0.3% ~ 1%, crosslink agent DCP 0.6% ~ 1.2%.
According to another embodiment of the invention, the microplate thickness comprising described Graphene powder is further not more than 8 μm.
According to another embodiment of the invention, the particle diameter comprising described carbon black is further not more than 50 μm.
According to another embodiment of the invention, comprising described oxidation inhibitor is further 4,4'-thiobis.
According to another embodiment of the invention, comprising described mass percentage is further: ethylene-vinyl acetate copolymer 55%, Graphene powder 1%, graphitized carbon black 30%, white oil 12%, oxidation inhibitor 0.5%, Zinic stearas 0.3%.
According to another embodiment of the invention, comprising described mass percentage is further: polyethylene 59%, Graphene powder 3%, carbon black 25.8%, white oil 10%, oxidation inhibitor 1%, Zinic stearas 0.6%.
According to another embodiment of the invention, comprising described mass percentage is further: ethylene-vinyl acetate copolymer 62%, Graphene powder 5%, carbon black 22%, white oil 8%, oxidation inhibitor 0.9%, Zinic stearas 1%.
According to another embodiment of the invention, comprise this preparation method further to comprise:
The first step, mixing,
A, Graphene powder is first miscible in white oil;
B, ethylene-vinyl acetate copolymer or polyethylene, graphitized carbon black powder are added high mixer and stir 2 minutes;
C, the mixing solutions of Graphene powder and white oil and oxidation inhibitor 4,4'-thiobis, Zinic stearas are joined high mixer, stir 1-2 minute together;
D, all material of mixing preliminary in high mixer is sent into Banbury mixer by connecting tube, mixing 10-12 minute at 95-105 DEG C of temperature;
Second step, plasticizing, granulation,
A, material good for banburying in Banbury mixer is carried out extruding pelletization, water-cooled and processed by single screw extrusion machine;
B, by dehydration after plastic pellet by transport pipe send into another high mixer and add in proportion linking agent stir 1-2 minute;
C, plastic pellet is sent into storage warehouse and weighing and bagging.
According to another embodiment of the invention, comprising described extruding pelletization is further cylindrical particle, and its diameter is 3.5mm, highly for 3mm.
According to another embodiment of the invention, comprising described extruding pelletization is further cylindrical particle, and its diameter is 3.5mm, highly for 3mm.
The invention has the beneficial effects as follows: this carbon black, the Graphene prior art that has been the functionalized macromolecular matrix material customer service of conducting medium only uses carbon black compound semiconductive shieldin material to affect problem because carbon black conductive is not ideal enough and conductive filler material adding proportion is excessive to cable quality, except significantly improving the conductivity of semiconductive shieldin material product, also greatly improve its thermostability.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the step structural representation of preparation method of the present invention.
Embodiment
A kind of carbon black for out semiconductor layer in the crosslinked polyetylene insulated high-tension cable of 6-220kV of the present invention/Graphene corporate conductive medium low resistance high heat stability peroxide crosslinking semi-conductive high polymer matrix material, be made up of following mass percentage: ethylene-vinyl acetate copolymer (EVA) or polyethylene (PE) 55% ~ 62%, graphitized carbon black 23% ~ 30%, Graphene powder 1% ~ 5%, white oil 8% ~ 12%, oxidation inhibitor 0.5% ~ 1%, Zinic stearas 0.3% ~ 1%, crosslink agent DCP 0.6% ~ 1.2%.
The microplate thickness of Graphene powder is not more than 8 μm.
The particle diameter of carbon black is not more than 50 μm.
Oxidation inhibitor is 4,4'-thiobis (the 6-tertiary butyl-3-methylphenol).
In high-tension cable of the present invention, external shield carbon black/Graphene is jointly as the low resistance high heat stability peroxide crosslinking semi-conductive high polymer matrix material of conducting medium, at the volume specific resistance≤20 Ω cm of 20 DEG C.At the volume specific resistance≤100 Ω cm of 90 DEG C.
The preparation method of material of the present invention, as shown in Figure 1, comprises the following steps:
The first step, mixing,
A, Graphene powder is first miscible in white oil;
B, ethylene-vinyl acetate copolymer or polyethylene, graphitized carbon black powder are added high mixer and stir 2 minutes;
C, the mixing solutions of Graphene powder and white oil and oxidation inhibitor 4,4'-thiobis, Zinic stearas are joined high mixer, stir 1-2 minute together;
D, all material of mixing preliminary in high mixer is sent into Banbury mixer by connecting tube, mixing 10-12 minute at 95-105 DEG C of temperature;
Second step, plasticizing, granulation,
A, material good for banburying in Banbury mixer is carried out extruding pelletization, water-cooled and processed by single screw extrusion machine;
B, by dehydration after plastic pellet by transport pipe send into another high mixer and add in proportion linking agent stir 1-2 minute;
C, plastic pellet is sent into storage warehouse and weighing and bagging.The effect of each constituent materials
The base-material acting as material of ethylene-vinyl acetate copolymer (EVA) or polyethylene (PE).
Graphene powder and carbon black are jointly as conductive filler material, and graphene powder is a kind of material with excellent electric conductivity energy, and its shape is microplate shape, has very large specific surface area, mutually can put up a bridge have complementary advantages with the particulate state of carbon black.The volume specific resistance of shielding material and thermostability obtain mainly through the add-on of conductive filler material and the adjustment of bi-material ratio.
White oil act as lubricant and assisted demoulding agent, materials processing performance is protected.
Acting as of oxidation inhibitor suppresses or delays the oxidative degradation of material, extends the work-ing life of material.
What Zinic stearas was act as lubricant, reduce material in the course of processing with the friction of machine internal, improve the mobility of material.
In the high-tension cable that the inventive method prepares, external shield carbon black, Graphene are jointly as the low resistance high heat stability peroxide crosslinking semi-conductive high polymer matrix material of conducting medium, by GB/T1033-2008 test density, by GB/T1040-2006 test tensile strength, test 20 DEG C of volume specific resistances by GB/T3048.3-2007.Carry out air heat ageing test, by GB/T1040-2006 test tensile strength velocity of variation, by GB/T2951.12-2008 elongation at break velocity of variation.Test is carried out and current standards (JB/T10738-2007) comparing result sees attached list with aforesaid method.
Embodiment 1,
One, mass percentage is: EVA55%, Graphene powder 1%, carbon black 30%, white oil 12%, oxidation inhibitor 0.5%, Zinic stearas 0.3%.2 minutes are uniformly mixed with the rotating speed of 300rpm.
Two, in Banbury mixer, banburying is carried out, banburying temperature 95 DEG C, 10 minutes time.
Three, material good for banburying is carried out extruding pelletization, water-cooled and processed by single screw extrusion machine.
Extruder screw rotating speed is 120rpm, and plasticization temperature is:
Granulation is of a size of the cylindrical particle of diameter 3.5mm × height 3mm.
Four, the plastic pellet after dehydration is sent into another high mixer by transport pipe, and add linking agent according to 0.6% ratio, stir 1 minute with the rotating speed of 300rpm.
Five, plastic pellet is sent into storage warehouse and weighing and bagging.
Embodiment 2,
One, mass percentage is: PE59%, Graphene powder 3%, carbon black 25.8%, white oil 10%, oxidation inhibitor 1%, Zinic stearas 0.6%.2 minutes are uniformly mixed with the rotating speed of 300rpm.
Two, in Banbury mixer, banburying is carried out, banburying temperature 100 DEG C, 11 minutes time.
Three, material good for banburying is carried out extruding pelletization, water-cooled and processed by single screw extrusion machine.
Extruder screw rotating speed is 106rpm, and plasticization temperature is:
Granulation is of a size of the cylindrical particle of diameter 3.5mm × height 3mm.
Four, the plastic pellet after dehydration is sent into another high mixer by transport pipe, and add linking agent according to 1.2% ratio, stir 1 minute with the rotating speed of 300rpm.
Five, plastic pellet is sent into storage warehouse and weighing and bagging.
Embodiment 3,
One, mass percentage is: EVA62%, Graphene powder 5%, carbon black 22%, white oil 8%, oxidation inhibitor 0.9%, Zinic stearas 1%.2 minutes are uniformly mixed with the rotating speed of 300rpm.
Two, in Banbury mixer, banburying is carried out, banburying temperature 105 DEG C, 12 minutes time.
Three, material good for banburying is carried out extruding pelletization, water-cooled and processed by single screw extrusion machine.
Extruder screw rotating speed is 106rpm, and plasticization temperature is:
Granulation is of a size of the cylindrical particle of diameter 3.5mm × height 3mm.
Four, the plastic pellet after dehydration is sent into another high mixer by transport pipe, and add linking agent according to 1.1% ratio, stir 1.5 minutes with the rotating speed of 300rpm.
Five, plastic pellet is sent into storage warehouse and weighing and bagging
Subordinate list test result his-and-hers watches
As can be seen from contrast, the present invention is compared with current standards, and the volume specific resistance of material declines more than 5 times, and thermostability improves more than 20 times.
Originally instant invention overcomes prior art only uses carbon black compound semiconductive shieldin material to affect problem because carbon black conductive is not ideal enough and conductive filler material adding proportion is excessive to cable quality, except significantly improving the conductivity of semiconductive shieldin material product, also greatly improve its thermostability.
Claims (9)
1. a carbon black, Graphene are the functionalized macromolecular matrix material of conducting medium, it is characterized in that, comprise following mass percentage composition: ethylene-vinyl acetate copolymer or polyethylene 55% ~ 62%, graphitized carbon black 23% ~ 30%, Graphene powder 1% ~ 5%, white oil 8% ~ 12%, oxidation inhibitor 0.5% ~ 1%, Zinic stearas 0.3% ~ 1%, crosslink agent DCP 0.6% ~ 1.2%.
2. carbon black as claimed in claim 1, Graphene are the functionalized macromolecular matrix material of conducting medium, and it is characterized in that, the microplate thickness of described Graphene powder is not more than 8 μm.
3. carbon black as claimed in claim 1, Graphene are the functionalized macromolecular matrix material of conducting medium, and it is characterized in that, the particle diameter of described carbon black is not more than 50 μm.
4. carbon black as claimed in claim 1, Graphene are the functionalized macromolecular matrix material of conducting medium, and it is characterized in that, described oxidation inhibitor is 4,4'-thiobis.
5. carbon black as claimed in claim 1, Graphene are the functionalized macromolecular matrix material of conducting medium, it is characterized in that, described mass percentage is: ethylene-vinyl acetate copolymer 55%, Graphene powder 1%, graphitized carbon black 30%, white oil 12%, oxidation inhibitor 0.5%, Zinic stearas 0.3%.
6. carbon black as claimed in claim 1, Graphene are the functionalized macromolecular matrix material of conducting medium, it is characterized in that, described mass percentage is: polyethylene 59%, Graphene powder 3%, carbon black 25.8%, white oil 10%, oxidation inhibitor 1%, Zinic stearas 0.6%.
7. carbon black as claimed in claim 1, Graphene are the functionalized macromolecular matrix material of conducting medium, it is characterized in that, described mass percentage is: ethylene-vinyl acetate copolymer 62%, Graphene powder 5%, carbon black 22%, white oil 8%, oxidation inhibitor 0.9%, Zinic stearas 1%.
8. the preparation method of polymer composite as claimed in claim 1, it is characterized in that, this preparation method comprises:
The first step, mixing,
A, Graphene powder is first miscible in white oil;
B, ethylene-vinyl acetate copolymer or polyethylene, graphitized carbon black powder are added high mixer and stir 2 minutes;
C, the mixing solutions of Graphene powder and white oil and oxidation inhibitor 4,4'-thiobis, Zinic stearas are joined high mixer, stir 1-2 minute together;
D, all material of mixing preliminary in high mixer is sent into Banbury mixer by connecting tube, mixing 10-12 minute at 95-105 DEG C of temperature;
Second step, plasticizing, granulation,
A, material good for banburying in Banbury mixer is carried out extruding pelletization, water-cooled and processed by single screw extrusion machine;
B, by dehydration after plastic pellet by transport pipe send into another high mixer and add in proportion linking agent stir 1-2 minute;
C, plastic pellet is sent into storage warehouse and weighing and bagging.
9. the preparation method of polymer composite as claimed in claim 1, it is characterized in that, described extruding pelletization is cylindrical particle, and its diameter is 3.5mm, highly is 3mm.
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Cited By (16)
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| CN105803814A (en) * | 2016-04-20 | 2016-07-27 | 常州中超石墨烯电力科技有限公司 | Graphene-based high-strength conductive cloth and preparation method thereof |
| CN106046638A (en) * | 2016-07-14 | 2016-10-26 | 东莞市成天泰电线电缆有限公司 | Super-smooth semiconductive shield cable special material and shield cable made of super-smooth semiconductive shield cable special material |
| CN106279959A (en) * | 2016-08-24 | 2017-01-04 | 张伟 | A kind of graphene battery material of magnetic conductive and preparation method thereof |
| CN107011568A (en) * | 2017-04-19 | 2017-08-04 | 上海电气集团股份有限公司 | Composite graphite alkene/carbon black is the semi-conducting polymer and preparation method of conducting medium |
| CN107474376A (en) * | 2017-09-12 | 2017-12-15 | 哈尔滨理工大学 | A kind of cable semi-conductive shielding material and preparation method thereof |
| CN107987337A (en) * | 2017-09-11 | 2018-05-04 | 江苏宝安电缆有限公司 | A kind of shield machine high-tension cable reflecting sheath |
| CN108164804A (en) * | 2017-12-22 | 2018-06-15 | 上海至正道化高分子材料股份有限公司 | Compound semiconductive shieldin material of middle-high voltage power cable graphene and preparation method thereof |
| CN108269654A (en) * | 2016-12-30 | 2018-07-10 | 杭州电缆股份有限公司 | A kind of middle jewelling alloy overhead insulated cable and preparation method thereof |
| CN108864527A (en) * | 2018-05-30 | 2018-11-23 | 上海交通大学 | Semi-conductive screen layer material and preparation method for high-tension cable polypropylene insulation |
| CN109535529A (en) * | 2018-11-30 | 2019-03-29 | 东莞市德诚塑化科技有限公司 | A kind of conductive polyethylene, preparation method and its usage |
| CN109535577A (en) * | 2018-11-30 | 2019-03-29 | 东莞市德诚塑化科技有限公司 | A kind of conduction polybutene, preparation method and its usage |
| CN109575398A (en) * | 2017-11-16 | 2019-04-05 | 山东方大新材料科技有限公司 | Mining type graphene, carbon black, polyethylene composite pipe and preparation method thereof |
| CN111303526A (en) * | 2020-04-02 | 2020-06-19 | 成都鑫成鹏高分子科技股份有限公司 | Multilayer graphene modified semiconductive shielding material and preparation method thereof |
| WO2020206979A1 (en) * | 2019-04-08 | 2020-10-15 | 江苏德威新材料股份有限公司 | Semi-conductive shielding material for high voltage cable, and preparation method and use thereof |
| CN114729149A (en) * | 2019-11-27 | 2022-07-08 | 韩华思路信株式会社 | Conductive resin composition for anti-slip and molded article comprising same |
| CN117457260A (en) * | 2023-12-26 | 2024-01-26 | 深圳市绚图新材科技有限公司 | Novel conductive carbon black-modified graphene composite slurry and preparation method thereof |
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| CN108269654A (en) * | 2016-12-30 | 2018-07-10 | 杭州电缆股份有限公司 | A kind of middle jewelling alloy overhead insulated cable and preparation method thereof |
| CN107011568A (en) * | 2017-04-19 | 2017-08-04 | 上海电气集团股份有限公司 | Composite graphite alkene/carbon black is the semi-conducting polymer and preparation method of conducting medium |
| CN107011568B (en) * | 2017-04-19 | 2019-12-20 | 上海电气集团股份有限公司 | Semiconductor polymer with composite graphene/carbon black as conductive medium and preparation method thereof |
| CN107987337A (en) * | 2017-09-11 | 2018-05-04 | 江苏宝安电缆有限公司 | A kind of shield machine high-tension cable reflecting sheath |
| CN107474376A (en) * | 2017-09-12 | 2017-12-15 | 哈尔滨理工大学 | A kind of cable semi-conductive shielding material and preparation method thereof |
| CN109575398A (en) * | 2017-11-16 | 2019-04-05 | 山东方大新材料科技有限公司 | Mining type graphene, carbon black, polyethylene composite pipe and preparation method thereof |
| CN108164804A (en) * | 2017-12-22 | 2018-06-15 | 上海至正道化高分子材料股份有限公司 | Compound semiconductive shieldin material of middle-high voltage power cable graphene and preparation method thereof |
| CN108864527A (en) * | 2018-05-30 | 2018-11-23 | 上海交通大学 | Semi-conductive screen layer material and preparation method for high-tension cable polypropylene insulation |
| CN109535529A (en) * | 2018-11-30 | 2019-03-29 | 东莞市德诚塑化科技有限公司 | A kind of conductive polyethylene, preparation method and its usage |
| CN109535577A (en) * | 2018-11-30 | 2019-03-29 | 东莞市德诚塑化科技有限公司 | A kind of conduction polybutene, preparation method and its usage |
| WO2020206979A1 (en) * | 2019-04-08 | 2020-10-15 | 江苏德威新材料股份有限公司 | Semi-conductive shielding material for high voltage cable, and preparation method and use thereof |
| CN114729149A (en) * | 2019-11-27 | 2022-07-08 | 韩华思路信株式会社 | Conductive resin composition for anti-slip and molded article comprising same |
| CN111303526A (en) * | 2020-04-02 | 2020-06-19 | 成都鑫成鹏高分子科技股份有限公司 | Multilayer graphene modified semiconductive shielding material and preparation method thereof |
| CN117457260A (en) * | 2023-12-26 | 2024-01-26 | 深圳市绚图新材科技有限公司 | Novel conductive carbon black-modified graphene composite slurry and preparation method thereof |
| CN117457260B (en) * | 2023-12-26 | 2024-04-12 | 深圳市绚图新材科技有限公司 | Novel conductive carbon black-modified graphene composite slurry and preparation method thereof |
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