CN108164804A - Compound semiconductive shieldin material of middle-high voltage power cable graphene and preparation method thereof - Google Patents
Compound semiconductive shieldin material of middle-high voltage power cable graphene and preparation method thereof Download PDFInfo
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- CN108164804A CN108164804A CN201711408418.6A CN201711408418A CN108164804A CN 108164804 A CN108164804 A CN 108164804A CN 201711408418 A CN201711408418 A CN 201711408418A CN 108164804 A CN108164804 A CN 108164804A
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- 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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- 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
- C08L23/0869—Acids or derivatives thereof
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
A kind of compound semiconductive shieldin material of middle-high voltage power cable graphene disclosed by the invention, is prepared by following materials in percentage by mass：Polar polyolefin hydrocarbon copolymer 30% 80%, the compounding mixture of grapheme material and conductive black 15% 35%, lubricant 1% 6%, antioxidant 0.2% 1%.The invention also discloses the preparation methods of the compound semiconductive shieldin material of middle-high voltage power cable graphene.Compared with prior art, the present invention the conductive black content of shielding material can be reduced effectively, improve the extrusion performance of shielding material, improve the surface flatness of shielded layer, available for the interior external shield of middle-high voltage power cable, cable shield homogenizing electric field effect is improved, increases the reliability of cable longtime running.
Description
Technical field
The present invention relates to a kind of mesohigh transmission ＆ distribution cable material and preparation method thereof, particularly a kind of middle-high voltage power cable
With compound semiconductive shieldin material of graphene and preparation method thereof.
Background technology
In middle-high voltage power cable, should there are a conductor shielding and insulation shielding, effect is so that insulating layer and cable, leading
Body insulating layer and protective metal shell have preferable contact, eliminate the rough increasing for causing Electric Field Indensity on Surface of Conductor of conductive surface
Add, mitigate cable internal electric field stress concentration, improve cable internal electric field radial distribution, to improve the electrical strength of cable.
The crosslinked polyetylene insulated inside and outside shielding material of middle-high voltage power cable generally using semiconductive shieldin material, composition by
Polar polyolefin resin compounded conductive carbon black is made.Vistanex has stronger electrical insulating property in itself, and material is shielded in manufacture
During material, need to add in a large amount of conductive black to improve the electric conductivity of material, but a large amount of conductive black addition makes
The physicochemical property and processing performance for obtaining shielding material all substantially reduce, and the surface flatness of shielded layer is poor after thin-walled squeezes out.
If semiconductive shieldin material itself cannot be guaranteed that surface is smooth (rough surface even has sharp protrusion), there is the recessed of injustice
Cheat or have crack, fracture, with insulated contact it is insufficient the defects of, be just difficult to play the role of uniform cable electric field or even have can
Serious electric field can be caused to concentrate, lead to shelf depreciation or insulation breakdown.On the other hand, since the resistivity of conductive black is with temperature
Degree variation is very big, makes 20 DEG C of cable shield widely different with 90 DEG C of resistance, cable electric field is caused to be distributed and is changed with temperature.
Invention content
The first technical problem to be solved by the present invention is to reduce shielding material volume resistance for the susceptibility of temperature, is carried
The smoothness of layer surface is shielded when high thin-walled squeezes out and a kind of compound semi-conductive screen of middle-high voltage power cable graphene is provided
Material, the compound semiconductive shieldin material of middle-high voltage power cable graphene can be used for inside and outside middle-high voltage power cable polyethylene insulation
Shielded layer increases cable shield homogenizing electric field effect, improves the reliability of cable longtime running.
The present invention also provides a kind of preparation method of the compound semiconductive shieldin material of middle-high voltage power cable graphene simultaneously,
This method can make graphene and conductive black during mixed at high speed, the multilayer knot of the graphene intercalation such as carbon black of single layer structure
In structure so that the two be combined with each other, interaction, reduces the surface energy of graphene to a certain extent, reduces agglomerating effect,
Being uniformly dispersed in shielding material.
The lattice structure that the purpose of the present invention is stablized using grapheme material, using its outstanding conduction, heat conductivility,
Partially electronically conductive carbon black is substituted, the conductive black dosage in shielding material is reduced, improves the electric conductivity and thermal conductivity of shielding material, change
Kind extrusion processability energy improves the surface flatness of shielded layer.
The technology path of the present invention is that grapheme material and conductive black are made conductive compounding mixture in advance first to make
For conductive carrier, then it is granulated with the copolymer blended plasticizing of polar polyolefin and polyolefin semiconductive shieldin material, quality percentage is made
Content forms：The compounding mixture 15%-35% of Polar polyolefin hydrocarbon copolymer 30%-80%, grapheme material and conductive black,
Lubricant 0.1%-0.6%, antioxidant 0.2%-1%.
The grapheme material of the present invention and the compounding mixture quality percentage composition of conductive black form：Grapheme material
5%-30%, conductive black 95%-70%.
Thickness 10nm, D50 grain size≤1.5/um of grapheme material.
Conductive black specific surface area (75-120) * 103m2/kg, DBP the suction values of the present invention：130-150.
The Polar polyolefin hydrocarbon copolymer of the present invention uses ethylene-vinyl acetate copolymer, and wherein vinyl acetate content is
Ethylene-ethylacrylate, ethylene butyl acrylate can also be used in 18%-28%.
The lubricant is for microcrystalline wax and in polyethylene wax, oxidized polyethylene wax, white oil and silicone master batch
A kind of combination of or arbitrary two or more mixture, and microcrystalline wax accounts for the weight ratio of lubricant not less than 50%.
The antioxidant is antioxidant 1010, antioxidant 300, anti-oxidant DLTP and one kind in antioxidant 1024 or is appointed
It anticipates the combination of two or more mixtures.
The preparation method of the compound semiconductive shieldin material of middle-high voltage power cable graphene of the present invention, including following step
Suddenly：
(1) preparation of the compounding mixture of grapheme material and conductive black：Graphene powder presses quality with conductive black
Percentage carries out mixed at high speed 1min-5min after being compounded and obtains the compounding mixture of grapheme material and conductive black, high
The rotating speed of fast mixing machine turns/min for 300 turns/min-500；
(2) the compounding mixture of the grapheme material to step (1) preparation and conductive black injects formula ratio in proportion again
Antioxidant, lubricant；
(3) it is plasticized mixing granulator：By formula by Polar polyolefin hydrocarbon resin, the grapheme material containing antioxidant, lubricant
Entered in kneading machine by different spouts respectively from the compounding mixture of conductive black, through kneading machine mixing extrusion, water ring
Pelletizing, drying are cooled down and are made.
The compound semiconductive shieldin material of middle-high voltage power cable middle-high voltage power cable graphene of the present invention is due to using
As above technical solution, the present invention have following advantageous effect:
For the crosslinked polyetylene insulated inside and outside semiconductive shieldin material of power cable, it usually needs reach 20 DEG C of volume resistivities
≤ 100 Ω .cm, the Ω .cm of volume resistivity at 90 DEG C≤2500, for the requirement of satisfaction more than volume resistivity, need to add in about
More than 30% conductive black causes the more difficult thin-walled of material to squeeze out, and after squeezing out shielded layer surface flatness it is poor.At present, it is electric
Power cable generally uses the cable of higher and higher grade, and the use, even higher voltage grade such as 110kV, 220kV cable will
The cable asked proposes higher want to shielding material carbon black dispersion, physicochemical property, gel impurity content and processing stability
It asks.
In order to which semiconductive shieldin material is made to have good processing performance and physical mechanical property, reducing conductive black dosage is
Effective method.But the reduction of conductive black dosage will influence electric conductivity.Grapheme material compares conductive black, volume resistance
Rate can decline 10--200 times, and electric conductivity accordingly increases.When electronics in graphene moves in track, it will not be lacked because of lattice
It falls into or introduces foreign atom and scatter.Since interatomic force is very strong, at normal temperatures, even if surrounding carbon atom occurs
It telescopes, the interference that electronics is subject in graphene is also very small.Its good heat conductivility can improve the thermal stability of shielding material
Can, shorten the change rate of volume resistance between 20 DEG C and 90 DEG C, optimize shielded layer surface flatness and physical mechanical after extrusion
Performance.
Compared with prior art, the present invention the conductive black content of shielding material can be reduced effectively, improve the extrusion of shielding material
Performance improves the surface flatness of shielded layer, available for the interior external shield of middle-high voltage power cable, improves cable shield homogenizing electricity
Field effect increases the reliability of cable longtime running.
Specific embodiment
The middle-high voltage power cable of the present invention is by following mass percentage group with the compound semiconductive shieldin material of graphene
Into：The compounding mixture 15%- of ethylene-vinyl acetate copolymer (EVA) 30%-80%, grapheme material and conductive black
35%, lubricant 0.1%-0.6%, antioxidant 0.2%-1%.
The grapheme material of the present invention and the compounding mixture quality percentage composition of conductive black form：Grapheme material
5%-20%, conductive black 95%-80%.
Thickness 10nm, D50 grain size≤1.5/um of grapheme material
Conductive black specific surface area (75-120) * 103m2/kg, DBP the suction values of the present invention：130-150
The polar polyolefin of the present invention is 18%- using ethylene-vinyl acetate copolymer, wherein vinyl acetate content
Ethylene-ethylacrylate, ethylene butyl acrylate can also be used in 28%, melt index 2-10g/10min.
The preparation method of the compound semiconductive shieldin material of middle-high voltage power cable graphene, includes the following steps：
(1) preparation of the compounding mixture of grapheme material and conductive black：Graphene powder presses quality with conductive black
Percentage carries out mixed at high speed 1min-5min after being compounded and obtains the compounding mixture of grapheme material and conductive black, high
The rotating speed of fast mixing machine turns/min for 300 turns/min-500；
(2) the compounding mixture of the grapheme material to step (1) preparation and conductive black injects formula ratio in proportion again
Antioxidant, lubricant；
(3) it is plasticized mixing granulator：By formula by Polar polyolefin hydrocarbon resin, the grapheme material containing antioxidant, lubricant
Entered in BUSS kneading machines by different spouts respectively from the compounding mixture of conductive black, through BUSS machine mixing extrusions,
Water ring pelletizing, drying are cooled down and are made.Low speed will be put into after conduction compounding mixture and polar polyolefin metering in mass ratio
Mixing machine is mixed, and becomes mixture.The rotating speed of mixing machine turns/min for 20 turns/min-50.Incorporation time is 5min-
10min。
It is plasticized mixing granulator：It is kneaded, is plasticized, is granulated using the reciprocating mixing extrusion granulating unit of WF140-180 types,
Host groups include the reciprocating mixing area of main feeding and lateral feeding, and with granulation zone, subsidiary engine group includes centrifugal dehydrator and boiling
Bed entirely mixes, plasticizing, squeeze out, be granulated, dehydrates and completed on this unit.
Polar polyolefin, conductive compounding mixture are carried out by formula rate requirement respectively using segmentation feeding method automatic
Metering feeding, wherein conductive compounding mixture is respectively from main spout and lateral spout feeding BUSS kneading machine screw rods, warp
Semiconductive shieldin material is made in BUSS machine mixing extrusions, water ring pelletizing, dry cooling.Wherein：The temperature setting of BUSS kneading machines is：
85 DEG C~95 DEG C of compression section, 105 DEG C~125 DEG C of homogenizing zone, 100 DEG C~125 DEG C of head temperature.
Below in conjunction with specific embodiment, the present invention will be further described in detail.The raw material used in following embodiment
It is commercially available standard industry product.For example, vistanex can be from there is the purchases such as Tao Shi, Du Pont, Exxon, domestic Yangba
It buys.
The composition of raw materials of embodiment 1-5 is referring to table 1.
Table 1
The compound semiconductive shieldin material of middle-high voltage power cable graphene that embodiment 1-5 is prepared is by GB/T3048.3
Test volume resistivity, the results are shown in Table 2.Surface flatness estimates its apparent table using 45 Single screw extrusion tie rod modes of Ф
Face, the mouth mold of extruder is 1mm thickness, 10mm wide, and the temperature of extruder is：
| 1st area | 2nd area | 3rd area | 4th area | Head |
| 95 | 110 | 135 | 150 | 155 |
Table 2
Claims (9)
1. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene, which is characterized in that by following mass percent
Raw material is prepared：The compounding mixture 15%- of Polar polyolefin hydrocarbon copolymer 30%-80%, grapheme material and conductive black
35%, lubricant 0.1%-0.6%, antioxidant 0.2%-1%.
2. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene as described in claim 1, which is characterized in that
The grapheme material and the compounding mixture quality percentage composition of conductive black form：Grapheme material 5%-30%, leads
Electric carbon black 95%-70%.
3. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene as claimed in claim 2, which is characterized in that
Thickness 10nm, D50 grain size≤1.5/um of the grapheme material.
4. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene as claimed in claim 2, which is characterized in that
The conductive black specific surface area 75-120*103m2/ kg, DBP suction value：130-150.
5. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene as described in claim 1, which is characterized in that
The Polar polyolefin hydrocarbon copolymer is ethylene-vinyl acetate copolymer, ethylene-ethylacrylate, in ethylene butyl acrylate
One kind or arbitrary two or more mixing.
6. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene as claimed in claim 5, which is characterized in that
Vinyl acetate content in the ethylene-vinyl acetate copolymer is 18%-28%.
7. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene as described in claim 1, which is characterized in that
The lubricant is microcrystalline wax and one kind or arbitrary two in polyethylene wax, oxidized polyethylene wax, white oil and silicone master batch
Kind or more mixture combination, and microcrystalline wax account for lubricant weight ratio be not less than 50%.
8. a kind of compound semiconductive shieldin material of middle-high voltage power cable graphene as described in claim 1, which is characterized in that
The antioxidant is antioxidant 1010, antioxidant 300, anti-oxidant DLTP and one kind in antioxidant 1024 or it is arbitrary two kinds with
On mixture combination.
9. the compound semiconductive shieldin material of middle-high voltage power cable graphene described in any one of claim 1 to 8 claim
Preparation method, which is characterized in that include the following steps：
(1) preparation of the compounding mixture of grapheme material and conductive black：Graphene powder presses quality percentage with conductive black
The compounding mixture of grapheme material and conductive black is obtained than carrying out mixed at high speed 1min-5min after being compounded, it is mixed at a high speed
The rotating speed of conjunction machine turns/min for 300 turns/min-500；
(2) the compounding mixture of the grapheme material to step (1) preparation and conductive black injects the anti-of formula ratio in proportion again
Oxygen agent, lubricant；
(3) it is plasticized mixing granulator：By formula by Polar polyolefin hydrocarbon resin, containing antioxidant, lubricant grapheme material with leading
The compounding mixture of electric carbon black is entered by different spouts in kneading machine respectively, through kneading machine mixing extrusion, water ring pelletizing,
Drying is cooled down and is made.
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Cited By (14)
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| CN109206731A (en) * | 2018-08-27 | 2019-01-15 | 芜湖市元奎新材料科技有限公司 | A kind of power cable shielding material of containing graphene and preparation method thereof |
| CN109370027A (en) * | 2018-09-18 | 2019-02-22 | 特变电工(德阳)电缆股份有限公司 | A kind of compound semi-conductive shielding material of graphene, preparation method and applications |
| CN109721812A (en) * | 2019-02-27 | 2019-05-07 | 山西永东化工股份有限公司 | The preparation method and its device of a kind of graphene/conductive black composite material and application |
| CN110128736A (en) * | 2019-04-08 | 2019-08-16 | 江苏德威新材料股份有限公司 | A kind of high-tension cable semiconductive shieldin material and its preparation method and application |
| 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 |
| CN112280231A (en) * | 2020-10-14 | 2021-01-29 | 南方电网科学研究院有限责任公司 | Shielding material for polypropylene-based thermoplastic cable and preparation method thereof |
| CN112457567A (en) * | 2020-11-27 | 2021-03-09 | 南方电网科学研究院有限责任公司 | High-voltage cable semi-conductive shielding material and preparation method thereof |
| CN112724500A (en) * | 2020-12-29 | 2021-04-30 | 浙江万马高分子材料集团有限公司 | Semiconductive shielding material and preparation method and application thereof |
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| CN113943454A (en) * | 2021-09-16 | 2022-01-18 | 江苏上上电缆集团新材料有限公司 | Graphene and carbon nanotube synergistic high-electrical-property semiconductive shielding material and preparation method thereof |
| CN114316461A (en) * | 2021-11-18 | 2022-04-12 | 江苏东方电缆材料有限公司 | Non-crosslinked semiconductive shielding material for power cable and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206731A (en) * | 2018-08-27 | 2019-01-15 | 芜湖市元奎新材料科技有限公司 | A kind of power cable shielding material of containing graphene and preparation method thereof |
| CN109370027A (en) * | 2018-09-18 | 2019-02-22 | 特变电工(德阳)电缆股份有限公司 | A kind of compound semi-conductive shielding material of graphene, preparation method and applications |
| CN109370027B (en) * | 2018-09-18 | 2021-01-05 | 特变电工(德阳)电缆股份有限公司 | Graphene composite semiconductive shielding material, preparation method and application thereof |
| CN109721812A (en) * | 2019-02-27 | 2019-05-07 | 山西永东化工股份有限公司 | The preparation method and its device of a kind of graphene/conductive black composite material and application |
| CN110128736A (en) * | 2019-04-08 | 2019-08-16 | 江苏德威新材料股份有限公司 | A kind of high-tension cable semiconductive shieldin material and its preparation method and application |
| 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 |
| CN112980085A (en) * | 2019-12-18 | 2021-06-18 | 中广核三角洲（江苏）塑化有限公司 | Preparation method of semiconductive polyethylene shielding material |
| 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 |
| CN112280231A (en) * | 2020-10-14 | 2021-01-29 | 南方电网科学研究院有限责任公司 | Shielding material for polypropylene-based thermoplastic cable and preparation method thereof |
| CN112457567A (en) * | 2020-11-27 | 2021-03-09 | 南方电网科学研究院有限责任公司 | High-voltage cable semi-conductive shielding material and preparation method thereof |
| WO2022111152A1 (en) * | 2020-11-27 | 2022-06-02 | 南方电网科学研究院有限责任公司 | Semi-conductive shielding material for high-voltage cable, and preparation method therefor |
| CN112457567B (en) * | 2020-11-27 | 2022-12-06 | 南方电网科学研究院有限责任公司 | High-voltage cable semi-conductive shielding material and preparation method thereof |
| CN112724500A (en) * | 2020-12-29 | 2021-04-30 | 浙江万马高分子材料集团有限公司 | Semiconductive shielding material and preparation method and application thereof |
| CN113943454A (en) * | 2021-09-16 | 2022-01-18 | 江苏上上电缆集团新材料有限公司 | Graphene and carbon nanotube synergistic high-electrical-property semiconductive shielding material and preparation method thereof |
| WO2023065429A1 (en) * | 2021-10-18 | 2023-04-27 | 南方电网科学研究院有限责任公司 | Method for preparing semi-conductive shielding material used for high-voltage cable from low-impurity conductive carbon black |
| CN114316461A (en) * | 2021-11-18 | 2022-04-12 | 江苏东方电缆材料有限公司 | Non-crosslinked semiconductive shielding material for power cable and preparation method thereof |
| CN115304854A (en) * | 2022-08-12 | 2022-11-08 | 四川大学 | High-voltage cable semiconductive shielding material based on graphene oxide dispersed conductive carbon black and preparation method thereof |
| CN116082741A (en) * | 2022-11-07 | 2023-05-09 | 万华化学（宁波）有限公司 | Cable shielding material and preparation method and application thereof |
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