CN111138747A - EVA semiconductive cable shielding material and preparation method thereof - Google Patents
EVA semiconductive cable shielding material and preparation method thereof Download PDFInfo
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- CN111138747A CN111138747A CN201911301679.7A CN201911301679A CN111138747A CN 111138747 A CN111138747 A CN 111138747A CN 201911301679 A CN201911301679 A CN 201911301679A CN 111138747 A CN111138747 A CN 111138747A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/001—Conductive additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- C08L2312/08—Crosslinking by silane
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Abstract
The invention discloses an EVA semiconductive cable shielding material, which comprises the following raw materials in parts by weight: 2-20 parts of composite conductive agent, 0-10 parts of dispersing agent, 100 parts of ethylene-vinyl acetate copolymer (EVA), 0-8 parts of auxiliary dispersing agent, 0-3 parts of cross-linking agent, 0-5 parts of lubricating agent and 0-2 parts of antioxidant. The method adopts polyvinylpyrrolidone as a dispersing agent, and a composite conductive agent consisting of graphene and conductive carbon fibers is added into a mixer for pre-dispersion treatment; then, the EVA resin material, the auxiliary dispersant vinyl silane coupling agent and other auxiliary agents are added for secondary mixing, so that the high effective dispersion of the conductive material is ensured. By utilizing the superconductivity and different space dimensions of the graphene and the carbon fibers, compared with the traditional conductive carbon black, the addition amount of the conductive agent can be greatly reduced, and the prepared cable shielding material has the characteristics of high strength and good conductivity, simplifies the production and processing process and reduces black pollution.
Description
Technical Field
The invention relates to the technical field of cable material manufacturing, in particular to an EVA semi-conductive cable shielding material and a preparation method thereof.
Background
The semiconductive shielding material of the cable is generally prepared by adding conductive carbon black into EVA resin, banburying the mixture by an internal mixer and then extruding the mixture by a single-screw extruder. Generally speaking, to meet the conductivity requirement of the cable for the semiconductive shielding material, a high carbon black addition is required, which not only causes the mechanical properties of the base resin to be reduced and the production process to be complicated, but also increases black pollution. If the amount of the conductive carbon black added is reduced or the carbon black is not effectively dispersed, a conductive path cannot be formed and the conductivity requirement of the semiconductive shield material cannot be satisfied.
In order to solve the above contradiction, it is an important solution to replace the traditional conductive carbon black by adding other carbon materials with higher conductivity and easier conductive path formation. In recent years, the rapid development of nano-carbon materials such as graphene and conductive carbon fibers provides a feasible and effective way for the development.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a novel EVA semi-conductive cable shielding material and a preparation method thereof, the cable shielding material has the advantages of high strength, good conductivity, simple production and processing technology, small pollution and the like, and the problems in the background art are solved.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: an EVA semiconductive cable shielding material comprises the following raw materials in parts by weight:
2-20 parts of a composite conductive carbon material, 0-10 parts of a dispersing agent, 100 parts of an ethylene-vinyl acetate copolymer (EVA), 0-8 parts of a dispersion aid, 0-3 parts of a crosslinking agent, 0-5 parts of a lubricating agent and 0-2 parts of an antioxidant.
Preferably, the composite conductive carbon material is a binary composition of graphene and conductive carbon fibers; wherein, the graphene is powder with the purity of more than or equal to 99 percent, and the diameter of the conductive carbon fiber is nano-scale.
Preferably, the dispersant is polyvinylpyrrolidone with a K value of more than or equal to 30.
Preferably, the EVA is an ethylene-vinyl acetate copolymer with the VA content of more than or equal to 10%, the melt index of the ethylene-vinyl acetate copolymer is 2.0-20.0 g/10min (190 ℃/2.16KG), the tensile strength is more than or equal to 10MPa, and the elongation at break is more than or equal to 400%.
Preferably, the auxiliary dispersing agent is a vinyl silane coupling agent, such as vinyl trimethoxy silane and vinyl triethoxy silane.
Preferably, the crosslinking agent is an organic peroxide, such as di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane (bis 25), and the like.
Preferably, the lubricant is a high molecular weight silicone lubricant such as E525, P121, 4042 or 6441P manufactured by the german winning creation company; the antioxidant is 1010, 1024, 1330 or 1098.
The invention also provides a preparation method of the EVA semiconductive cable shielding material, which comprises the following steps:
s1, adding the composite conductive carbon material and the dispersing agent into a mixer respectively, mixing at a low speed for 2-3 min at 80 ℃, and then mixing at a high speed for 3-5 min;
s2, sequentially adding an ethylene-vinyl acetate copolymer (EVA), an auxiliary dispersant, a cross-linking agent, a lubricant and an antioxidant into the mixer in S1, and then mixing at a high speed for about 10 min;
and S3, transferring the mixed material in the S2 into a screw extruder, and extruding and granulating to obtain the EVA semiconductive cable shielding material.
Preferably, the mixer is an SHR series high-speed mixer with the rotating speed of more than or equal to 300 r/min.
Preferably, the screw extruder is double-stage and comprises two parts, namely a double screw and a single screw; wherein the length-diameter ratio of the twin-screw is 40: 1.
(III) advantageous effects
Compared with the prior art, the invention provides the EVA semiconductive cable shielding material and the preparation method thereof, and the EVA semiconductive cable shielding material has the following beneficial effects:
1. according to the EVA semiconductive cable shielding material and the preparation method thereof, the two-dimensional nano carbon material graphene and the one-dimensional nano carbon material conductive carbon fiber are adopted, the nano effect and the super conductivity of different latitudes of the two-dimensional nano carbon material graphene are utilized, the dispersion effect of a conductive agent is improved by adopting a dispersant polyvinylpyrrolidone to perform pre-dispersion treatment with the graphene and the conductive carbon fiber, the composite conductive agent consisting of the graphene and the conductive carbon fiber is easier to form a conductive path, the addition amount of the composite conductive agent is far smaller than that of the carbon black added in the prior art, and the conductive requirement of the cable on the semiconductive shielding material can be met.
2. According to the EVA semiconductive cable shielding material and the preparation method thereof, the adopted auxiliary dispersing agent is vinyl triethoxysilane, which not only can play a role in assisting the dispersion of the nano conductive agent, but also can generate a crosslinking reaction to play a role in assisting the crosslinking, so that the phenomenon that the cable surface bulges due to pyrolysis in the subsequent vulcanization of the cable is avoided.
3. Compared with the traditional conductive carbon black, the addition amount of the composite conductive agent consisting of the graphene and the conductive carbon fiber is greatly reduced, banburying is not needed in production and processing, all materials are directly transferred into an extruder after being mixed, and granulation is carried out to prepare the EVA semi-conductive cable shielding material.
Detailed Description
The invention will be further elucidated with reference to the following specific examples.
Example 1:
the invention provides an EVA semiconductive cable shielding material, which comprises the following raw materials in parts by weight:
2-20 parts of a composite conductive carbon material, 0-10 parts of a dispersing agent, 100 parts of an ethylene-vinyl acetate copolymer (EVA), 0-8 parts of a dispersion aid, 0-3 parts of a crosslinking agent, 0-5 parts of a lubricating agent and 0-2 parts of an antioxidant.
Specifically, the composite conductive carbon material is a binary composition of graphene and conductive carbon fibers; wherein, the graphene is powder with the purity of more than or equal to 99 percent, and the diameter of the conductive carbon fiber is nano-scale.
In this embodiment, the graphene is preferably a powder with a carbon content of 99.9% or more, a particle size D50 of 10 μm or less, and a specific surface area of 50m or more2The average thickness is less than or equal to 5nm, and the conductivity is more than or equal to 5000S/M; the preferred conductive carbon fiber has the purity of more than or equal to 99.9 percent, the fiber diameter of 150-200 nm, the length of 10-20 mu m and the resistivity of less than or equal to 0.012 omega-cm.
Specifically, the dispersing agent is polyvinylpyrrolidone with a K value of more than or equal to 30.
In the embodiment, the dispersant polyvinylpyrrolidone K90 is preferable, the K value of the dispersant polyvinylpyrrolidone K90 is 88-96, the dispersant polyvinylpyrrolidone K90 is white powder in appearance, the melting point of the dispersant polyvinylpyrrolidone is about 165 ℃, and the density of the dispersant polyvinylpyrrolidone K3 is 1.69 g/cm.
Specifically, the EVA is an ethylene-vinyl acetate copolymer with the VA content of more than or equal to 10%, the melt index of the ethylene-vinyl acetate copolymer is 2.0-20.0 g/10min (190 ℃/2.16KG), the tensile strength is more than or equal to 10MPa, and the elongation at break is more than or equal to 400%.
In this embodiment, the preferable EVA has a VA content of 28%, a Shore hardness of 80A, a melt index of 6.0g/10min (190 ℃/2.16KG), a tensile strength of not less than 15MPa, and an elongation at break of not less than 600%.
Specifically, the auxiliary dispersing agent is a vinyl silane coupling agent, such as vinyl trimethoxy silane and vinyl triethoxy silane.
In this embodiment, the preferable dispersion aid is vinyltriethoxysilane, which has a boiling point of 160-161 ℃, is a colorless transparent liquid, and has a relative density of 0.9.
Specifically, the crosslinking agent is an organic peroxide, such as di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane (bis 25), and the like.
In this example, the preferred crosslinker is bis-25, with a decomposition temperature of 179 ℃ (half-life of 1 minute), and a pale yellow liquid in appearance.
Specifically, the lubricant is a high molecular weight silicone lubricant, such as E525, P121, 4042 or 6441P produced by German winning and creating company; the antioxidant is 1010, 1024, 1330 or 1098.
In this embodiment, the preferred lubricant is E525 in the form of a white powder in appearance; the preferable binary composition of the antioxidant is 1010 and 1024, and the addition ratio of the antioxidant to the binary composition is 1: 1. wherein the melting point of the antioxidant 1010 is 110-125 ℃, and the density is 1.15g/cm 3; the melting point of the antioxidant 1024 is 224-229 ℃, and the antioxidant is white powder.
The embodiment also provides a preparation method of the EVA semiconductive cable shielding material, which comprises the following steps:
s1, adding the composite conductive carbon material and the dispersing agent into a mixer respectively, mixing at a low speed for 2-3 min at 80 ℃, and then mixing at a high speed for 3-5 min;
s2, sequentially adding an ethylene-vinyl acetate copolymer (EVA), an auxiliary dispersant, a cross-linking agent, a lubricant and an antioxidant into the mixer in S1, and then mixing at a high speed for about 10 min;
and S3, transferring the mixed material in the S2 into a screw extruder, and extruding and granulating to obtain the EVA semiconductive cable shielding material.
Specifically, the mixer is an SHR series high-speed mixer with the rotating speed of more than or equal to 300 r/min.
In the embodiment, a high-speed mixer is preferably selected, the rotating speed of the high-speed mixer is 400-800 r/min, and the stirring blade is of a three-blade structure.
Specifically, the screw extruder is double-stage and comprises a double screw and a single screw; wherein the length-diameter ratio of the twin-screw is 40: 1.
the raw material grades and physical properties used in the following examples and comparative examples of the present invention are listed in Table 1:
the same processing technology is adopted in the embodiments 1-3 and the comparative examples 4-8, namely the materials are fully and uniformly mixed and then directly transferred into an extruder for granulation. The formulation and composition are shown in table 2:
the test results and performance indexes of the above examples 1 to 3 and comparative examples 4 to 8 of the present invention are shown in Table 3:
the hardness of the EVA semiconductive cable shielding materials obtained in the above examples and comparative examples is tested by using a shore durometer, and the value of the shore durometer is read at 10 seconds; the mechanical and mechanical properties and the heat resistance of the material are tested according to the standard of GB/T2951.11-2008: the stretching is carried out on a universal electronic tensile machine, and the stretching speed is 250 mm/min; the heat aging condition is aging at 136 ℃ for 168 hours; the temperature of the hot extension was 200 ℃. The resistivity of the alloy is tested by a resistance meter according to the standard of GB/T12706-2002.
In summary, examples 1 to 3: the EVA semiconductive cable shielding material prepared by adopting graphene and conductive carbon fiber as a composite conductive agent, adding polyvinylpyrrolidone as a dispersing agent and vinyl triethoxysilane as an auxiliary dispersing agent has high conductivity and strength, the resistivity of the EVA semiconductive cable shielding material is less than or equal to 30 omega-cm, the tensile strength of the EVA semiconductive cable shielding material is more than or equal to 15.9MPa, and the elongation at break of the EVA semiconductive cable shielding material is more than or equal to 340%. Other physical indexes such as hardness, thermal aging, thermal extension and appearance also meet the use requirements of the cable.
Comparative examples 1 to 3, comparative examples 4 and 5 only added graphene or conductive carbon fiber as a conductive aid, and both increased resistivity, 90 Ω · cm and 126 Ω · cm, respectively; while the resistivity of comparative example 6, to which no dispersing aid was added, was increased to 285 Ω. Comparative example 7, with the same total amount of carbon black added as the conductive agent, has a resistivity as high as 1.5 x 109Omega.cm, the conductive requirement of the cable semiconductive shielding material is far not met; in comparative example 8 in which the amount of carbon black was greatly increased (60 parts), the carbon black having a high added amount was poorly dispersed, and the resistivity was still 2.1X 103Omega cm, strength of only 8.3 MPa.
The above examples show that, in the invention, polyvinylpyrrolidone is used as a dispersant, and the polyvinylpyrrolidone, graphene and conductive carbon fiber are added into a mixer for pre-dispersion treatment; then, other auxiliary agents such as EVA base material, auxiliary dispersing agent vinyl silane coupling agent and the like are added for secondary mixing, so that the high effective dispersion of the conductive carbon material is ensured. By utilizing the superconductivity and different space dimensions of the graphene and the carbon fibers, compared with the traditional conductive carbon black, the addition amount of the conductive agent can be greatly reduced, and the prepared cable shielding material has the characteristics of high strength and good conductivity, simplifies the production and processing process and reduces black pollution.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.
Claims (10)
1. The EVA semiconductive cable shielding material is characterized by comprising the following raw materials in parts by weight:
2-20 parts of a composite conductive carbon material, 0-10 parts of a dispersing agent, 100 parts of an ethylene-vinyl acetate copolymer (EVA), 0-8 parts of a dispersion aid, 0-3 parts of a crosslinking agent, 0-5 parts of a lubricating agent and 0-2 parts of an antioxidant.
2. The EVA semiconductive cable shielding material of claim 1, wherein the composite conductive carbon material is a binary composition of graphene and conductive carbon fibers; wherein, the graphene is powder with the purity of more than or equal to 99 percent, and the diameter of the conductive carbon fiber is nano-scale.
3. The EVA semiconductive cable shielding material of claim 1, wherein the dispersant is polyvinylpyrrolidone having a K value of not less than 30.
4. The EVA semiconductive cable shielding material according to claim 1, wherein the EVA is an ethylene-vinyl acetate copolymer with a VA content of not less than 10%, and has a melt index of 2.0-20.0 g/10min (190 ℃/2.16KG), a tensile strength of not less than 10MPa, and an elongation at break of not less than 400%.
5. The EVA semiconductive power cable shielding material of claim 1, wherein the dispersion aid additive is a vinyl silane coupling agent, such as vinyl trimethoxysilane or vinyl triethoxysilane.
6. The EVA semiconductive cable shielding material of claim 1, wherein the crosslinking agent is an organic peroxide, such as di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (bis 25), and the like.
7. The EVA semiconductive power cable shielding material of claim 1, wherein the lubricant is a high molecular weight silicone lubricant such as E525, P121, 4042 or 6441P available from Woodson GmbH of Germany; the antioxidant is 1010, 1024, 1330 or 1098.
8. The preparation method of the EVA semiconductive cable shielding material according to any one of claims 1 to 7, comprising the steps of:
s1, adding the composite conductive carbon material and the dispersing agent into a mixer respectively, mixing at a low speed for 2-3 min at 80 ℃, and then mixing at a high speed for 3-5 min;
s2, sequentially adding an ethylene-vinyl acetate copolymer (EVA), an auxiliary dispersant, a cross-linking agent, a lubricant and an antioxidant into the mixer in S1, and then mixing at a high speed for about 10 min;
and S3, transferring the mixed material in the S2 into a screw extruder, and extruding and granulating to obtain the EVA semiconductive cable shielding material.
9. The EVA semiconductive cable shielding material of claim 8, wherein the mixer is an SHR series high-speed mixer with a rotation speed of 300r/min or more.
10. The EVA semiconductive power cable shielding material of claim 8, wherein the screw extruder is a double stage comprising two parts, a twin screw and a single screw; wherein the length-diameter ratio of the twin-screw is 40: 1.
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| CN112480751A (en) * | 2020-11-12 | 2021-03-12 | 深圳科诺桥科技股份有限公司 | Electromagnetic shielding heat shrinkable tube and manufacturing method thereof |
| CN112500631A (en) * | 2020-11-08 | 2021-03-16 | 江苏北化新橡新材料科技有限公司 | Halogen-free flame-retardant cable material with electromagnetic shielding function and preparation method thereof |
| CN113881133A (en) * | 2021-11-18 | 2022-01-04 | 深圳供电局有限公司 | High-voltage cable semiconductive shielding material with conductive carbon black efficiently dispersed and preparation method thereof |
| WO2023065430A1 (en) * | 2021-10-18 | 2023-04-27 | 深圳供电局有限公司 | High-voltage cable semi-conductive shielding material featuring high-efficiency dispersion of conductive carbon black and preparation method therefor |
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