CN113527795A - Semiconductive sheath material and preparation method and application thereof - Google Patents
Semiconductive sheath material and preparation method and application thereof Download PDFInfo
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- CN113527795A CN113527795A CN202110925043.0A CN202110925043A CN113527795A CN 113527795 A CN113527795 A CN 113527795A CN 202110925043 A CN202110925043 A CN 202110925043A CN 113527795 A CN113527795 A CN 113527795A
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- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 43
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 43
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 38
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 38
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims abstract description 34
- 239000003063 flame retardant Substances 0.000 claims abstract description 34
- -1 polyethylene Polymers 0.000 claims abstract description 29
- 239000004698 Polyethylene Substances 0.000 claims abstract description 23
- 229920000573 polyethylene Polymers 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 25
- 229920000098 polyolefin Polymers 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a semiconductive sheath material and a preparation method and application thereof. The semiconductive sheath material comprises the following components: ethylene-vinyl acetate copolymer, linear low density polyethylene, metallocene polyethylene, conductive carbon black and additives; wherein the mass ratio of the ethylene-vinyl acetate copolymer to the linear low density polyethylene to the metallocene polyethylene is 1:0.1-1:2.5-6, preferably 1:0.2-0.6: 3-5. The semiconductive sheath material can replace the conventional double-sheath structure of flame-retardant polyethylene and high-voltage semiconductive sheath, solves the problem of interface air gap of the double sheaths of the high-voltage cable, prolongs the service life of the cable, simplifies the production and processing process of the cable, and saves the cost.
Description
Technical Field
The invention relates to a semiconductive sheath material, a preparation method and application thereof, in particular to a flame-retardant semiconductive sheath material for a high-voltage cable, and belongs to the technical field of production of materials for cables.
Background
In the manufacture of 110KV and above ultra-high voltage cables, the semiconductive PE jacket is replacing the graphite layer for use as a semiconductive sheath for the cable. The outer sheath of the extra-high voltage cable is made of a material with large insulation resistance, when the extra-high voltage cable cannot be continuously grounded at multiple points, dangerous voltage is formed on the sheath at a position far away from the place, and the safe operation of the cable can be endangered, so the extra-high voltage power cable needs to adopt a semi-conductive outer sheath, the function of the extra-high voltage power cable is that charges induced on the sheath can be discharged to a contact body (such as the ground) through the semi-conductive layer, and meanwhile, the semi-conductive layer on the wire and cable outer sheath can also be used for cable sheath detection.
The conventional ultrahigh-voltage cable semi-conductive protective layer is mostly coated with graphite, and the graphite coating method sometimes causes uneven coating due to coating equipment, process and the like, is easy to damage and fall off during cable laying, and can influence normal detection in the cable installation process. Moreover, the coated graphite causes environmental pollution in factories during cable manufacturing and is not popular with cable laying constructors. At present, more and more cable plants are adopted to manufacture the ultrahigh-voltage cable by replacing a graphite coating with an extruded semi-conducting layer.
Citation 1 discloses a wire and cable sheath material for a high-speed railway, which comprises the following raw materials in parts by weight: 20-30 parts of linear low-density polyethylene, 15-20 parts of metallocene polyethylene, 30-40 parts of ethylene-vinyl acetate copolymer, 35-50 parts of magnesium hydroxide, 2-4 parts of white carbon black, 5-8 parts of bisphenol A-bis (diphenyl phosphate), 2-3 parts of pentaerythritol phosphate, 3-4 parts of melamine cyanurate, 2-3 parts of methyl phenyl polysiloxane, 1-2 parts of silane coupling agent, 1-2 parts of di-tert-butyl peroxydicumyl benzene, 0.5-1 part of triallyl isocyanurate, 3-10 parts of plasticizer and 0.5-1 part of antioxidant. The material has no conductivity, can not replace a graphite coating to be applied to the outer sheath of a submarine cable or a high-voltage cable, contains a silane coupling agent in the components, has strong water absorption, is easy to absorb water and damp when a finished product is stored, and can not be exposed in the air for a long time.
Citation 2 discloses an ultraviolet-resistant semiconductive polyethylene sheath material and application thereof. The jacking material comprises the following components in parts by weight: 50-60 parts of linear low-density polyethylene resin, 20-30 parts of semiconductive master batch, 5-10 parts of dispersing agent, 3-5 parts of composite antioxidant and 2-5 parts of composite processing aid; the melt index of the linear low-density polyethylene resin is more than or equal to 4g/10 min; and (3) putting the components into a double-screw extruder for granulation through a weight-increasing type blanking system. The material uses linear low-density polyethylene as a main base material, has poor aging performance under a high-temperature condition, and does not have flame retardance.
Cited documents:
cited document 1: CN111647223A
Cited document 2: CN109593256A
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the invention provides a semiconductive sheath material which can replace a double-sheath structure of flame-retardant polyethylene and a semiconductive sheath, eliminate an interface air gap between the flame-retardant polyethylene and a double-sheath layer of a high-voltage semiconductive sheath, prolong the service life of a cable, simplify the production and processing process of the cable and save the cost.
Furthermore, the invention also provides a preparation method of the semiconductive sheath material, which is easy to obtain raw materials and simple and feasible in preparation steps.
Means for solving the problems
The invention provides a semiconductive sheath material, which comprises the following components: ethylene-vinyl acetate copolymer, linear low density polyethylene, metallocene polyethylene, conductive carbon black and additives; wherein,
the mass ratio of the ethylene-vinyl acetate copolymer, the linear low-density polyethylene and the metallocene polyethylene is 1:0.1-1:2.5-6, preferably 1:0.2-0.6: 3-5.
The semiconductive sheath material provided by the invention has the following components, wherein the content of the ethylene-vinyl acetate copolymer is 10-30 parts by weight, preferably 12-14 parts by weight; the content of the linear low-density polyethylene is 2 to 10 parts, preferably 4 to 6 parts; 20-60 parts of metallocene polyethylene, preferably 49-53 parts; the content of the conductive carbon black is 24 to 34 parts, preferably 28 to 30 parts.
The semiconductive sheath material provided by the invention is characterized in that the additive comprises one or more of a lubricant, a flame retardant, a dispersant and an antioxidant;
preferably, the lubricant is present in an amount of 1.5 to 6 parts, preferably 2.5 to 3.7 parts, by weight; the content of the flame retardant is 5-10 parts, preferably 7-10 parts; the content of the dispersant is 0.05-1 part, preferably 0.1-0.4 part; the content of the antioxidant is 0.05-1 part, preferably 0.1-0.4 part.
The semiconductive sheathing compound according to the present invention, wherein the lubricant comprises polyethylene wax and/or silicone, preferably, the polyethylene wax has a number average molecular weight of 1500-.
The semiconductive sheathing compound according to the present invention, wherein the flame retardant includes magnesium hydroxide and/or aluminum hydroxide.
The semiconductive sheath material provided by the invention is characterized in that the dispersant is a wetting dispersant, preferably a multifunctional wetting dispersant.
The semiconductive sheath material according to the present invention, wherein the antioxidant comprises 4, 4' -thiobis (6-tert-butyl-m-cresol) and/or pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The semiconductive sheath material provided by the invention is characterized in that the melt index of the ethylene-vinyl acetate copolymer at 190 ℃ under the condition of 2.16kg is 4-6g/10min, and the content of vinyl acetate is 26-29%; and/or
The linear low density polyethylene has a melt index of 2-3g/10min at 190 ℃ under the condition of 2.16 kg.
The invention also provides a preparation method of the semiconductive sheath material, which comprises the step of mixing the components of the semiconductive sheath material.
The invention also provides an application of the semiconductive sheath material in preparation of a high-voltage cable.
ADVANTAGEOUS EFFECTS OF INVENTION
The semiconductive sheath material can replace the conventional double-sheath structure of flame-retardant polyethylene and high-voltage semiconductive sheath, solves the problem of interface air gap of the double sheaths of the high-voltage cable, prolongs the service life of the cable, simplifies the production and processing process of the cable, and saves the cost.
Furthermore, the preparation method of the semiconductive sheath material is easy to obtain raw materials, simple and feasible in preparation steps, and suitable for mass production.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
<First aspect>
The invention provides a semiconductive sheath material in a first aspect, which comprises the following components: ethylene-vinyl acetate copolymer, linear low density polyethylene, metallocene polyethylene, conductive carbon black and additives; wherein,
the mass ratio of the ethylene-vinyl acetate copolymer, the linear low-density polyethylene and the metallocene polyethylene is 1:0.1-1:2.5-6, preferably 1:0.2-0.6: 3-5.
The flame-retardant semiconductive polyolefin sheath material for the high-voltage cable takes the ethylene-vinyl acetate copolymer, the linear low-density polyethylene and the metallocene polyethylene as the matrix, can replace the existing double-sheath structure of the polyethylene and the high-voltage semiconductive sheath, solves the problem of interface air gaps of the double-sheath structure of the high-voltage cable, and prolongs the service life of the cable.
The ethylene-vinyl acetate copolymer has good flexibility and elasticity, good chemical stability, good aging resistance and ozone resistance and no toxicity, so that the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable with excellent performance is prepared, and particularly, the ethylene-vinyl acetate copolymer with the melt index of 4-6g/10min and the vinyl acetate content of 26-29 percent under the conditions of 190 ℃ and 2.16kg is preferably used in the invention, for example: elvax260, and the like.
The invention uses ethylene-vinyl acetate copolymer as a matrix, and simultaneously adds linear low-density polyethylene and metallocene polyethylene, thereby ensuring that the extrusion surface of the material is smooth and flat.
In some specific embodiments, the ethylene-vinyl acetate copolymer is present in an amount of 10 to 30 parts, preferably 12 to 14 parts, by weight, for example: 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 21 parts, 23 parts, 25 parts, 27 parts, 29 parts and the like; when the content of the ethylene-vinyl acetate copolymer is 10-30 parts, the semiconductive sheath material disclosed by the invention has good crust formation property in combustion, and the material is not easy to embrittle at low temperature.
The linear low-density polyethylene has the melt index of 2-3g/10min at 190 ℃ and under the condition of 2.16kg, and the linear low-density polyethylene with the melt index has better compatibility in a system.
In some specific embodiments, the linear low density polyethylene is present in an amount of 2 to 10 parts, preferably 4 to 6 parts, by weight, for example: 3 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts and the like; when the content of the linear low-density polyethylene is 2-10 parts, the semiconductive sheath material disclosed by the invention has good tensile strength, so that a system has good compatibility.
The present inventors have found that metallocene polyethylene has excellent properties such as good processability, high strength, good rigidity and transparency, high and low temperature resistance, and chemical resistance. When metallocene polyethylene is compounded with ethylene-vinyl acetate copolymer and linear low-density polyethylene, the excellent performance of the metallocene polyethylene can be fully exerted, and the semiconductive sheath material with excellent performance is obtained.
In some specific embodiments, the metallocene polyethylene is present in an amount of 20 to 60 parts, preferably 49 to 53 parts, by weight, for example: 23 parts, 25 parts, 28 parts, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts and the like; when the content of the metallocene polyethylene is 20-60 parts, the semiconductive sheath material disclosed by the invention can have excellent ageing resistance, and the material has excellent elongation at break.
Further, in the present invention, the mass ratio of the ethylene-vinyl acetate copolymer of the present invention, the linear low density polyethylene and the metallocene polyethylene is 1:0.1 to 1:2.5 to 6, preferably 1:0.2 to 0.6:3 to 5. When the mass ratio of the ethylene-vinyl acetate copolymer to the linear low-density polyethylene to the metallocene polyethylene is 1:0.1-1:2.5-6, the mechanical property of the material is good, and the tensile strength can reach more than 15 MPa. Specifically, the ethylene-vinyl acetate copolymer and the linear low density polyethylene of the present invention may have a metallocene polyethylene mass ratio of 1:0.15-0.9:2.5-5.4, or 1:0.25-0.75:3.5-4.6, or 1:0.3-0.65: 3-4.
Further, the semiconductive sheath material also comprises conductive carbon black, and the semiconductive sheath material with proper conductivity can be obtained by adding the conductive carbon black. Specifically, the content of the conductive carbon black is 24 to 34 parts, preferably 28 to 30 parts, by weight, for example: 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts and the like; when the content of the conductive carbon black is 24-34 parts, the conductive carbon black can better play a role in conducting electricity.
Specifically, in the present invention, the conductive carbon black of the present invention may be Yondoto YD-250C, Yondoto 260, Columbia 7090, Carbott carbon black VXC500, Carbott carbon black VXC200, Carbott carbon black VXC68, or the like.
In some specific embodiments, the additive comprises one or a combination of two or more of a lubricant, a flame retardant, a dispersant, and an antioxidant.
The lubricating performance of the semiconductive sheath material is improved by using the lubricant. In view of the fact that the lubricating effect can be exerted to the maximum extent, the content of the lubricant is 1.5 to 6 parts, preferably 2.5 to 3.7 parts, by weight, for example: 1.8 parts, 2 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 parts, 5.5 parts, 5.8 parts and the like.
In particular, the lubricant comprises polyethylene wax and/or silicone. The present invention can protect the ethylene-vinyl acetate copolymer from decomposition by using polyethylene wax. Preferably, the number average molecular weight of the polyethylene wax is 1500-3000, and when the number average molecular weight of the polyethylene wax is 1500-3000, the dispersion of the conductive carbon black in the system is facilitated. In addition, silicone has a more excellent lubricating effect than other external lubricants and is less likely to precipitate.
Further, in the present invention, the polyethylene wax is contained in an amount of 0.5 to 2 parts, preferably 1 to 1.2 parts, by weight, for example: 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts and the like. When the polyethylene wax content is 0.5-2 parts, the material can be extruded for a long time during processing. The silicone is present in an amount of 1 to 4 parts, preferably 1.5 to 2.5 parts, by weight, for example: 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts and the like. When the content of the silicone is 1 to 4 parts, the effect of the silicone can be exerted to the maximum extent.
In some specific embodiments, the dispersion of the conductive carbon black may be ensured by using a dispersant. Specifically, the method comprises the following steps: the content of the dispersant is 0.05 to 1 part, preferably 0.1 to 0.4 part, by weight, for example: 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.55 part, 0.6 part, 0.65 part, 0.7 part, 0.75 part, 0.8 part, 0.85 part, 0.9 part and the like; when the content of the dispersing agent is 0.05-1 part, the dispersing agent can help the conductive carbon black to be better dispersed, and the extruded surface is more smooth and flat.
Further, the dispersant of the present invention is a wetting dispersant, preferably a polyfunctional dispersant. In particular, the dispersant may be TEGO Dispers 760W (an aqueous solution of a multifunctional surfactant with pigment affinity groups).
In some specific embodiments, the present invention improves the flame retardant performance of the semiconductive jacket material of the present invention by using a flame retardant. In some specific embodiments, the flame retardant is present in an amount of 5 to 10 parts, preferably 7 to 10 parts, by weight, for example: 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts and the like; when the content of the flame retardant is 5-10 parts, the semiconductive sheath material provided by the invention has a good oxygen index, and the mechanical properties of the material cannot be influenced. Specifically, in the present invention, the flame retardant includes magnesium hydroxide and/or aluminum hydroxide.
Further, the semiconductive sheath material of the present invention further comprises an antioxidant, specifically, the content of the antioxidant is 0.05 to 1 part by weight, preferably 0.1 to 0.4 part by weight, and in the present invention, the antioxidant is 4, 4' -thiobis (6-tert-butyl-m-cresol) and/or tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the like.
<Second aspect of the invention>
A second aspect of the present invention provides a method for preparing the semiconductive sheathing compound according to the first aspect of the present invention, which includes a step of mixing components of the semiconductive sheathing compound.
In some specific embodiments, the preparation method comprises the steps of:
mixing the lubricant, the antioxidant and the dispersant to obtain an additive premix for later use;
mixing ethylene-vinyl acetate copolymer, linear low-density polyethylene, metallocene polyethylene, conductive carbon black and a flame retardant, adding an additive premix, continuously mixing until the temperature of the dough reaches 145-150 ℃ to obtain the cured rubber.
And extruding, bracing and granulating the cooked rubber, screening out irregular particles, air-drying, cooling and packaging to obtain the semiconductive sheath material.
Further, the invention also provides an application of the semiconductive sheath material according to the first aspect of the invention in preparation of high-voltage cables.
Further, the invention also provides a high-voltage cable which comprises the semiconductive sheath material of the first aspect.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the examples: ethylene-vinyl acetate copolymer: the melt index of the ethylene-vinyl acetate copolymer is 4-6g/10min under the conditions of 190 ℃ and 2.16kg, and the content of vinyl acetate is 28 percent.
Linear low density polyethylene: the linear low-density polyethylene has a melt index of 2-3g/10min at 190 ℃ under the condition of 2.16 kg;
metallocene polyethylene: exxon Mobil corporation;
polyethylene wax: HONEYWELL CORPORATION;
silicone: polymer materials group ltd, wangma, zhejiang;
magnesium hydroxide: weifang Hailong magnesium industries Ltd.
In the examples: the contents of all components are calculated by weight parts.
Example 1
The method comprises the following steps: 1.1 parts of polyethylene wax with the number average molecular weight of 1500-3000, 0.4 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester as an antioxidant, 0.2 part of polyfunctional dispersant TEGO dispers 760W and 2.1 parts of silicone are added into a stirrer for premixing.
Step two: and (2) putting 12 parts of ethylene-vinyl acetate copolymer, 4 parts of linear low-density polyethylene, 49 parts of metallocene polyethylene, 50028 parts of cabot carbon black VXC and 7 parts of magnesium hydroxide into an internal mixer, sealing and mixing for 60 seconds, adding the raw materials pretreated in the step one, sealing and mixing for 300 seconds again, mixing until the temperature of the material mass reaches 148 ℃, and mixing the materials into the cured rubber.
Step three: and feeding the mixed cooked rubber into a single screw for extrusion, bracing and granulation, screening out irregular particles from the obtained particles through a vibrating screen, and then air-drying, cooling and packaging to obtain a final product, namely the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable.
Example 2
The difference between the present example and example 1 is 14 parts of ethylene-vinyl acetate copolymer, 6 parts of linear low density polyethylene, 53 parts of metallocene polyethylene, 50030 parts of cabot carbon black VXC, and the rest is the same as example 1. And the preparation process of the embodiment 2 is the same as that of the embodiment 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Example 3
The difference between the present example and example 1 is that the ethylene-vinyl acetate copolymer 13 parts, the linear low density polyethylene 5 parts, the metallocene polyethylene 51 parts, the cabot carbon black VXC 50029 parts, and the rest of the composition is the same as example 1. And the preparation process of the embodiment 3 is the same as that of the embodiment 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Example 4
The difference between the present example and example 1 is that 12 parts of ethylene-vinyl acetate copolymer, 4 parts of linear low density polyethylene, 53 parts of metallocene polyethylene, 50028 parts of cabot carbon black VXC, and the rest of the composition is the same as that of example 1. And the preparation process of the embodiment 3 is the same as that of the embodiment 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Example 5
The difference between the present example and example 1 is 14 parts of ethylene-vinyl acetate copolymer, 6 parts of linear low density polyethylene, 49 parts of metallocene polyethylene, 50030 parts of cabot carbon black VXC, and the rest is the same as example 1. And the preparation process of the embodiment 3 is the same as that of the embodiment 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Example 6
The difference between the present example and example 1 is that 12 parts of ethylene-vinyl acetate copolymer, 5 parts of linear low density polyethylene, 49 parts of metallocene polyethylene, 50030 parts of cabot carbon black VXC, and the rest of the composition is the same as that of example 1. And the preparation process of the embodiment 3 is the same as that of the embodiment 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Comparative example 1
The ethylene-vinyl acetate copolymer in example 6 was replaced with linear low density polyethylene, that is, 0 part of ethylene-vinyl acetate copolymer and 17 parts of low density polyethylene, and the rest was the same as in example 6, and the preparation process of comparative example 1 was the same as in example 6, to prepare the flame-retardant semiconductive polyolefin sheath material for high-voltage cables.
Comparative example 2
The metallocene polyethylene in example 6 was replaced with linear low density polyethylene, and the rest was the same as in example 6, that is, 0 part of metallocene polyethylene and 54 parts of linear low density polyethylene, and the rest of the composition was the same as in example 6. And the preparation process of comparative example 2 is the same as that of example 6, and the flame-retardant semiconductive polyolefin sheath material for high-voltage cables is prepared.
Comparative example 3
The polyethylene wax in example 6 was replaced with metallocene polyethylene, i.e., 50.1 parts metallocene polyethylene and 0 part polyethylene wax, and the rest of the composition was the same as in example 6. And the preparation process of the comparative example 3 is the same as that of the example 6, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Comparative example 4
The silicone in example 1 was replaced with ethylene-vinyl acetate copolymer, i.e., 14.1 parts of ethylene-vinyl acetate copolymer and 0 part of silicone, and the composition was the same as in example 1. And the preparation process of the comparative example 4 is the same as that of the example 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Comparative example 5
The multi-functional dispersant TEGO dispers 760W in example 1 was replaced by ethylene-vinyl acetate copolymer, i.e., ethylene-vinyl acetate copolymer 12.2 parts, and the multi-functional dispersant TEGO dispers 760W was 0 parts, all the other compositions being the same as in example 1. And the preparation process of the comparative example 5 is the same as that of the example 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Comparative example 6
3 parts of ethylene-vinyl acetate copolymer in the ethylene-vinyl acetate copolymer in example 1 was replaced with a polyfunctional dispersant TEGO dispers 760W, that is, 9 parts of ethylene-vinyl acetate copolymer, 3.2 parts of the polyfunctional dispersant TEGO dispers 760W, and the remaining composition was the same as in example 1. And the preparation process of the comparative example 6 is the same as that of the example 1, and the flame-retardant semiconductive polyolefin sheath material for the high-voltage cable is prepared.
Performance testing
The semiconductive shield materials of examples 1-6 and comparative examples 1-6 were subjected to the relevant performance tests according to the test standards and requirements of table 1 below, and the results are shown in tables 2 and 3:
TABLE 1
TABLE 2
TABLE 3
The flame-retardant semiconductive polyolefin sheath material for the high-voltage cable disclosed by the embodiments 1-6 can replace the conventional double-sheath structure of flame-retardant polyethylene and a high-voltage semiconductive sheath, so that the problem of interface air gaps of the double-sheath structure of the high-voltage cable is solved, and the service life of the cable is prolonged.
As can be seen from example 6 and comparative example 1, when the ethylene-vinyl acetate copolymer is not used, the carbon forming property of the material is poor, and the oxygen index is far lower than that of example 6; in addition, the elongation at break and tensile strength of the comparative example 1 are low and cannot meet the requirements; in addition, comparative example 1 also had poor resistance properties.
As can be seen from example 6 and comparative example 2, the aging properties were poor when metallocene polyethylene was not used; in addition, the elongation at break and tensile strength of the comparative example 2 are low and cannot meet the requirements; in addition, comparative example 2 also had poor resistance properties.
From example 6 and comparative example 3, it can be seen that when polyethylene wax is not used, its elongation at break is too low, only 321%, much lower than in example 6; also, comparative example 3 has a lower tensile strength than example 6; in addition, comparative example 3 also had poor resistance properties.
From example 1 and comparative example 4, it can be seen that when no silicone is used, its elongation at break is too low, only 315%, much lower than example 1, and also lower in tensile strength than example 1.
As can be seen from example 1 and comparative example 5, when no dispersant is used, the carbon black dispersion effect in the system is poor, the tensile strength is low, and the electrical resistance is not ideal.
As can be seen from example 1 and comparative example 6, when the content of the dispersant is too high, the tensile strength is low and does not meet the standard requirements when the content of the dispersant is high. The dispersant used in the invention has higher unit price and higher cost.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. The semiconductive sheath material is characterized by comprising the following components: ethylene-vinyl acetate copolymer, linear low density polyethylene, metallocene polyethylene, conductive carbon black and additives; wherein,
the mass ratio of the ethylene-vinyl acetate copolymer, the linear low-density polyethylene and the metallocene polyethylene is 1:0.1-1:2.5-6, preferably 1:0.2-0.6: 3-5.
2. The semiconductive sheath material according to claim 1, wherein the ethylene-vinyl acetate copolymer is present in an amount of 10 to 30 parts, preferably 12 to 14 parts; the content of the linear low-density polyethylene is 2 to 10 parts, preferably 4 to 6 parts; 20-60 parts of metallocene polyethylene, preferably 49-53 parts; the content of the conductive carbon black is 24 to 34 parts, preferably 28 to 30 parts.
3. The semiconductive sheath material according to claim 1 or 2, wherein the additive comprises one or a combination of two or more of a lubricant, a flame retardant, a dispersant and an antioxidant;
preferably, the lubricant is present in an amount of 1.5 to 6 parts, preferably 2.5 to 3.7 parts, by weight; the content of the flame retardant is 5-10 parts, preferably 7-10 parts; the content of the dispersant is 0.05-1 part, preferably 0.1-0.4 part; the content of the antioxidant is 0.05-1 part, preferably 0.1-0.4 part.
4. The semiconductive sheath material according to claim 3, wherein the lubricant comprises polyethylene wax and/or silicone, preferably the polyethylene wax has a number average molecular weight of 1500-3000.
5. The semiconductive sheath material according to claim 3 or 4, wherein the flame retardant comprises magnesium hydroxide and/or aluminium hydroxide.
6. The semiconductive sheath material according to any one of claims 3 to 5, wherein the dispersant is a wetting dispersant, preferably a multifunctional wetting dispersant.
7. The semiconductive sheath material according to any one of claims 3 to 6, wherein the antioxidant comprises 4, 4' -thiobis (6-tert-butyl-m-cresol) and/or pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
8. The semiconductive sheath material according to any one of claims 1 to 7, wherein the ethylene-vinyl acetate copolymer has a melt index of 4 to 6g/10min at 190 ℃ and 2.16kg, and a vinyl acetate content of 26 to 29%; and/or
The linear low density polyethylene has a melt index of 2-3g/10min at 190 ℃ under the condition of 2.16 kg.
9. A method for preparing a semiconductive jacket composition according to any of claims 1 to 8, comprising a step of mixing the components of the semiconductive jacket composition.
10. Use of the semiconductive sheath material according to any one of claims 1 to 8 for the preparation of high voltage cables.
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