WO1988006341A1 - Method of producing an electrically semi-conducting, strippable plastics mixture - Google Patents

Method of producing an electrically semi-conducting, strippable plastics mixture Download PDF

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Publication number
WO1988006341A1
WO1988006341A1 PCT/DK1988/000031 DK8800031W WO8806341A1 WO 1988006341 A1 WO1988006341 A1 WO 1988006341A1 DK 8800031 W DK8800031 W DK 8800031W WO 8806341 A1 WO8806341 A1 WO 8806341A1
Authority
WO
WIPO (PCT)
Prior art keywords
premix
organic
mixture
polyolefin
plastics
Prior art date
Application number
PCT/DK1988/000031
Other languages
French (fr)
Inventor
Inger-Margrete Procida
Keld Venø POULSEN
Original Assignee
Aktieselskabet Nordiske Kabel- Og Traadfabriker
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aktieselskabet Nordiske Kabel- Og Traadfabriker filed Critical Aktieselskabet Nordiske Kabel- Og Traadfabriker
Publication of WO1988006341A1 publication Critical patent/WO1988006341A1/en
Priority to NO884569A priority Critical patent/NO884569L/en
Priority to FI884819A priority patent/FI884819A0/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
    • H01B13/145—Pretreatment or after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion

Definitions

  • the present invention relates to a method of producing an electrically semi-conducting, strippable plastics mixture, in particular for use as screening material for electric wires and cables.
  • Electric wires and cables such as copper wires, are often covered with a coating material or a protective sheath, which may be a plastics material.
  • a coating material or a protective sheath which may be a plastics material.
  • the wire or cable is coated with several layers, e.g. a combination of one or several layers of semi-conducting material, one or more layers of insulating material and possibly with a metal taping or metal braid and an outer sheath.
  • GB patent specification No. 1 286 460 describes a method of producing a cross-linked polyolefin, in which thermo- plastic polyethylene or a copolymer of ethylene and a small amount of propylene and/or butylene is mixed with an unsaturated hydrolyzable silan in the presence of a free-radical-forming compound, e.g. a peroxide, the reaction being carried out at a temperature preferably within the range 160-220°C, whereafter the mixture or a shaped product thereof is moisture-exposed to complete the cross-linking reaction.
  • a free-radical-forming compound e.g. a peroxide
  • GB patent specification No. 1 526 398 describes the production of similar cross-linked polyolefins or copolymerizates which are particularly suited for insulating electric cables and for tube manufacture. This material is not semi-conducting either. It is, however, possible to add carbon black, but only in small amounts, and with the aim of achieving colouring or protection against sunlight, but not of achieving semi ⁇ conducting properties.
  • the invention relates to a method of producing an electrically semi-conducting, strippable plastics mixture, in particular for use as screening material for electric wires and cables, according to which a poly ⁇ olefin and/or a copolymerizate of several olefins is mixed with a hydrolyzable unsaturated organic silan, a free-radical-forming organic compound, possible suited plastics additives and hot comminuted carbon, the method being characterized in that a premix containing the polyolefin and/or the copolymerizate of olefins, the organic silan, the free-radical-forming organic compound and optional conventional additives are intimately mixed in a hot state, until the unsaturated organic silan has reacted substantially with the polyolefin and/or the copolymerizate of olefins, the comminuted carbon subsequently being added to the premix while it is still hot.
  • the free-radical-forming organic compound is preferably peroxide.
  • the premix is treated for ? - 30 min. at a temperature within the range 180°C-230°C, whereafter while the premix is still hot the comminuted carbon is admixed under continued mixing, the mixture subesquently being cooled and granulated.
  • a Banbury-mixer or an extruder is well-suited for kneading and homogenising the premix and for the subse ⁇ quent admixing of comminuted carbon.
  • Preferred carbon is carbon black having a BET-surface larger than 150 m 2 /g.
  • the invention also relates to a method of applying the coating material according to the invention around a wire or a cable. This is advantageously done by extrud ⁇ ing the plastics mixture at a temperature within the range 180°C-210°C, as a conventional extruder can be used.
  • the electrically semi-conducting plastics mixture may be an ethylene-copolymer, in which the second monomer in an amount of 15-45% may be of the type methylacrylate, vinylacrylate, ethylacrylate or vinylacetate or mixtures thereof in an amount of 40-70 weight-%, mixed with poly ⁇ olefin of the type polyethylene, polypropylene or copolymers hereof or mixtures thereof in an amount of 10-30 weight-%, and an elastomeric ethylenepropylene- copolymer or ethylenepropyleneterpolymer in an amount of 3-15 weight-%.
  • the organic peroxide is advantageously present in an amount of 0.01-1.0 weight-%, and the organic silan in an amount of 0.2-2.0 weight-%. Further ⁇ more, an antioxydant may be admixed in an amount of 0.2- 2 weight-%, and one or more lubricants in an amount of 0.001-5 weight-%.
  • the comminuted carbon imparting the electrically semi-conducting properties to the plastics mixture is preferably carbon black having a surface (according to the BET-method) in excess of 150 m 2 /g.
  • the volumetric resistance of the electrically semi-conduct ⁇ ing plastics mixtures measured according ASTM d257 is less than 1000 ohm x cm at 20°C and 90°C.
  • Components I-IX are introduced into a mixer in the stated order, the temperature in the mass during the tumbling being raised to 215-220°C. After few minutes the carbon-component is added, and the mixture is cooled and granulated.
  • Hot set test according to IEC 502 / 540; 200°C / 20N / 15 min.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

An electrically semi-conducting, strippable coating material for electric wires and cables is produced by intimately mixing a premix of a polyolefin with an unsaturated organic silan, a free-radical-forming organic compound and possible plastics additives in a hot state, until the unsaturated organic silan has reacted significantly with the polyolefin and/or the copolymerizate of olefins, preferably for 1/2-30 min. at 180-230°C, and subsequently admixing comminuted carbon while the mixture is still hot.

Description

Method of producing an electrically semi-conducting, strippable plastics mixture.
The present invention relates to a method of producing an electrically semi-conducting, strippable plastics mixture, in particular for use as screening material for electric wires and cables.
Electric wires and cables, such as copper wires, are often covered with a coating material or a protective sheath, which may be a plastics material. Sometimes the wire or cable is coated with several layers, e.g. a combination of one or several layers of semi-conducting material, one or more layers of insulating material and possibly with a metal taping or metal braid and an outer sheath.
It is known to use a coating consisting of an electrically semi-conducting plastics mixture which must be strippable to allow wire or cable ends to be stripped for connection.
It is the object of the present invention to produce an electrically semi-conducting strippable plastics mixture which is suited for use as screening material for electric wires and cables.
GB patent specification No. 1 286 460 describes a method of producing a cross-linked polyolefin, in which thermo- plastic polyethylene or a copolymer of ethylene and a small amount of propylene and/or butylene is mixed with an unsaturated hydrolyzable silan in the presence of a free-radical-forming compound, e.g. a peroxide, the reaction being carried out at a temperature preferably within the range 160-220°C, whereafter the mixture or a shaped product thereof is moisture-exposed to complete the cross-linking reaction. The known material thus produced possess high stress crazing resistance and a high tensile strength.
Furthermore, it possess high organic solvent resistance.
Because of these properties, the material has been suggested for use as electric insulation materials and for containers and tubes which come into contact with hot fluids. On the other hand, it has not been possible on the basis of such a mixture or on the basis of other¬ wise known technique to produce satisfactory, electrically semi-conducting, strippable coating materials suited for live electric wires and cables.
GB patent specification No. 1 526 398 describes the production of similar cross-linked polyolefins or copolymerizates which are particularly suited for insulating electric cables and for tube manufacture. This material is not semi-conducting either. It is, however, possible to add carbon black, but only in small amounts, and with the aim of achieving colouring or protection against sunlight, but not of achieving semi¬ conducting properties.
In order to produce an electrically semi-conducting material it would be obvious to modify one of the above known processes by admixing larger amounts of comminuted carbon, such as carbon black. Experiments, however, have shown that no satisfactory cross-linking of the semi¬ conducting material and consequently unsatisfactory mechanical properties are obtained by that procedure.
According to the present invention it has now surprisingly been found that a cross-linkable material with optimum semi-conducting properties and which is also strippable can be obtained if the comminuted carbon is admixed when the other plastics components have been intimately mixed and the cross-linking agent already has reacted with the polymeric materials. The stated mixing order is decisive to the achievement of the aimed at electric and in particular mechanical properties at the cable operating temperature.
Thus the invention relates to a method of producing an electrically semi-conducting, strippable plastics mixture, in particular for use as screening material for electric wires and cables, according to which a poly¬ olefin and/or a copolymerizate of several olefins is mixed with a hydrolyzable unsaturated organic silan, a free-radical-forming organic compound, possible suited plastics additives and hot comminuted carbon, the method being characterized in that a premix containing the polyolefin and/or the copolymerizate of olefins, the organic silan, the free-radical-forming organic compound and optional conventional additives are intimately mixed in a hot state, until the unsaturated organic silan has reacted substantially with the polyolefin and/or the copolymerizate of olefins, the comminuted carbon subsequently being added to the premix while it is still hot.
The free-radical-forming organic compound is preferably peroxide.
According to a preferred embodiment of the method according to the invention the premix is treated for ?- 30 min. at a temperature within the range 180°C-230°C, whereafter while the premix is still hot the comminuted carbon is admixed under continued mixing, the mixture subesquently being cooled and granulated.
Temperature and treatment time as well as the kind and amount of peroxide are so adjusted that the silan- compound reacts significantly with the polymeric material, however, without formation of cross-linkages between the polymeric chains. The reaction progresses most rapidly at the highest temperature. At temperatures above 230σC there is risk of the cross-linkage continu¬ ing to completion, thus making it impossible subse¬ quently to shape the plastics mixture.
A Banbury-mixer or an extruder is well-suited for kneading and homogenising the premix and for the subse¬ quent admixing of comminuted carbon. Preferred carbon is carbon black having a BET-surface larger than 150 m2/g.
The invention also relates to a method of applying the coating material according to the invention around a wire or a cable. This is advantageously done by extrud¬ ing the plastics mixture at a temperature within the range 180°C-210°C, as a conventional extruder can be used.
According to one embodiment of the invention the electrically semi-conducting plastics mixture may be an ethylene-copolymer, in which the second monomer in an amount of 15-45% may be of the type methylacrylate, vinylacrylate, ethylacrylate or vinylacetate or mixtures thereof in an amount of 40-70 weight-%, mixed with poly¬ olefin of the type polyethylene, polypropylene or copolymers hereof or mixtures thereof in an amount of 10-30 weight-%, and an elastomeric ethylenepropylene- copolymer or ethylenepropyleneterpolymer in an amount of 3-15 weight-%. The organic peroxide is advantageously present in an amount of 0.01-1.0 weight-%, and the organic silan in an amount of 0.2-2.0 weight-%. Further¬ more, an antioxydant may be admixed in an amount of 0.2- 2 weight-%, and one or more lubricants in an amount of 0.001-5 weight-%. The comminuted carbon imparting the electrically semi-conducting properties to the plastics mixture is preferably carbon black having a surface (according to the BET-method) in excess of 150 m2/g. The volumetric resistance of the electrically semi-conduct¬ ing plastics mixtures measured according ASTM d257 is less than 1000 ohm x cm at 20°C and 90°C.
In the following the method according to the invention is further described by way of an example.
Example
A series of plastics mixtures were produced having compositions within the following ranges, all stated in parts by weight:
I Ethylene-copolymer of type 1 28 to 63
II Ethylene-copolymer of type 2 0 to 32
III Polyolefin of type 1 15 to 20
IV Polyolefin of type 2 1 to 3 V Elastomers 3 to 6
VI Organic peroxide 0.06 to 0.14
VII Organic silan 1.2 to 1.8
VIII Antioxydant 0.4 to 1
IX Lubricant 0.1 to 0.2 X Carbon 12 to 18
Components I-IX are introduced into a mixer in the stated order, the temperature in the mass during the tumbling being raised to 215-220°C. After few minutes the carbon-component is added, and the mixture is cooled and granulated.
From the semi-conducting plastics mixture formed there were partly pressed a 1.5 mm thick sheet at 185°C, and partly extruded a 1.5 mm thick band by introducing the mixture into an extruder equipped with a 30 mm screw having an L:D-ratio of 20:1. Both the pressed sheet and the extruded band were cross- linked by submersion for 16 hours in 85°C hot water ad¬ mixed 0.5 weight-% dibutylindilaurate.
The cross-linked blanks thus produced were tested as follows:
1. Hot set test according to IEC 502 / 540; 200°C / 20N / 15 min.
Measured value: 25%
2. Permanent elongation according to IEC 502 / 540; 200°C / 20N / 15 min. Measured value: 0%
3. Gel-content after boiling for 6 hours in decahydronaphtalene:
Measured value: 70%
Volumetric resistance according to ASTM D 257 at
20°C.
Measured value: 75 ohm x cm.

Claims

C l a i m s :
1. Method of producing an electrically semi-conduct¬ ing, strippable plastics mixture, in particular for use as coating material for electric wires and cables, according to which a polyolefin and/or copolymerizate of several olefins is mixed with a hydrolyzable unsaturated organic silan, an organic free-radical-forming compound, possible suited plastics additives and hot comminuted carbon, c h a r a c t e r i z e d in that a premix con¬ taining the polyolefin and/or copolymerizate of olefins, the organic silan, the free-radical-forming organic compound and possible plastics additives are intimately mixed in a hot state until the unsaturated organic silan has reacted substantially with the polyolefin and/or copolymerizate of olefins, the comminuted carbon subsequently being added to the premix while it is still hot.
2. Method according to claim 1, c h a r a c t e r ¬ i z e d in that the said premix is treated for ?-30 min. at a temperature within the range 180°C-230°C, whereafter while the premix is still hot the comminuted carbon is admixed under continued tumbling, the mixture subsequently being cooled and granulated.
3. Method according to claim 2, c h a r a c t e r ¬ i z e d in that the premix is treated for |-5 min. at 200°C-220°C before admixing the comminuted carbon.
4. Method according to any of the claims 1-3, c h a r a c t e r i z e d in that the premix is kneaded in a Banbury-mixer.
5. Method according to any of the claims 1-4, c h a r a c t e r i z e d in that the premix is kneaded in an extruder having a L:D-ratio beween 1:10 and 1:30, preferably about 1:15.
6. Method according to any of the claims 1-5, c h a r a c t e r i z e d in that the comminuted carbon is carbon black having a BET-surface larger than 150 m2/g.
7. Method according to any of the claims 1-6, c h a r a c t e r i z e d in that the organic free- radical-forming compound, is an organic peroxide.
8. Method of applying the coating material produced according to claim 1 as a mantle around an electric wire or a cable, c h a r a c t e r i z e d in that the plastics mixture is extruded at a temperature around the wire or cable within the range 180°C-210°C, whereafter the plastics mixture is aftercured by water treatment or steaming.
PCT/DK1988/000031 1987-02-20 1988-02-19 Method of producing an electrically semi-conducting, strippable plastics mixture WO1988006341A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
NO884569A NO884569L (en) 1987-02-20 1988-10-13 PROCEDURE FOR THE PREPARATION OF AN ELECTRIC SEMICONDUCTIVE, REMOVABLE PLASTIC MIXTURE.
FI884819A FI884819A0 (en) 1987-02-20 1988-10-19 FOERFARANDE FOER FRAMSTAELLNING AV EN ELEKTRISKT HALVLEDANDE, LOSSNANDE PLASTBLANDNING.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DK089087A DK89087A (en) 1987-02-20 1987-02-20 METHOD FOR MANUFACTURING AN ELECTRIC SEMI-CONDUCTIVE, STRIPABLE PLASTIC BLENDER
DK890/87 1987-02-20

Publications (1)

Publication Number Publication Date
WO1988006341A1 true WO1988006341A1 (en) 1988-08-25

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Family Applications (1)

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PCT/DK1988/000031 WO1988006341A1 (en) 1987-02-20 1988-02-19 Method of producing an electrically semi-conducting, strippable plastics mixture

Country Status (5)

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US (1) US4915889A (en)
EP (1) EP0302927A1 (en)
DK (1) DK89087A (en)
FI (1) FI884819A0 (en)
WO (1) WO1988006341A1 (en)

Cited By (1)

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WO1995009198A1 (en) * 1993-09-28 1995-04-06 Asea Brown Boveri Ab An extrudable conducting polymer compound

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AU776970B2 (en) 1999-12-02 2004-09-30 Cabot Corporation Carbon blacks useful in wire and cable compounds
JP4967216B2 (en) * 2003-12-05 2012-07-04 株式会社Ｇｓユアサ Non-aqueous electrolyte battery
CA2516415C (en) * 2003-02-21 2012-03-27 Dow Global Technologies Inc. Moisture-crosslinkable polymeric composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995009198A1 (en) * 1993-09-28 1995-04-06 Asea Brown Boveri Ab An extrudable conducting polymer compound

Also Published As

Publication number Publication date
FI884819A (en) 1988-10-19
DK89087A (en) 1988-08-21
EP0302927A1 (en) 1989-02-15
FI884819A0 (en) 1988-10-19
DK89087D0 (en) 1987-02-20
US4915889A (en) 1990-04-10

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