WO2002003398A1 - Cable with recyclable covering - Google Patents

Cable with recyclable covering Download PDF

Info

Publication number
WO2002003398A1
WO2002003398A1 PCT/EP2001/006820 EP0106820W WO0203398A1 WO 2002003398 A1 WO2002003398 A1 WO 2002003398A1 EP 0106820 W EP0106820 W EP 0106820W WO 0203398 A1 WO0203398 A1 WO 0203398A1
Authority
WO
WIPO (PCT)
Prior art keywords
cable
copolymer
equal
propylene
olefin
Prior art date
Application number
PCT/EP2001/006820
Other languages
English (en)
French (fr)
Inventor
Luca Castellani
Luca Martinotto
Cristiana Scelza
Enrico Albizzati
Original Assignee
Pirelli Cavi E Sistemi Spa
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 Pirelli Cavi E Sistemi Spa filed Critical Pirelli Cavi E Sistemi Spa
Priority to EP01951601A priority Critical patent/EP1295301B1/en
Priority to DE60102817T priority patent/DE60102817T2/de
Priority to AU2001272485A priority patent/AU2001272485B2/en
Priority to AU7248501A priority patent/AU7248501A/xx
Priority to AT01951601T priority patent/ATE264539T1/de
Priority to US10/312,407 priority patent/US6908673B2/en
Priority to CA002412891A priority patent/CA2412891C/en
Priority to BRPI0112004-2A priority patent/BR0112004B1/pt
Publication of WO2002003398A1 publication Critical patent/WO2002003398A1/en

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • H01B3/22Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/44Insulators 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
    • H01B3/441Insulators 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/294Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/294Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942Plural coatings
    • Y10T428/2947Synthetic resin or polymer in plural coatings, each of different type

Definitions

  • the present invention relates to a cable with recyclable covering.
  • the invention relates to a cable for transporting or distributing medium or high voltage electric energy, wherein an extruded covering layer based on a thermoplastic polymer material in admixture with a dielectric liquid with superior mechanical and electrical properties is present, enabling, in particular, the use of high operating temperatures and the transportation of high power energy.
  • the requirement for products of high environmental compatibility, composed of materials which, in addition to not being harmful to the environment during production or utilization, can be easily recycled at the end of their life, is now fully accepted in the field of electrical and telecommunications cables.
  • the use of materials compatible with the environment is conditioned by the need to limit costs while, for the more common uses, providing a performance equal to or better than that of conventional materials.
  • the various coverings surrounding the conductor commonly consist of polyolefin-based crosslinked polymer, in particular crosslinked polyethylene (XLPE), or elastomeric ethylene/propylene (EPR) or ethylene/ propylene /diene (EPDM) copolymers, also crosslinked.
  • XLPE crosslinked polyethylene
  • EPR elastomeric ethylene/propylene
  • EPDM ethylene/ propylene /diene
  • Electric cables are also known having their insulation consisting of a multi-layer wrapping of a paper or paper/ polypropylene laminate impregnated with a large quantity of a dielectric liquid (commonly known as mass impregnated cables or also oil-filled cables). By completely filling the spaces present in the multi-layer wrapping, the dielectric liquid prevents partial discharges arising with consequent perforation of the electrical insulation.
  • dielectric liquids products are commonly used such as mineral oils, polybutenes, alkylbenzenes and the like (see for example US-4, 543,207, US- 4,621,302, EP-A-0987718, WO 98/32137).
  • mass impregnated cables have numerous drawbacks compared with extruded insulation cables, so that their use is currently restricted to specific fields of application, in particular to the construction of high and very high voltage direct current transmission lines, both for terrestrial and in particular for underwater installations.
  • the production of mass impregnated cables is particularly complex and costly, both for the high cost of the laminates and for the difficulties encountered during the steps of wrapping the laminate and then of impregnating it with the dielectric liquid.
  • the dielectric liquid used must have low viscosity under cold conditions to allow rapid and uniform impregnation, while at the same time it must have a low tendency to migrate during installation and operation of the cable to prevent liquid loss from the cable ends or following breakage.
  • mass impregnated cables cannot be recycled and their use is limited to an operating temperature of less than 90°C.
  • HDPE high density polyethylene
  • Thermoplastic low density polyethylene (LDPE) insulating coverings are also used in medium and high voltage cables: again in this case, these coverings are limited by too low an operating temperature (about 70°C).
  • WO 99/ 13477 describes an insulating material consisting of a thermoplastic polymer forming a continuous phase which incorporates a liquid or easily meltable dielectric forming a mobile interpenetrating phase within the solid polymer structure. The weight ratio of thermoplastic polymer to dielectric is between 95:5 and 25:75.
  • the insulating material can be produced by mixing the two components while hot either batchwise or continuously (for example by means of an extruder).
  • the resultant mixture is then granulated and used as insulating material for producing a high voltage electric cable by extrusion onto a conductor.
  • the material can be used either in thermoplastic or crosslinked form.
  • thermoplastic polymers are indicated: polyolefins, polyacetates, cellulose polymers, polyesters, polyketones, polyacrylates, polyamides and polya ines.
  • the use of polymers of low crystallinity is particularly suggested.
  • the dielectric is preferably a synthetic or mineral oil of low or high viscosity, in particular a polyisobutene, naphthene, polyaromatic, ⁇ -olefin or silicone oil.
  • the Applicant considers as still unsolved the technical problem of producing an electric cable with a covering made from a thermoplastic polymer material having mechanical and electrical properties comparable to those of cables with an insulating covering of crosslinked material.
  • the Applicant has considered the problem of producing a cable with a non- crosslinked insulating covering having good flexibilty and high mechanical strength under both hot and cold conditions, while at the same time possessing high dielectric strength, without using products potentially polluting during the life cycle of the cable, i.e. from its production to its disposal.
  • the Applicant considers that the addition of dielectric liquids to polymer materials as proposed in the cited WO 99/ 13477 gives totally unsatisfactory results.
  • the Applicant maintains that adding a dielectric liquid to an insulating material should both determine a significant increase in its electrical properties (in particular its dielectric strength), without changing the material characteristics (thermomechanical properties, manageability) and without resulting in exudation of the dielectric liquid.
  • the resultant cable should give substantially constant performance with time and hence high reliability, even at high operating temperatures (at least 90°C and beyond).
  • the Applicant has now found it possible to solve said technical problem by using, as recyclable polymer base material, a thermoplastic propylene homopolymer or copolymer mixed with a dielectric liquid as hereinafter defined.
  • the resultant composition possesses good flexibility even when cold, excellent thermomechanical strength and high electrical performance, such as to make it particularly suitable for forming at least one covering layer, and in particular an electrical insulating layer, of a medium or high voltage cable of high operating temperature, of at least 90°C and beyond.
  • the dielectric liquid suitable for implementing the invention has high compatibility with the base polymer and high efficiency in the sense of improving electrical performance, consequently allowing the use of small quantities of additive such as not to impair the thermomechanical characteristics of the insulating layer.
  • the dielectric liquid suitable for forming the cable of the invention is free of polar groups, it absorbs water in extremely small quantities, hence preventing formation of insulation defects due to the presence of steam which normally forms during the process of high temperature extrusion.
  • the invention therefore relates to a cable (1) comprising at least one electrical conductor (2) and at least one extruded covering layer (3, 4, 5) based on a thermoplastic polymer material in admixture with a dielectric liquid, wherein: said thermoplastic material comprises a propylene homopolymer or a copolymer of propylene with at least an olefin comonomer selected from ethylene and an ⁇ -olefin other than propylene, said homopolymer or copolymer having a melting point greater than or equal to 140°C and a melting , enthalpy of from 30 to 100 J/g; said liquid comprises at least one alkylaryl hydrocarbon having at least two non-condensed aromatic rings and a ratio of number of aryl carbon atoms to total number of carbon atoms greater than or equal to 0.6, and preferably greater than or equal to 0.7.
  • said thermoplastic material comprises a propylene homopolymer or a copolymer of propylene with at least
  • said extruded covering layer based on said thermoplastic polymer material in admixture with said dielectric liquid is an electrically insulating layer.
  • said extruded covering layer based on said thermoplastic polymer material in admixture with said dielectic liquid is a semiconductive layer.
  • the propylene homopolymer or copolymer has a melting point of from 145 to 170°C.
  • the propylene homopolymer or copolymer has a melting enthalpy of from 30 to 85 J/g.
  • the propylene homopolymer or copolymer has a . flexural modulus, measured in accordance with ASTM D790, at room temperature, of from30 to 1400 MPa, and more preferably from 60 to 1000 MPa.
  • the propylene homopolymer or copolymer has a melt flow index (MFI), measured at 230°C with a load of 21.6 N in accordance with ASTM D1238/L, of from 0.05 to 10.0 dg/min, more preferably from 0.5 to 5.0 dg/ in.
  • MFI melt flow index
  • a copolymer of propylene with an olefin comonomer is used, this latter is preferably present in a quantity of less than or equal to 15 mol%, and more preferably of less than or equal to 10 mol%.
  • the olefin comonomer is, in particular, ethylene or an ⁇ -olefin of formula CH ⁇ CH-R, where R is a linear or branched C2-C o alkyl, selected for example from: 1-butene, 1-pentene, 4- methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like, or combinations thereof.
  • Propylene /ethylene copolymers are particularly preferred.
  • said thermoplastic material is selected from: a) a propylene homopolymer or a copolymer of propylene with at least one olefin comonomer selected from ethylene and an ⁇ -olefin other than propylene, having a fiexural modulus generally of from 30 to 900 MPa, and preferably of from 50 to 400 MPa; b) a heterophase copolymer comprising a thermoplastic phase based on propylene and an elastomeric phase based on ethylene copolymerized with an ⁇ -olef ⁇ n, preferably with propylene, in which the elastomeric phase is present in a quantity of at least 45 wt% on the total weight of the heterophase copolymer.
  • the homopoly ers or copolymers of class a) show a single-phase microscopic structure, i.e. substantially devoid of heterogeneous phases dispersed as molecular domains of size greater than one micron. These materials do not show in fact the optical phenomena typical of heterophase polymer materials, and in particular are characterised by better transparency and reduced whitening due to local mechanical stresses (commonly known as "stress whitening").
  • Particularly preferred of said class a) is a propylene homopolymer or a copolymer of propylene with at least one olefin comonomer selected from ethylene and an ⁇ -olef ⁇ n other than propylene, said homopolymer or copolymer having: a melting point of from 140 to 165°C; a melting enthalpy of from 30 to 80 J/g; a fraction soluble in boiling diethyl ether in an amount of less than or equal to 12 wt%, preferably from 1 to 10 wt%, having a melting enthalpy of less than or equal to 4 J/g, preferably less than or equal to 2 J/g; a fraction soluble in boiling n-heptane in an amount of from 15 to 60 wt%, preferably from 20 to 50 wt%, having a melting enthalpy of from 10 to 40 J/g, preferably from 15 to 30 J/g; and a fraction insoluble in boiling n-
  • the heterophase copolymers of class b) are thermoplastic elastomers obtained by sequential copolymerization of: i) propylene, possibly containing minor quantities of at least one olefin comonomer selected from ethylene and an ⁇ -olefin other than propylene; and then of: ii) a mixture of ethylene with an ⁇ -olefin, in particular propylene, and possibly with minor portions of a diene.
  • This class of product is also commonly known by the term "thermoplastic reactor elastomers”.
  • the said class b) is a heterophase copolymer in which the elastomeric phase consists of an elastomeric copolymer of ethylene and propylene comprising from 15 to 50 wt% of ethylene and from 50 to 85 wt% of propylene on the weight of the elastomeric phase. Further details of these materials and their use in covering cables are given in European patent application 98830800 filed on 30.12.1998 in the name of the Applicant, incorporated herein for reference.
  • thermoplastic base material a propylene homopolymer or copolymer as hereinabove defined can be used in mechanical mixture with a low crystallinity polymer, generally with a melting enthalpy of less than 30 J/g, which mainly acts to increase flexibility of the material.
  • the quantity of low crystallinity polymer is generally less than 70 wt%, and preferably of from 20 to 60 wt%, on the total weight of the thermoplastic material.
  • the low crystallinity polymer is a copolymer of ethylene with a C3-C12 ⁇ -olefin, and possibly with a diene.
  • the ⁇ -olefin is preferably selected from propylene, 1-hexene and 1 -octene. If a diene comonomer is present, this is generally C4-C20.
  • conjugated or non-conjugated linear diolefins such as 1,3-butadiene, 1,4-hexadiene, 1,6- octadiene or their mixtures and the like; monocyclic or polycyclic dienes, such as 1,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene or their mixtures and the like.
  • Particularly preferred ethylene copolymers are:
  • copolymers having the following monomer composition: 35-90 mol% of ethylene; 10-65 mol% of an ⁇ -olefin, preferably propylene; 0-10 mol% of a diene, preferably 1,4-hexadiene or 5-ethylene-2-norbornene (EPR and EPDM rubbers are within this class);
  • the alkylaryl hydrocarbon of the invention preferably has a dielectric constant, at 25°C, of less than or equal to 3.5 and preferably less than 3 (measured in accordance with IEC 247) .
  • the alkylaryl hydrocarbon of the invention has a predetermined viscosity such as to prevent fast diffusion of the liquid within the insulating layer and hence its outward migration, while at the same time such as to enable it to be easily fed and mixed into the polymer.
  • the dielectric liquid of the invention has a kinematic viscosity, at 20°C, of between 1 and 500 mm ⁇ /s, preferably between 5 and 100 mm ⁇ /s (measured in accordance with ISO 3104).
  • the alkylaryl hydrocarbon of the invention has a hydrogen absorption capacity greater than or equal to 5 mm ⁇ /min, preferably greater than or equal to 50 mm ⁇ /min (measured in accordance with IEC 628-A).
  • an epoxy resin can be added to the dielectric liquid suitable for forming the cable of the invention, generally in a quantity of less than or equal to 1 wt% on the weight of the liquid, this being considered to mainly act to reduce the ion migration rate under an electrical field, and hence the dielectric loss of the insulating material.
  • the dielectric liquid of the invention comprises at least one alkylaryl hydrocarbon having at least three non- condensed aromatic rings.
  • the dielectric liquid of the invention comprises at least one alkylaryl hydrocarbon having at least three non-condensed aromatic rings in a quantity of not less than 10 wt% on the total weight of the dielectric liquid.
  • the dielectric liquid of the invention comprises at least one alkylaryl hydrocarbon having the structural formula:
  • Rl, R2, R3 and R4, equal or different are hydrogen or methyl; nl and n2, equal or different, are zero, 1 or 2, with the proviso that the sum nl+n2 is less than or equal to 3.
  • the dielectric liquid can also contain minor quantities of at least one triphenylmethane, either unsubstituted or substituted by at least one radical selected from methyl, benzyl and methylbenzyl.
  • triphenylmethanes are: ditoluylphenylmethane, dixylylphenylmethane, xylyltoluylphenylmethane and the like, or their mixtures.
  • the dielectric liquid of the invention comprises at least one alkylaryl hydrocarbon of the aforegiven formula (I) in which the sum nl+n2 is other than zero.
  • Alkylaryl hydrocarbons corresponding to formula (I) in which the sum nl+n2 is equal to zero, and usable advantageously in this invention, are for example: benzyltoluene, benzylxylene, (methylbenzyl)toluene, (methylbenzyl)xylene and the like, or their mixtures.
  • Alkylaryl hydrocarbons corresponding to formula (I) in which the sum nl+n2 is other than zero, and usable advantageously in this invention, are for example: dibenzyltoluene, dibenzylxylene, di(methylbenzyl)toluene, di(methylbenzyl)xylene and the like, or their mixtures.
  • the alkylaryl hydrocarbons of formula (I) are generally prepared by reacting benzylchloride, methylbenzylchloride or their mixtures, with an aromatic hydrocarbon selected from benzene, toluene, xylene or their mixtures, in the presence of a Friedel-Crafts catalyst (for example FeCl3, SbCl ⁇ , TiCl_ ⁇ or AICI3) . Further details regarding the preparation of alkylaryl hydrocarbons of formula (I) are given for example in US-5, 192,463, US-5,446,228, US- 5,545,355 and US-5,601,755.
  • a Friedel-Crafts catalyst for example FeCl3, SbCl ⁇ , TiCl_ ⁇ or AICI3
  • the dielectric liquid suitable for implementing the invention has good heat resistance, considerable gas absorption capacity, in particular for hydrogen, and hence high resistance to partial discharges, so that dielectric loss is not high even at high temperature and high electrical gradient.
  • the weight ratio of dielectric liquid to base polymer material of the invention is generally between 1:99 and 25:75, preferably between 2:98 and 20:80, and more preferably between 3:97 and 15:85.
  • the cable of the invention has at least one extruded covering layer with electrical insulation properties formed from the thermoplastic polymer material in admixture with the aforedescribed dielectric liquid.
  • the cable of the invention has at least one extruded covering layer with semiconductive properties formed from the thermoplastic polymer material in admixture with the aforedescribed dielectric liquid.
  • a conductive filler is generally added to the polymer material.
  • this latter is preferably selected from propylene homopolymers or copolymers comprising at least 40 wt% of amorphous phase, on the total polymer weight.
  • the cable of the invention has at least one electrical insulation layer and at least one semiconductive layer formed from a thermoplastic polymer material in admixture with a dielectric liquid as hereinabove described. This prevents the semiconductive layers from absorbing, with time, part of the dielectric liquid present in the insulating layer, so reducing its quantity just at the interface between the insulating layer and semiconductive layer, in particular the inner semiconductive layer where the electrical field is higher.
  • the invention relates to a polymer composition
  • a thermoplastic polymer material in admixture with a dielectric liquid
  • said thermoplastic material comprises a propylene homopolymer or a copolymer of propylene with at least one olefin comonomer selected from ethylene and an ⁇ -olefin other than propylene, said homopolymer or copolymer having a melting point of greater than or equal to 140°C and a melting enthalpy of from 30 to 100 J/g
  • - said liquid comprises at least one alkylaryl hydrocarbon with at least two non-condensed aromatic rings and a ratio of number of aryl carbon atoms to total number of carbon atoms greater than or equal to 0.6, preferably greater than or equal to 0.7.
  • the invention relates to the use of a polymer composition, as described hereinabove, as the base polymer material for preparing a covering layer (4) with electrical insulation properties, or for preparing a covering layer (3, 5) with semiconductive properties.
  • a covering layer for the cable of the invention In forming a covering layer for the cable of the invention, other conventional components can be added to the aforedefined polymer composition, such as antioxidants, processing aids, water tree retardants, and the like.
  • antioxidants suitable for the purpose are for example distearyl-thiopropionate and pentaerithryl-tetrakis [3-(3,5-di-tertbutyl-4- hydroxyphenyl)propionate] and the like, or their mixtures.
  • Processing aids which can be added to the polymer base include, for example, calcium stearate, zinc stearate, stearic acid, paraffin wax and the like, or mixtures thereof.
  • the polymer materials as defined hereinabove can be advantageously used to form an insulating layer.
  • these polymer materials show indeed good mechanical characteristics both at ambient temperature and under hot conditions, and also show improved electrical properties.
  • they enable high operating temperature to be employed, comparable with or even exceeding that of cables with coverings consisting of crosslinked polymer base materials.
  • a conductive filler in particular carbon black, is generally dispersed within the polymer material in a quantity such as to provide the material with semiconductive characteristics
  • This quantity is generally between 5 and 80 wt%, and preferably between 10 and 50 wt%, of the total weight of the mixture.
  • the possibility to use the same type of polymer composition for both the insulating layer and the semiconductive layers is particularly advantageous in producing cables for medium or high voltage, in that it ensures excellent adhesion between adjacent layers and hence better electrical behaviour, particularly at the interface between the insulating layer and the inner semiconductive layer, where the electrical field and hence the risk of partial discharges are higher.
  • compositions of the invention can be prepared by mixing together the base polymer material, the dielectric liquid and any other additives possibly present by methods known in the art. Mixing can be carried out for example by an internal mixer of the type with tangential rotors (Banbury) or with interpenetrating rotors, or, preferably, in a continuous mixer of Ko-Kneader (Buss) type, or of co- or counter-rotating double-screw type.
  • the dielectric liquid of the invention can be added to the polymer material during the extrusion step by direct injection into the extruder cylinder.
  • the use of the aforedefined polymer composition in covering cables for medium or high voltage enables recyclable, flexible coverings to be obtained with excellent mechanical and electrical properties.
  • the cables of the invention can carry, for the same voltage, a power at least equal to or even greater than that transportable by a traditional cable with XLPE covering.
  • the term “medium voltage” generally means a voltage of between 1 and 35 kV, whereas “high voltage” means voltages higher than 35 kV.
  • the polymer composition of the invention can be used for covering electrical devices in general and in particular cables of different type, for example low voltage cables, telecommunications cables or combined energy/ telecommunications cables, or accessories used in constructing electrical lines, such as terminals or connectors.
  • FIG. 1 is a perspective view of an electric cable, particularly suitable for medium or high voltage, according to the invention.
  • the cable 1 comprises a conductor 2, an inner layer with semiconductive properties 3, an intermediate layer with insulating properties 4, an outer layer with semiconductive properties 5, a metal screen 6, and an outer sheath 7.
  • the conductor 2 generally consists of metal wires, preferably of copper or aluminium, stranded together by conventional methods. At least one covering layer selected from the insulating layer 4 and the semiconductive layers 3 and 5 comprises the composition of the invention as heretofore defined.
  • a screen 6 generally of electrically conducting wires or strips wound helically. This screen is then covered by a sheath 7 of a thermoplastic material, for example non-crosslinked polyethylene (PE) or preferably a propylene homopolymer or copolymer as heretofore defined.
  • PE non-crosslinked polyethylene
  • propylene homopolymer or copolymer as heretofore defined.
  • the cable can also be provided with an outer protective structure (not shown in Figure 1) the main purpose of which is to mechanically protect the cable against impact or compression.
  • This protective structure can be, for example, a metal reinforcement or a layer of expanded polymer as described in WO 98/52197.
  • FIG. 1 shows only one possible embodiment of a cable according to the invention. Suitable modifications known in the art can evidently be made to this embodiment, but without departing from the scope of the invention.
  • the cable of the invention can be constructed in accordance with known methods for depositing layers of thermoplastic material, for example by extrusion.
  • the extrusion is advantageously carried out in a single pass, for example by the tandem method in which individual extruders are arranged in series, or by co-extrusion with a multiple extrusion head.
  • the following examples illustrate the invention, but without limiting it.
  • Table 1 shows the characteristics of the dielectric liquids used in the following examples.
  • the dielectric liquids according to the invention were: Jarylec ⁇ Exp4 (commercial product of Elf Atochem): a mixture containing 85 wt% of monoxylybcylene (MXX)
  • the comparison dielectric liquids were: Baysilone- PD5 (commercial product of General Electric - Bayer): polyphenylmethylsiloxane (PPMS), polyaromatic dielectric oil as described in IEEE Transactions on Electrical Insulation Vol. 26, No.4,
  • Example 1-6 a propylene heterophase copolymer with an ethylene/propylene elastomeric phase content of about 65 wt% (propylene 72 wt% in the elastomeric phase), melting enthalpy 32 J/g, melting point 163°C, MFI 0.8 dg/min and flexural modulus of about 70 MPa (Hifax R KSO81 - commercial product of Montell).
  • Composition preparation The polymer in granular form was preheated to 80°C in a tUrbomixer.
  • the dielectric liquid was added, in the quantities specified for the formulations given in Table 2, to the polymer preheated in the turbomixer under agitation at
  • the resultant material was kneaded in a laboratory double-screw Brabender Plasticorder PL2000 at a temperature of 185°C to complete homogenization.
  • the material left the double-screw mixer in the form of granules.
  • the dielectric strength of the polymer compositions obtained was evaluated on test-pieces of insulating material having the geometry proposed by the EFI (Norwegian Electric Power Research Institute) in the publication "The EFI Test Method for Accelerated Growth of Water Trees” (IEEE International Symposium on Electrical insulation, Toronto, Canada, June 3-6 1990).
  • the cable is simulated with glass-shaped test pieces of insulating material having their base coated on both sides with a semiconductive material coating.
  • the glass-shaped test-pieces were formed by moulding discs of insulating material at 160- 170°C from a plate of thickness 10 mm obtained by compressing granules at about 190°C.
  • the inner and outer surfaces of the base which had a thickness of about 0.40-0.45 mm, were coated with a semiconductive coating.
  • the DS measurement was made by applying to these specimens, immersed in silicone oil at 20°C, an alternating current at 50 Hz starting with a voltage of 25 kV and increasing in steps of 5 kV every 30 minutes until perforation of the test-piece occurred. Each measurement was repeated on 10 test-pieces.
  • the values given in Table 2 are the arithmetic mean of the individual measured values.
  • the dielectric strength values given in Table 2 highlight the improvement in electrical performance deriving from the dielectric liquids of the invention, compared to that of the base polymer as such or when mixed with the comparison dielectric liquids.
  • the loss of dielectric liquid (expressed as percentage by weight on the initial quantity) was measured against time at 20°C in air in order to verify the diffusivity of the dielectric liquids in the polymer and hence their stability with time in these compositions.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/EP2001/006820 2000-06-28 2001-06-15 Cable with recyclable covering WO2002003398A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP01951601A EP1295301B1 (en) 2000-06-28 2001-06-15 Cable with recyclable covering
DE60102817T DE60102817T2 (de) 2000-06-28 2001-06-15 Kabel mit wiederverwertbarer ummantelung
AU2001272485A AU2001272485B2 (en) 2000-06-28 2001-06-15 Cable with recyclable covering
AU7248501A AU7248501A (en) 2000-06-28 2001-06-15 Cable with recyclable covering
AT01951601T ATE264539T1 (de) 2000-06-28 2001-06-15 Kabel mit wiederverwertbarer ummantelung
US10/312,407 US6908673B2 (en) 2000-06-28 2001-06-15 Cable with recyclable covering
CA002412891A CA2412891C (en) 2000-06-28 2001-06-15 Cable with recyclable covering
BRPI0112004-2A BR0112004B1 (pt) 2000-06-28 2001-06-15 Cabo para transporte ou distribuição de energia elétrica em média e alta voltagens, e, composição polimérica usada para confecção do cabo.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00113661 2000-06-28
EP00113661.3 2000-06-28
US21603200P 2000-07-03 2000-07-03
US60/216,032 2000-07-03

Publications (1)

Publication Number Publication Date
WO2002003398A1 true WO2002003398A1 (en) 2002-01-10

Family

ID=8169094

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/006820 WO2002003398A1 (en) 2000-06-28 2001-06-15 Cable with recyclable covering

Country Status (11)

Country Link
EP (1) EP1295301B1 (zh)
CN (1) CN1249732C (zh)
AR (1) AR028766A1 (zh)
AT (1) ATE264539T1 (zh)
AU (2) AU2001272485B2 (zh)
BR (1) BR0112004B1 (zh)
CA (1) CA2412891C (zh)
DE (1) DE60102817T2 (zh)
ES (1) ES2219544T3 (zh)
MY (1) MY123591A (zh)
WO (1) WO2002003398A1 (zh)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004066317A1 (en) * 2003-01-20 2004-08-05 Gabriele Perego Cable with recycable covering layer
US6861143B2 (en) * 1999-11-17 2005-03-01 Pirelli Cavi E Sistemi S.P.A. Cable with recyclable covering
WO2008058572A1 (en) * 2006-11-15 2008-05-22 Prysmian S.P.A. Energy cable
US7514633B2 (en) * 2003-12-03 2009-04-07 Prysmian Cavi E Sistemi Energia S.R.L. Impact resistant cable
US7744950B2 (en) 2000-12-06 2010-06-29 Prysmian Cavi E Sistemi Energia S.R.L. Process for producing a cable with a recyclable coating comprising a thermoplastic polymer and a dielectric liquid
US7884284B2 (en) 2005-10-25 2011-02-08 Prysmian Cavi E Sistemi Energia S.R.L. Energy cable comprising a dielectric fluid and a mixture of thermoplastic polymers
WO2011092533A1 (en) 2010-01-29 2011-08-04 Prysmian S.P.A. Energy cable
US7999188B2 (en) 2007-06-28 2011-08-16 Prysmian S.P.A. Energy cable
WO2012069864A1 (en) 2010-11-25 2012-05-31 Prysmian S.P.A. Energy cable having a voltage stabilized thermoplastic electrically insulating layer
WO2012085612A1 (en) 2010-12-23 2012-06-28 Prysmian S.P.A. Energy cable having stabilized dielectric resistance
WO2012084055A1 (en) 2010-12-23 2012-06-28 Prysmian S.P.A. Continuous process for manufacturing a high voltage power cable
WO2013017916A1 (en) 2011-08-04 2013-02-07 Prysmian S.P.A. Energy cable having a thermoplastic electrically insulating layer
WO2013171550A1 (en) 2012-05-18 2013-11-21 Prysmian S.P.A. Process for producing an energy cable having a thermoplastic electrically insulating layer
WO2016005791A1 (en) 2014-07-08 2016-01-14 Prysmian S.P.A. Energy cable having a thermoplastic electrically insulating layer
WO2016097819A1 (en) 2014-12-17 2016-06-23 Prysmian S.P.A. Energy cable having a cold-strippable semiconductive layer
WO2017068398A1 (en) 2015-10-23 2017-04-27 Prysmian S.P.A. Joint for electric cables with thermoplastic insulation and method for manufacturing the same
US9697927B2 (en) 2011-12-23 2017-07-04 Prysmian S.P.A. Cable comprising an element indicating water infiltration and method using said element
WO2018100409A1 (en) 2016-11-30 2018-06-07 Prysmian S.P.A. Power cable
WO2018122572A1 (en) 2016-12-27 2018-07-05 Prysmian S.P.A. Electric cable having a protecting layer
US20180254123A1 (en) * 2015-09-25 2018-09-06 Prysmian S.P.A. Power cable comprising an aluminium corrosion inhibitor
US10153069B2 (en) 2015-03-20 2018-12-11 Prysmian S.P.A Water-tight power cable with metallic screen rods
WO2018234697A1 (fr) 2017-06-21 2018-12-27 Nexans Composition polymère comprenant un liquide diélectrique polaire
WO2019025718A1 (fr) 2017-08-01 2019-02-07 Nexans Procédé de fabrication d'un câble électrique par extrusion d'une composition à base d'un polymère de proprylène et d'un liquide diélectrique
WO2019072388A1 (en) 2017-10-12 2019-04-18 Prysmian S.P.A. ELECTRICAL CABLE WITH ENHANCED THERMOPLASTIC INSULATING LAYER
US10297372B2 (en) 2012-05-18 2019-05-21 Prysmian S.P.A Process for producing an energy cable having a thermoplastic electrically insulating layer
EP3605559A1 (en) 2018-08-03 2020-02-05 Prysmian S.p.A. High voltage three-phase cable
US10662323B2 (en) 2013-08-12 2020-05-26 Nkt Hv Cables Ab Thermoplastic blend formulations for cable insulations
IT202000032015A1 (it) 2020-12-23 2022-06-23 Prysmian Spa Cavo elettrico di media tensione con miglior comportamento al fuoco
FR3125354A1 (fr) 2021-07-19 2023-01-20 Nexans Procédé de fabrication d’un câble électrique par extrusion d’une composition à base d’un polymère de propylène et d’un liquide diélectrique avec une vis barrière comportant une section de mélange
EP4390976A1 (en) 2022-12-23 2024-06-26 Nexans Covering layer obtained from a polymer composition comprising at least one thermoplastic polymer material and at least one compound comprising at least one nitrile group

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011075786A1 (de) * 2011-05-13 2012-11-15 Siemens Aktiengesellschaft Elektrisches Bauelement
BR112015006260B1 (pt) * 2012-09-27 2021-11-09 Dow Global Technologies Llc Composição, artigo reticulado e cabo de força de média ou alta voltagem
CN103714902A (zh) * 2014-01-14 2014-04-09 深圳市东佳信电线电缆有限公司 变压器连接用特种结构环保型电力电缆
CN105845226B (zh) * 2016-04-05 2019-04-26 江苏亨通高压海缆有限公司 一种防水海底电缆

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330439A (en) * 1979-11-08 1982-05-18 Kureha Kagaku Kogyo Kabushiki Kaisha Electric device comprising impregnated insulating materials and electric elements
US5017733A (en) * 1986-09-04 1991-05-21 Nippon Petrochemicals Company, Limited Electrical insulating oil composition
WO1998032137A1 (en) * 1997-01-17 1998-07-23 Nkt Cables A/S Electric cable
WO1999013477A1 (en) * 1997-09-09 1999-03-18 Nkt Research Center A/S An electrically insulating material, method for the preparation thereof, and insulated objects comprising said material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330439A (en) * 1979-11-08 1982-05-18 Kureha Kagaku Kogyo Kabushiki Kaisha Electric device comprising impregnated insulating materials and electric elements
US5017733A (en) * 1986-09-04 1991-05-21 Nippon Petrochemicals Company, Limited Electrical insulating oil composition
WO1998032137A1 (en) * 1997-01-17 1998-07-23 Nkt Cables A/S Electric cable
WO1999013477A1 (en) * 1997-09-09 1999-03-18 Nkt Research Center A/S An electrically insulating material, method for the preparation thereof, and insulated objects comprising said material

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6861143B2 (en) * 1999-11-17 2005-03-01 Pirelli Cavi E Sistemi S.P.A. Cable with recyclable covering
US7744950B2 (en) 2000-12-06 2010-06-29 Prysmian Cavi E Sistemi Energia S.R.L. Process for producing a cable with a recyclable coating comprising a thermoplastic polymer and a dielectric liquid
WO2004066318A1 (en) * 2003-01-20 2004-08-05 Pirelli & C. S.P.A. Cable with recyclable covering layer
US7196270B2 (en) 2003-01-20 2007-03-27 Prysmian Cavi E Sistemi Energia S.R.L. Cable with recyclable covering layer
CN100356482C (zh) * 2003-01-20 2007-12-19 皮雷利&C.有限公司 带可回收覆盖层的电缆
WO2004066317A1 (en) * 2003-01-20 2004-08-05 Gabriele Perego Cable with recycable covering layer
AU2004206275B2 (en) * 2003-01-20 2009-05-14 Prysmian Cavi E Sistemi Energia S.R.L. Cable with recyclable covering layer
US7514633B2 (en) * 2003-12-03 2009-04-07 Prysmian Cavi E Sistemi Energia S.R.L. Impact resistant cable
US7884284B2 (en) 2005-10-25 2011-02-08 Prysmian Cavi E Sistemi Energia S.R.L. Energy cable comprising a dielectric fluid and a mixture of thermoplastic polymers
US20100126756A1 (en) * 2006-11-15 2010-05-27 Prysmian Caviesistemi Energia Energy cable
US8378216B2 (en) 2006-11-15 2013-02-19 Prysmian S.P.A. Energy cable
WO2008058572A1 (en) * 2006-11-15 2008-05-22 Prysmian S.P.A. Energy cable
AU2006350918B2 (en) * 2006-11-15 2013-10-24 Prysmian S.P.A. Energy cable
US7999188B2 (en) 2007-06-28 2011-08-16 Prysmian S.P.A. Energy cable
WO2011092533A1 (en) 2010-01-29 2011-08-04 Prysmian S.P.A. Energy cable
US10811163B2 (en) 2010-01-29 2020-10-20 Prysmian S.P.A. Energy cable
WO2012069864A1 (en) 2010-11-25 2012-05-31 Prysmian S.P.A. Energy cable having a voltage stabilized thermoplastic electrically insulating layer
US9576703B2 (en) 2010-12-23 2017-02-21 Prysmian S.P.A. Energy cable having stabilized dielectric resistance
WO2012084055A1 (en) 2010-12-23 2012-06-28 Prysmian S.P.A. Continuous process for manufacturing a high voltage power cable
WO2012085612A1 (en) 2010-12-23 2012-06-28 Prysmian S.P.A. Energy cable having stabilized dielectric resistance
WO2013017916A1 (en) 2011-08-04 2013-02-07 Prysmian S.P.A. Energy cable having a thermoplastic electrically insulating layer
US9697927B2 (en) 2011-12-23 2017-07-04 Prysmian S.P.A. Cable comprising an element indicating water infiltration and method using said element
WO2013171550A1 (en) 2012-05-18 2013-11-21 Prysmian S.P.A. Process for producing an energy cable having a thermoplastic electrically insulating layer
US10297372B2 (en) 2012-05-18 2019-05-21 Prysmian S.P.A Process for producing an energy cable having a thermoplastic electrically insulating layer
US10662323B2 (en) 2013-08-12 2020-05-26 Nkt Hv Cables Ab Thermoplastic blend formulations for cable insulations
WO2016005791A1 (en) 2014-07-08 2016-01-14 Prysmian S.P.A. Energy cable having a thermoplastic electrically insulating layer
WO2016097819A1 (en) 2014-12-17 2016-06-23 Prysmian S.P.A. Energy cable having a cold-strippable semiconductive layer
US10153069B2 (en) 2015-03-20 2018-12-11 Prysmian S.P.A Water-tight power cable with metallic screen rods
US10217546B2 (en) 2015-09-25 2019-02-26 Prysmian S.P.A. Power cable having an aluminum corrosion inhibitor
US20180254123A1 (en) * 2015-09-25 2018-09-06 Prysmian S.P.A. Power cable comprising an aluminium corrosion inhibitor
WO2017068398A1 (en) 2015-10-23 2017-04-27 Prysmian S.P.A. Joint for electric cables with thermoplastic insulation and method for manufacturing the same
WO2018100409A1 (en) 2016-11-30 2018-06-07 Prysmian S.P.A. Power cable
WO2018122572A1 (en) 2016-12-27 2018-07-05 Prysmian S.P.A. Electric cable having a protecting layer
WO2018234697A1 (fr) 2017-06-21 2018-12-27 Nexans Composition polymère comprenant un liquide diélectrique polaire
WO2019025718A1 (fr) 2017-08-01 2019-02-07 Nexans Procédé de fabrication d'un câble électrique par extrusion d'une composition à base d'un polymère de proprylène et d'un liquide diélectrique
WO2019072388A1 (en) 2017-10-12 2019-04-18 Prysmian S.P.A. ELECTRICAL CABLE WITH ENHANCED THERMOPLASTIC INSULATING LAYER
US10839978B2 (en) 2017-10-12 2020-11-17 Prysmian S.P.A. Electric cable with improved thermoplastic insulating layer
EP3605559A1 (en) 2018-08-03 2020-02-05 Prysmian S.p.A. High voltage three-phase cable
IT202000032015A1 (it) 2020-12-23 2022-06-23 Prysmian Spa Cavo elettrico di media tensione con miglior comportamento al fuoco
EP4020504A1 (en) 2020-12-23 2022-06-29 Prysmian S.p.A. Medium voltage electric cable with improved behaviour under fire
US11694822B2 (en) 2020-12-23 2023-07-04 Prysmian S.P.A. Medium voltage electric cable with improved behavior under fire
FR3125354A1 (fr) 2021-07-19 2023-01-20 Nexans Procédé de fabrication d’un câble électrique par extrusion d’une composition à base d’un polymère de propylène et d’un liquide diélectrique avec une vis barrière comportant une section de mélange
WO2023002102A1 (fr) 2021-07-19 2023-01-26 Nexans Procédé de fabrication d'un câble électrique par extrusion d'une composition à base d'un polymère de propylène et d'un liquide diélectrique avec une vis barrière comportant une section de mélange
EP4390976A1 (en) 2022-12-23 2024-06-26 Nexans Covering layer obtained from a polymer composition comprising at least one thermoplastic polymer material and at least one compound comprising at least one nitrile group

Also Published As

Publication number Publication date
AR028766A1 (es) 2003-05-21
AU7248501A (en) 2002-01-14
AU2001272485B2 (en) 2005-04-28
BR0112004A (pt) 2003-05-13
CN1503977A (zh) 2004-06-09
EP1295301B1 (en) 2004-04-14
BR0112004B1 (pt) 2010-11-16
DE60102817D1 (de) 2004-05-19
DE60102817T2 (de) 2004-09-30
EP1295301A1 (en) 2003-03-26
MY123591A (en) 2006-05-31
ES2219544T3 (es) 2004-12-01
CA2412891A1 (en) 2002-01-10
CN1249732C (zh) 2006-04-05
CA2412891C (en) 2009-09-22
ATE264539T1 (de) 2004-04-15

Similar Documents

Publication Publication Date Title
EP1295301B1 (en) Cable with recyclable covering
CA2425382C (en) Cable with recyclable covering
AU2001272485A1 (en) Cable with recyclable covering
DK1588387T3 (en) Cable with reusable cover
AU2001284030A1 (en) Cable with recyclable covering
EP2092535B1 (en) Energy cable
CA2626131C (en) Energy cable comprising a dielectric fluid and a mixture of thermoplastic polymers
CA2430426A1 (en) Process for producing a cable with a recyclable coating
US6908673B2 (en) Cable with recyclable covering
US6824870B2 (en) Cable with recyclable covering
RU2377677C1 (ru) Силовой кабель, включающий в себя диэлектрическую жидкость и смесь термопластичных полимеров

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2001951601

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2001272485

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2412891

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 10312407

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 01811959X

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2001951601

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWG Wipo information: grant in national office

Ref document number: 2001951601

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWG Wipo information: grant in national office

Ref document number: 2001272485

Country of ref document: AU