EP1295301B1 - Cable a gaine recyclable - Google Patents

Cable a gaine recyclable Download PDF

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Publication number
EP1295301B1
EP1295301B1 EP01951601A EP01951601A EP1295301B1 EP 1295301 B1 EP1295301 B1 EP 1295301B1 EP 01951601 A EP01951601 A EP 01951601A EP 01951601 A EP01951601 A EP 01951601A EP 1295301 B1 EP1295301 B1 EP 1295301B1
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EP
European Patent Office
Prior art keywords
cable
copolymer
equal
propylene
olefin
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EP01951601A
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German (de)
English (en)
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EP1295301A1 (fr
Inventor
Luca Castellani
Luca Martinotto
Cristiana Scelza
Enrico Albizzati
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Prysmian Cavi e Sistemi Energia SRL
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Pirelli and C SpA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20—Insulators 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
    • H01B3/22—Insulators 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
    • 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
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • Y10T428/2947—Synthetic 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 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).
  • LDPE low density polyethylene
  • 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 polyolefins, polyacetates, cellulose polymers, polyesters, polyketones, polyacrylates, polyamides and polyamines.
  • 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 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/min.
  • 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%.
  • Propylene/ethylene copolymers are particularly preferred.
  • thermoplastic material is selected from:
  • the homopolymers 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 ⁇ -olefin other than propylene, said homopolymer or copolymer having:
  • 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 C 3 -C 12 ⁇ -olefin, and possibly with a diene.
  • the ⁇ -olefin is preferably selected from propylene, 1-hexene and 1-octene.
  • a diene comonomer is present, this is generally C 4 -C 20 , and is preferably selected from: 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.
  • 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
  • Particularly preferred ethylene copolymers are:
  • 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 2 /s, preferably between 5 and 100 mm 2 /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 3 /min, preferably greater than or equal to 50 mm 3 /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: wherein:
  • 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 n1+n2 is other than zero.
  • Alkylaryl hydrocarbons corresponding to formula (I) in which the sum n1+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 n1+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 FeCl 3 , SbCl 3 , TiCl 4 or AlCl 3 ). 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 FeCl 3 , SbCl 3 , TiCl 4 or AlCl 3 .
  • 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 polymer composition comprising a thermoplastic polymer material in admixture with a dielectric liquid, in which:
  • 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 (i.e. such as to obtain a resistivity of less than 5 Ohm.m at ambient temperature).
  • 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 aforedefmed 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.
  • 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 comparison dielectric liquids were:
  • 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 80°C over 15 min. After the addition agitation was continued for a further hour at 80°C until the liquid was completely absorbed in the polymer granules.
  • 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.

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  • 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)

Claims (52)

  1. Câble (1) comprenant au moins un conducteur électrique (2) et au moins une couche de revêtement extrudé (3, 4, 5) à base d'un matériau polymère thermoplastique mélangé avec un liquide diélectrique, dans lequel câble
    ledit matériau thermoplastique comprend un homopolymère de propylène ou un copolymère de propylène et d'au moins une oléfine comonomère choisie parmi l'éthylène et une α-oléfine autre que le propylène, lequel homopolymère ou copolymère présente un point de fusion supérieur ou égal à 140 °C et une enthalpie de fusion de 30 à 100 J/g ;
    et ledit liquide comprend au moins un hydrocarbure alkyl-arylique qui comporte au moins deux cycles aromatiques non condensés et où le rapport du nombre d'atomes de carbone aryliques au nombre total d'atomes de carbone est supérieur ou égal à 0,6.
  2. Câble conforme à la revendication 1, dans lequel le rapport du nombre d'atomes de carbone aryliques au nombre total d'atomes de carbone est supérieur ou égal à 0,7.
  3. Câble conforme à la revendication 1 ou 2, dans lequel l'homopolymère ou copolymère de propylène présente un point de fusion de 145 à 170 °C.
  4. Câble conforme à l'une des revendications précédentes, dans lequel l'homopolymère ou copolymère de propylène présente une enthalpie de fusion de 30 à 85 J/g.
  5. Câble conforme à l'une des revendications précédentes, dans lequel l'homopolymère ou copolymère de propylène présente un module de flexion, mesuré à température ambiante, de 30 à 1400 MPa.
  6. Câble conforme à l'une des revendications précédentes, dans lequel l'homopolymère ou copolymère de propylène présente un module de flexion, mesuré à température ambiante, de 60 à 1000 MPa
  7. Câble conforme à l'une des revendications précédentes, dans lequel l'homopolymère ou copolymère de propylène présente un indice de fluidité à chaud, mesuré à 230 °C, de 0,05 à 10,0 dg/min.
  8. Câble conforme à l'une des revendications précédentes, dans lequel l'homopolymère ou copolymère de propylène présente un indice de fluidité à chaud, mesuré à 230 °C, de 0,5 à 5,0 dg/min.
  9. Câble conforme à l'une des revendications précédentes, dans lequel l'oléfine comonomère se trouve en une proportion molaire inférieure ou égale à 15 %.
  10. Câble conforme à l'une des revendications précédentes, dans lequel l'oléfine comonomère se trouve en une proportion molaire inférieure ou égale à 10 %.
  11. Câble conforme à l'une des revendications précédentes, dans lequel l'oléfine comonomère est de l'éthylène ou une α-oléfine de formule CH2=CH-R où R représente un groupe alkyle en C2-10, linéaire ou ramifié.
  12. Câble conforme à la revendication précédente, dans lequel l'α-oléfine est choisie parmi les 1-butène, 1-pentène, 4-méthyl-1-pentène, 1-hexène, 1-octène, 1-décène, 1-docécène et composés similaires, ainsi que leurs combinaisons.
  13. Câble conforme à l'une des revendications précédentes, dans lequel le matériau thermoplastique est choisi parmi :
    a) un homopolymère de propylène ou un copolymère de propylène et d'au moins une oléfine comonomère choisie parmi l'éthylène et une α-oléfine autre que le propylène, présentant un module de flexion de 30 à 900 MPa ;
    b) un copolymère hétérophasique, qui comprend une phase thermoplastique à base de propylène et une phase élastomère à base d'éthylène copolymérisé avec une α-oléfine, et dans lequel la phase élastomère se trouve en une quantité représentant au moins 45 % du poids total du polymère hétérophasique.
  14. Câble conforme à la revendication précédente, dans lequel l'homopolymère ou copolymère de propylène (a) présente un module de flexion de 50 à 400 MPa.
  15. Câble conforme à la revendication 13 ou 14, dans lequel l'homopolymère ou copolymère de propylène (a) présente
    un point de fusion de 140 à 165 °C ;
    une enthalpie de fusion de 30 à 80 J/g ;
    une fraction inférieure ou égale à 12 % en poids de matière soluble dans de l'éther diéthylique bouillant, présentant une enthalpie de fusion inférieure ou égale à 4 J/g ;
    une fraction de 15 à 60 % en poids de matière soluble dans du n-heptane bouillant, présentant une enthalpie de fusion de 10 à 40 J/g ;
    et une fraction de 40 à 85 % en poids de matière insoluble dans du n-heptane bouillant, présentant une enthalpie de fusion supérieure ou égale à 45 J/g.
  16. Câble conforme à l'une des revendications 13 à 15, dans lequel l'homopolymère ou copolymère de propylène (a) présente
    une fraction de 1 à 10 % en poids de matière soluble dans de l'éther diéthylique bouillant, présentant une enthalpie de fusion inférieure ou égale à 2 J/g ;
    une fraction de 20 à 50 % en poids de matière soluble dans du n-heptane bouillant, présentant une enthalpie de fusion de 15 à 30 J/g ;
    et une fraction de 50 à 80 % en poids de matière insoluble dans du n-heptane bouillant, présentant une enthalpie de fusion de 50 à 95 J/g.
  17. Câble conforme à la revendication 13, dans lequel l'a-oléfine incluse dans la phase élastomère du copolymère hétérophasique (b) est du propylène.
  18. Câble conforme à la revendication précédente, dans lequel la phase élastomère consiste en un copolymère élastomère d'éthylène et de propylène, constitué de 15 à 50 % en poids d'éthylène et de 50 à 85 % en poids de propylène, par rapport au poids de la phase élastomère.
  19. Câble conforme à l'une des revendications précédentes, dans lequel le matériau thermoplastique de base est un homopolymère ou copolymère de propylène, mélangé mécaniquement avec un polymère à bas taux de cristallinité dont l'enthalpie de fusion est inférieure ou égale à 30 J/g et qui représente au plus 70 % du poids total du matériau thermoplastique.
  20. Câble conforme à la revendication précédente, dans lequel le polymère à bas taux de cristallinité représente de 20 à 60 % du poids total du matériau thermoplastique.
  21. Câble conforme à la revendication 19 ou 20, dans lequel le polymère à bas taux de cristallinité est un copolymère d'éthylène et d'une α-oléfine en C3-12.
  22. Câble conforme à la revendication 19 ou 20, dans lequel le polymère à bas taux de cristallinité est un copolymère d'éthylène, d'une α-oléfine et d'un diène.
  23. Câble conforme à la revendication 21 ou 22, dans lequel le copolymère d'éthylène est choisi parmi
    i) un copolymère dont la composition en monomères est la suivante : 35 à 90 % en moles d'éthylène, 10 à 65 % en moles d'une α-oléfine, et 0 à 10 % en moles d'un diène ;
    ii) et un copolymère dont la composition en monomères est la suivante : 75 à 97 % en moles d'éthylène, 3 à 25 % en moles d'une α-oléfine, et 0 à 5 % en moles d'un diène.
  24. Câble conforme à la revendication précédente, dans lequel le copolymère d'éthylène est un copolymère dont la composition en monomères est la suivante : 90 à 95 % en moles d'éthylène, 5 à 10 % en moles d'une α-oléfine, et 0 à 2 % en moles d'un diène.
  25. Câble conforme à l'une des revendications 21 à 24, dans lequel l'α-oléfine est choisie parmi les propylène, 1-hexène et 1-octène.
  26. Câble conforme à l'une des revendications 22 à 25, dans lequel le diène comporte de 4 à 20 atomes de carbone.
  27. Câble conforme à l'une des revendications 22 à 26, dans lequel le diène est choisi parmi les dioléfines linéaires à doubles liaisons conjuguées ou non et les diènes monocycliques ou polycycliques.
  28. Câble conforme à l'une des revendications 22 à 27, dans lequel le diène est choisi parmi les 1,3-butadiène, 1,4-hexadiène, 1,6-octadiène, 1,4-cyclohexadiène, 5-éthylidène-2-norbornène, 5-méthylène-2-norbornène, 5-vinyl-2-norbornène et composés similaires, ainsi que leurs mélanges.
  29. Câble conforme à l'une des revendications précédentes, dans lequel l'hydrocarbure alkyl-arylique présente, à 25 °C, une constante diélectrique inférieure ou égale à 3,5.
  30. Câble conforme à l'une des revendications précédentes, dans lequel la constante diélectrique, à 25 °C, est inférieure ou égale à 3.
  31. Câble conforme à l'une des revendications précédentes, dans lequel le liquide diélectrique présente, à 20 °C, une viscosité cinématique de 1 à 500 mm2/s.
  32. Câble conforme à l'une des revendications précédentes, dans lequel le liquide diélectrique présente, à 20 °C, une viscosité cinématique de 5 à 100 mm2/s.
  33. Câble conforme à l'une des revendications précédentes, dans lequel l'hydrocarbure alkyl-arylique présente une capacité d'absorption d'hydrogène supérieure ou égale à 5 mm3/min.
  34. Câble conforme à la revendication précédente, dans lequel la capacité d'absorption d'hydrogène est supérieure ou égale à 50 mm3/min.
  35. Câble conforme à l'une des revendications précédentes, dans lequel une résine époxy est ajoutée au liquide diélectrique, en une quantité qui représente au plus 1 % du poids de ce liquide.
  36. Câble conforme à la revendication précédente, dans lequel l'hydrocarbure alkyl-arylique se trouve présent en une quantité qui représente au moins 10 % du poids total du liquide diélectrique.
  37. Câble conforme à l'une des revendications précédentes, dans lequel le liquide diélectrique contient au moins un hydrocarbure alkyl-arylique qui comporte au moins trois cycles aromatiques non condensés.
  38. Câble conforme à l'une des revendications précédentes, dans lequel l'hydrocarbure alkyl-arylique présente la formule structurale suivante :
    Figure 00390001
    dans laquelle
       R1, R2, R3 et R4, qui peuvent être identiques ou différents, représentent chacun un atome d'hydrogène ou un groupe méthyle,
       et n1 et n2, qui peuvent être identiques ou différents, valent chacun 0, 1 ou 2, sous réserve que la somme n1 + n2 soit inférieure ou égale à 3.
  39. Câble conforme à l'une des revendications précédentes, dans lequel l'hydrocarbure alkyl-arylique est choisi parmi les benzyltoluène, benzylxylène, (méthylbenzyl)toluène, (méthylbenzyl)xylène, dibenzyltoluène, dibenzylxylène, di(méthylbenzyl)toluène, di(méthylbenzyl)xylène et composés similaires, ainsi que leurs mélanges.
  40. Câble conforme à l'une des revendications précédentes, dans lequel le liquide diélectrique contient au moins un triphénylméthane qui ne comporte aucun substituant ou comporte au moins un substituant choisi parmi les groupes méthyle, benzyle et méthyl-benzyle.
  41. Câble conforme à la revendication précédente, dans lequel le triphénylméthane est choisi parmi les ditoluyl-phényl-méthane, dixylylphényl-méthane, xylyl-toluyl-phényl-méthane et composés similaires, ainsi que leurs mélanges.
  42. Câble conforme à l'une des revendications précédentes, dans lequel le rapport pondéral du liquide diélectrique au matériau polymère de base vaut de 1/99 à 25/75.
  43. Câble conforme à l'une des revendications précédentes, dans lequel le rapport pondéral du liquide diélectrique au matériau polymère de base vaut de 2/98 à 20/80.
  44. Câble conforme à l'une des revendications précédentes, dans lequel le rapport pondéral du liquide diélectrique au matériau polymère de base vaut de 3/97 à 15/85.
  45. Câble conforme à l'une des revendications précédentes, dans lequel la couche de revêtement extrudé est une couche (4) dotée de propriétés d'isolant électrique.
  46. Câble conforme à l'une des revendications 1 à 44, dans lequel la couche de revêtement extrudé est une couche (3, 5) dotée de propriétés de semi-conducteur.
  47. Câble conforme à la revendication précédente, dans lequel une charge conductrice est dispersée dans la couche dotée de propriétés de semi-conducteur.
  48. Câble conforme à l'une des revendications précédentes, dans lequel le matériau polymère de base est choisi parmi les homopolymères et copolymères de propylène comportant une phase amorphe qui constitue au moins 40 % du poids total du polymère.
  49. Câble conforme à l'une des revendications précédentes, dans lequel il y a au moins une couche dotée de propriétés d'isolant électrique et au moins une couche dotée de propriétés de semi-conducteur.
  50. Composition de polymère comportant un matériau polymère thermoplastique mélangé avec un liquide diélectrique, conforme à l'une des revendications 1 à 49.
  51. Emploi d'une composition de polymère, conforme à la revendication 50, en tant que matériau polymère de base dans la préparation d'une couche de revêtement (4) dotée de propriétés d'isolant électrique.
  52. Emploi d'une composition de polymère, conforme à la revendication 50, en tant que matériau polymère de base dans la préparation d'une couche de revêtement (3, 5) dotée de propriétés de semi-conducteur.
EP01951601A 2000-06-28 2001-06-15 Cable a gaine recyclable Expired - Lifetime EP1295301B1 (fr)

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EP01951601A EP1295301B1 (fr) 2000-06-28 2001-06-15 Cable a gaine recyclable
PCT/EP2001/006820 WO2002003398A1 (fr) 2000-06-28 2001-06-15 Cable a gaine recyclable

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WO2012084055A1 (fr) 2010-12-23 2012-06-28 Prysmian S.P.A. Procédé en continu pour la fabrication d'un câble de puissance haute tension
CN103339686B (zh) 2010-12-23 2016-01-06 普睿司曼股份公司 具有稳定化耐压电阻的能量电缆
DE102011075786A1 (de) * 2011-05-13 2012-11-15 Siemens Aktiengesellschaft Elektrisches Bauelement
CA2843308C (fr) 2011-08-04 2018-08-28 Prysmian S.P.A. Cable electrique comportant une couche thermoplastique electriquement isolante
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RU2590904C1 (ru) 2012-05-18 2016-07-10 Призмиан С.П.А. Способ изготовления силового кабеля, имеющего термопластичный электроизоляционный слой
US10297372B2 (en) 2012-05-18 2019-05-21 Prysmian S.P.A Process for producing an energy cable having a thermoplastic electrically insulating layer
JP5894710B2 (ja) * 2012-09-27 2016-03-30 ダウ グローバル テクノロジーズ エルエルシー 架橋性エチレン系ポリマー組成物中の過酸化物のマイグレーションを低減するための方法
KR101710873B1 (ko) 2013-08-12 2017-02-28 에이비비 테크놀로지 리미티드 케이블 절연을 위한 열가소성 블렌드 제제
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BR112017019444B1 (pt) 2015-03-20 2022-01-11 Prysmian S.P.A. Cabo de alimentação de múltiplas fases
EP3353334B1 (fr) * 2015-09-25 2020-09-23 Prysmian S.p.A. Câble d'alimentation en aluminium revêtu par un inhibiteur de corrosion à base d'un composé de tétrazole
CN108604786B (zh) 2015-10-23 2020-05-12 普睿司曼股份公司 用于具有热塑性绝缘的电缆的接头及其制造方法
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
CA3045056A1 (fr) 2016-11-30 2018-06-07 Prysmian S.P.A. Cable d'alimentation
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EP4390976A1 (fr) 2022-12-23 2024-06-26 Nexans Couche de revêtement obtenue à partir d'une composition polymère comprenant au moins un matériau polymère thermoplastique et au moins un composé comprenant au moins un groupe nitrile

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BR0112004A (pt) 2003-05-13
AU7248501A (en) 2002-01-14
CN1503977A (zh) 2004-06-09
MY123591A (en) 2006-05-31
ATE264539T1 (de) 2004-04-15
BR0112004B1 (pt) 2010-11-16
DE60102817T2 (de) 2004-09-30
CA2412891A1 (fr) 2002-01-10
WO2002003398A1 (fr) 2002-01-10
DE60102817D1 (de) 2004-05-19
ES2219544T3 (es) 2004-12-01
CN1249732C (zh) 2006-04-05
CA2412891C (fr) 2009-09-22
AU2001272485B2 (en) 2005-04-28
AR028766A1 (es) 2003-05-21

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