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    • 专利摘要:
    cable. a cable comprising at least one electrical conductor and at least one electrically insulating layer surrounding said electrical conductor, wherein the at least one electrically insulating layer comprises: (a) a thermoplastic polymer material selected from: at least one copolymer (1) of propylene having at least one olefin comonomer selected from ethylene and an α-olefin other than propylene, said copolymer having a melt plane greater than or equal to 130 ° C and a melt enthalpy of 20 j / g to 90 j / g; a mixture of at least one copolymer (i) with at least one ethylene copolymer (ii) with at least one α-olefin, said copolymer (ii) having a melt enthalpy of 0 µg / g to 70 µg / g; a mixture of at least one propylene homopolymer with at least one copolymer (i) or copolymer (ii), a mixture of at least one propylene homopolymer with at least one copolymer (i) or copolymer (ii), (b) at least minus a nano size charge; wherein at least one of copolymer (i) and copolymer (ii) is a heterophasic copolymer.
    公开号:BR112012018898B1
    申请号:R112012018898-4
    申请日:2010-01-29
    公开日:2019-11-26
    发明作者:Gabriele Perego；Sergio Belli
    申请人:Prysmian S.P.A.；
    IPC主号:
    专利说明:

    Fundamentals of the invention [01] The present invention relates to a power cable. In particular, the present invention relates to a cable for carrying or distributing electrical energy, especially medium or high voltage electrical energy, said cable having at least one layer of polypropylene nanocomposite. Said cable can be used for the transmission or distribution of direct current (DC) or alternating current (AC).
    [02] Cables for carrying electrical energy generally include at least one cable core. The cable core is usually formed by at least one conductor sequentially covered by an inner polymeric layer having semiconductive properties, an intermediate polymeric layer having electrically insulating properties, an outer polymeric layer having semiconductive properties. Cables for carrying medium or high voltage electrical power generally include at least one cable core surrounded by at least one layer of mesh, typically made of metal or metal and polymeric material. The layer of fabric can be made in the form of wires (braids), a ribbon helically wound around the cable core or a sheet longitudinally surrounding the cable core. The polymeric layers surrounding the at least one conductor are usually made of a crosslinked polymer based on polyolefin, in particular crosslinked polyethylene (XLPE), or elastomeric ethylene / propylene (EPR) or ethylene / propylene / diene copolymers (EPDM), also cross-linked, as described, for example, in WO 98/52197. The crosslinking step, performed after extruding the polymeric material onto the conductor, gives the material satisfactory mechanical and electrical properties even under high temperatures both during continuous use and with current overload.
    [03] To address the requirements for materials that should not
    Petition 870190096583, of 9/26/2019, p. 11/37 / 22 being harmful to the environment both during production and during use, and which must be recyclable at the end of the cable's life, power cables have recently been developed with a cable core made of thermoplastic materials, ie polymeric materials that are not cross-linked and thus can be recycled at the end of the cable's life.
    [04] In this respect, electrical cables comprising at least one sheath layer, for example, the insulation layer, based on a polypropylene matrix intimately mixed with a dielectric fluid are known and described in WO 02/03398, WO 02/27731, WO 04/066318, WO 07/048422, and WO 08/058572. The polypropylene matrix useful for this type of cables comprises polypropylene homopolymer or copolymer or both, characterized by a relatively low crystallinity such as to provide the cable with adequate flexibility, but not to communicate the mechanical properties and resistance to thermopressure at temperatures of operating cable and overload. The performance of the cable sheath, especially the insulating layer of the cable, is also affected by the presence of the dielectric fluid intimately mixed with the said polypropylene matrix. The dielectric fluid must not affect the mechanical properties mentioned and resistance to thermopressure and must be such that it is intimately and homogeneously mixed with the polymeric matrix.
    [05] Improvement in the electrical performance of polymeric materials added with inorganic nanocharges has been suggested. For example, Montanari et al., IEEE Transactions on Dielectrics and Electrical Insulation, Vol. 11, N 5, October 2004 describe electrical properties of nanocomposite insulating materials. In particular, research on isotactic polypropylene (iPP) added with a nanocharge that consists of a silicate in an organophilic layer, specifically synthetic fluorohectorite, modified by exchanging the sodium cations interlayered with protonated octadecylamine (ODA), NH3 + , is reported. Polypropylene required
    Petition 870190096583, of 9/26/2019, p. 12/37 / 22 the addition of a compatibilizer (20%) consisting of iPP + 3.5% maleic anhydride, grafted into the main chain of the iPP chain.
    [06] Reichert et al., Macromol. Mater. Eng. 275, 8-17 (2000) report that, although anisotropic nanocharges have been found to produce attractive combinations of hardness and strength when combined with polypropylene, limited commercial availability and dispersion problems due to the strong interparticle interactions of nanocharges have restricted the your application. The nanocomposites were prepared by combining polypropylene in the presence of fluoromic turned organophilic through ion exchange with protonated amines, in the presence of polypropylene grafted with maleic anhydride (PP-g-MA).
    Summary of the invention [07] The problem of improving the performance of power cables having an electrically insulating layer with a thermoplastic coating based on polypropylene was addressed. A cable jacket layer, especially an insulating layer, has to satisfy several requirements including safe electrical performance, without decomposition even at high operating temperature like 90 ° C to 110 ° C for continuous use, and up to 130 ° C in the case current overload, while having acceptable mechanical properties.
    [08] In order to improve said electrical properties, the use of charges, in particular inorganic nanocharges, was considered. However, the use of nanocharges in polypropylene compositions causes a reduction in the mechanical and insulating properties of the polymeric material, because of the decrease in the homogeneity capacity, unless compatibilizers are used.
    [09] The use of compatibilizers means a modification of the polymer base, such as by the addition of polyolefins grafted with maleic anhydride, and / or a nanocharge surface treatment, for example, by
    Petition 870190096583, of 9/26/2019, p. 13/37 / 22 application of surface treatment agents, such as silanes or fatty acids or derivatives thereof, typically used as binding agents between the mineral filler and the polymeric material.
    [10] The compatibilizers used to improve the homogeneity of polymeric / inorganic charge mixtures typically have polar groups. It is believed that the need for a compatibilizer between the polypropylene and the nanocharge is due to the lack of cohesion between the polypropylene and the nanocharge, resulting in the deterioration of the insulation properties due to an increased likelihood of formation, for example, of microvazios or discontinuous interfaces.
    [11] However, electrical properties, particularly in terms of dielectric strength (dielectric break strength) and accumulation of space charge, can be negatively affected by the addition of polar groups to the insulating material.
    [12] It has been found that the above problems can be solved by providing the power cable with at least one electrically insulating layer comprising a thermoplastic composition comprising at least one heterophasic propylene copolymer intimately mixed with a nanocharge. The use of a thermoplastic composition as defined below allows the use of a nanocharge without adding any compatibilizer even when the nanocharge is not treated, that is, free of surface treatment agents.
    [13] In a first aspect, the present invention relates to a cable comprising at least one electrical conductor and at least one electrically insulating layer that surrounds said electrical conductor, wherein the at least one electrically insulating layer comprises:
    (a) a thermoplastic polymer material selected from:
    - at least one propylene copolymer (i) with at least one olefin comonomer selected from ethylene and one α-olefin other than
    Petition 870190096583, of 9/26/2019, p. 14/37 / 22 non-propylene, said copolymer having a melting point greater than or equal to 130 ° C and a melting enthalpy of 20 J / g to 90 J / g;
    - a mixture of at least one copolymer (i) with at least one copolymer (ii) of ethylene with at least one α-olefin, said copolymer (ii) having a melting enthalpy of 0 J / g to 70 J / g;
    - a mixture of at least one propylene homopolymer with at least one copolymer (i) or copolymer (ii);
    (b) at least one nano-sized charge, wherein at least one of copolymer (i) and copolymer (ii) is a heterophasic copolymer.
    [14] For the purpose of this description and the claims that follow, except where otherwise indicated, all numbers expressing amounts, quantities, percentages, and so forth, are to be understood as being modified in all cases by the term "about". Also, all ranges include any combination of the maximum and minimum points described and include any of the intermediate ranges in them, which may or may not be specifically listed here.
    [15] In the present description and in the subsequent claims, as "conductor" is intended an electrically conductive element usually made of a metallic material, more preferably aluminum, copper or alloys thereof, as a rod or as a multiple filament wire, or a conductive element as above coated with a semiconductive layer.
    [16] For the purposes of the invention the term "average voltage" generally means a voltage between 1 kV and 35 kV, while "high voltage" means voltages higher than 35 kV.
    [17] As an “electrically insulating layer”, a covering layer made of a material having insulating properties is intended, that is, one having a dielectric strength (dielectric break strength) of at least
    Petition 870190096583, of 9/26/2019, p. 15/37 / 22 kV / mm, preferably greater than 10 kV / mm.
    [18] As a “semiconductive layer”, a covering layer made of a material having semiconductive properties, such as a polymeric matrix added, for example with carbon black, is intended as to obtain a volumetric resistivity value at room temperature, less than 500 µm, preferably less than 20 µm. Typically, the amount of carbon black can vary between 1 and 50% by weight, preferably between 3 and 30% by weight, relative to the weight of the polymer.
    [19] The fusion enthalpy (ÁHm) can be determined by the Differential Scanning Calorimetry (DSC) analysis.
    [20] With "heterophasic copolymer", a copolymer is desired in which the elastomeric domains, for example, ethylene propylene elastomer (EPR), are dispersed in a homopolymer or propylene copolymer matrix.
    [21] Preferably, the at least one nano-sized charge (b) is not treated. With "untreated" it is intended that the nano-sized charge is used without prior surface treatment, typically with a silane or fatty acid or derivatives thereof.
    [22] The electrically insulating layer according to the present invention is substantially devoid of any compatibilizer. With "compatibilizer" is intended any product capable of improving the compatibility of the nanocharge with the polymeric matrix, such as maleic anhydride or unsaturated silanes in the presence of peroxide.
    [23] Preferably, the thermoplastic polymer material (a) has a melt flow index (MFI), measured at 230 ° C with a load of 21.6 N according to ASTM Standard D1238-00, from 0, 05 degrees / min to 10.0 degrees / min, more preferably from 0.4 degrees / min to 5.0 degrees / min.
    [24] The olefin comonomer in copolymer (i) can be ethylene or an α-olefin of the formula CH 2 = CH-R, where R is linear C 2 -C 10 alkyl
    Petition 870190096583, of 9/26/2019, p. 16/37 / 22 or branched, selected, for example, from: 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, or mixtures thereof. Propylene / ethylene copolymers are particularly preferred.
    [25] The olefin comonomer in copolymer (i) is preferably present in an amount equal to or less than 15 mol%, more preferably equal to or lower than 10 mol%.
    [26] The olefin comonomer in copolymer (ii) can be an olefin of the formula CH2 = CHR, where R represents a linear or branched alkyl group containing from 1 to 12 carbon atoms. Preferably, said olefin is selected from propylene, 1-butene, isobutylene, 1-pentene, 4-methyl1-pentene, 1-hexene, 1-octene, 1-dodecene, or mixtures thereof. Propylene, 1-hexene and 1-octene are particularly preferred.
    [27] According to a preferred embodiment, copolymer (i) or copolymer (ii) is a random copolymer.
    [28] With “random copolymer” a copolymer is intended in which the comonomers are randomly distributed along the polymer chain.
    [29] Advantageously, in copolymer (i) or copolymer (ii) or both, when heterophasic, an elastomeric phase is present in an amount equal to or greater than 45% by weight with respect to the total weight of the copolymer.
    [30] Heterophasic copolymers (i) or (ii) particularly preferred are those in which the elastomeric phase consists of an elastomeric copolymer of ethylene and propylene comprising from 15% by weight to 50% by weight of ethylene and 50% by weight. weight to 85% by weight of propylene with respect to the weight of the elastomeric phase.
    [31] Preferred copolymers (ii) are heterophasic propylene copolymers, in particular:
    (ii-a) copolymers having the following monomer composition:
    Petition 870190096583, of 9/26/2019, p. 17/37 / 22 mol% to 90 mol% of ethylene; 10 mol% to 65 mol% of an aliphatic α-olefin, preferably propylene; from 0 mol% to 10 mol% of a polyene, preferably a diene, more preferably 1,4hexadiene or 5-ethylene-2-norbornene (EPR and EPDM rubbers belong to this class);
    (ii-b) copolymers having the following monomer composition: from 75 mol% to 97 mol%, preferably from 90 mol% to 95 mol%, of ethylene; from 3 mol% to 25 mol%, preferably from 5 mol% to 10 mol%, of an aliphatic α-olefin; from 0 mol% to 5 mol%, preferably from 0 mol% to 2 mol%, of a polyene, preferably a diene (e.g. ethylene / 1-octene copolymers).
    [32] Heterophasic copolymers can be obtained by sequential copolymerization of: 1) propylene, possibly containing lesser amounts of at least one olefin comonomer selected from ethylene and an α-olefin other than propylene; and after: 2) a mixture of ethylene with an α-olefin, in particular propylene, optionally with smaller portions of a polyene.
    [33] The term "polyene" in general means a conjugated or unconjugated diene, triene or tetraene. When a diene comonomer is present, this comonomer generally contains from 4 to 20 carbon atoms and is preferably selected from: conjugated or unconjugated linear diolefins such as, for example, 1,3-butadiene, 1,4-hexadiene, 1.6octadiene, and the like; monocyclic or polycyclic dienes such as, for example, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2norbornene, vinylnorbornene, or mixtures thereof. When a triene or tetraene comonomer is present, this comonomer generally contains 9 to 30 carbon atoms and is preferably selected from trienes or tetraenes containing a vinyl group in the molecule or a 5norbornen-2-yl group in the molecule. Specific examples of comonomers of
    Petition 870190096583, of 9/26/2019, p. 18/37 / 22 triene or tetraene that can be used in the present invention are: 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decathriene, 6,9-dimethyl-1 , 5,8decatriene, 6,8,9-trimethyl-1,6,8-decatriene, 6,10,14-trimethyl-1,5,9,13 pentadecatetraene or mixtures thereof. Preferably, the polyene is a diene.
    [34] Preferably, copolymer (i), copolymer (ii) or both have a melting point of 140 ° C to 180 ° C.
    [35] Preferably, the copolymer (i) has a melting enthalpy of 25 J / g to 80 J / g.
    [36] Preferably, the copolymer (ii) has a melting enthalpy of 10 J / g to 30 J / g.
    [37] Advantageously, when the thermoplastic material of the insulating layer comprises a mixture of copolymer (i) and copolymer (ii) the latter has a lower melting enthalpy than that of the former.
    [38] Advantageously, when the thermoplastic material of the insulating layer comprises a mixture of copolymer (i) and copolymer (ii), the ratio between copolymer (i) and copolymer (ii) is preferably 1: 9 to 8: 2 from 2: 8 to 7: 3.
    [39] Advantageously, when the thermoplastic material of the insulating layer comprises a mixture of a propylene homopolymer and at least one of copolymer (i) and copolymer (ii), the ratio between the propylene homopolymer and copolymer (i) or copolymer (ii) or both is 0.5: 9.5 to 5: 5, preferably 1: 9 to 3: 7.
    [40] In a preferred embodiment of the invention, the at least one electrically insulating layer of the cable further comprises at least one dielectric fluid (c), intimately mixed with the thermoplastic material.
    [41] High compatibility between the dielectric fluid and the base polymer material is necessary to obtain a microscopically dispersion
    Petition 870190096583, of 9/26/2019, p. 19/37 / 22 homogeneous dielectric fluid in the base polymer material. The dielectric fluid suitable to form the cable cover layer of the present invention should not comprise any of the polar compounds or only a limited amount of them, in order to avoid a significant increase in dielectric losses.
    [42] The presence of a dielectric fluid in the cable of the present invention can substantially improve its electrical properties.
    [43] Preferably, the weight concentration of said at least one dielectric fluid in said thermoplastic polymer material is lower than the saturation concentration of said dielectric fluid in said thermoplastic polymer material. The saturation concentration of the dielectric fluid in the thermoplastic polymer material can be determined by a fluid absorption method in Dumbell specimens as described, for example, in WO 04/066317.
    [44] By using the dielectric fluid in an amount as defined above, the thermo-mechanical properties of the insulating layer are maintained and exudation of the dielectric fluid from the thermoplastic polymer material is avoided.
    [45] The at least one dielectric fluid is generally compatible with the thermoplastic polymer material. "Compatible" means that the chemical composition of the fluid and the thermoplastic polymer material is such as to result in a microscopically homogeneous dispersion of the dielectric fluid within the polymer material in the mixture of the fluid in the polymer, similar to a plasticizer.
    [46] In general, the weight ratio between the at least one dielectric fluid (c) and the thermoplastic polymer material (a) can be from 1:99 to 25:75, preferably from 2:98 to 15:85.
    [47] It should also be mentioned that the use of a fluid
    Petition 870190096583, of 9/26/2019, p. 20/37 / 22 dielectric with a relatively low melting point or low spill point (for example a melting point or a spill point no higher than 80 ° C) allows easy handling of the meltable dielectric fluid without any need for additional and complex manufacturing steps (for example a melting step of the dielectric fluid) and / or apparatus for mixing the liquid with the polymer material.
    [48] According to another preferred embodiment, the dielectric fluid has a melting point or a spill point of 130 ° C to + 80 ° C.
    [49] The melting point can be determined by known techniques such as, for example, Differential Scanning Calorimetry (DSC) analysis.
    [50] According to another preferred embodiment, the dielectric fluid has a predetermined viscosity in order to prevent rapid diffusion of the liquid within the insulating layer and consequently its migration outward, as well as to allow the fluid dielectric is easily fed and mixed into the thermoplastic polymer material. In general, the dielectric fluid of the invention has a viscosity, at 40 ° C, of 10 cSt to 800 cSt, preferably 20 cSt to 500 cSt (measured according to the ASTM D445-03 standard).
    [51] For example, the dielectric fluid is selected from mineral oils, for example, naphthenic oils, aromatic oils, paraffinic oils, polyaromatic oils, said mineral oils optionally containing at least one heteroatom selected from oxygen, nitrogen or sulfur; liquid paraffins; vegetable oils, for example, soybean oil, linseed oil, castor oil; oligomeric aromatic polyolefins; paraffinic waxes, for example, polyethylene waxes, polypropylene waxes; synthetic oils, for example, silicone oils, alkyl benzenes (for example, dodecylbenzene, di (octylbenzyl) toluene), aliphatic esters (for example, tetraesters of
    Petition 870190096583, of 9/26/2019, p. 21/37
    12/22 pentaerythritol, sebacic acid esters, phthalic esters), olefin oligomers (for example, optionally hydrogenated polybutenes or polyisobutenes); or mixtures thereof. Paraffinic oils and naphthenic oils are particularly preferred.
    [52] Mineral oils as a dielectric fluid may comprise polar compound (s). The amount of polar compound (s) advantageously is up to 2.3% by weight. Such a low amount of polar compounds allows to obtain low dielectric losses.
    [53] The amount of polar compounds in the dielectric fluid can be determined according to the ASTM D2007-02 standard.
    [54] Alternatively, the dielectric fluid can comprise at least one alkylaryl hydrocarbon having the structural formula:
    on what:
    R1, R2, R3 and R4, the same or different, are hydrogen or methyl;
    nl and n2, equal or different, are zero, 1 or 2, with the proviso that the sum of nl + n2 is less than or equal to 3.
    [55] In another alternative, the dielectric fluid comprises at least one diphenyl ether having the following structural formula:
    where Rs and Ró are the same or different and represent hydrogen, an unsubstituted or substituted phenyl group with at least one alkyl group, or an unsubstituted or substituted alkyl group with at least one phenyl. An alkyl group is intended with a hydrocarbon radical
    Petition 870190096583, of 9/26/2019, p. 22/37 / 22 straight or branched C1-C24, preferably C1-C20.
    [56] Dielectric fluids suitable for use in the cover layer for the cable of the invention are described, for example, in WO 02/027731, WO 02/003398 or WO 04/066317, all in the name of the Applicant.
    [57] The at least one nano-sized charge to be used in accordance with the present invention generally has an average particle size (at least in one dimension) equal to or less than 2000 nm, preferably from 1 to 500 nm. nm.
    [58] As for the chemical nature of the nano-sized charge, it can be selected from a wide range of metal oxides, titanates, silicates, for example scaly montmorillonite, silica, alumina.
    [59] The nano-charge can be selected, for example, from: ZnO, MgO, TiO2, SiO2, A2O3, BaTiO3, SnO, MnO2, BiO3, CuO, In2O3, La2O3, NiO, Sb2O3, SnO2, SrTiO3, Y2O3, W2O3.
    [60] Preferably, the at least one nano-charge (b) is present in an amount of 0.2% by weight to 5% by weight, more preferably from 0.5% by weight to 2% by weight, with respect to the weight of the thermoplastic polymer material (a).
    [61] Other components may be added in smaller amounts to the thermoplastic polymer material according to the present invention, such as antioxidants, processing aids, water column retardants, or mixtures thereof.
    [62] Conventional antioxidants suitable for the purpose are, for example, distearyl- or dilauryl-thiopropionate and pentaerythrityl-tetracis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], or mixtures thereof .
    [63] Processing aids that can be added to the polymeric composition include, for example, calcium stearate, zinc stearate, stearic acid, or mixtures thereof.
    [64] According to a preferred embodiment, the cable
    Petition 870190096583, of 9/26/2019, p. 23/37 / 22 according to the present invention also includes at least one semiconductive layer comprising, in addition to components (a) and (b), and optionally (c), as defined above, (d) at least one conductive charge, preferably a carbon black charge. The at least one conductive charge is generally dispersed within the thermoplastic polymer material in an amount such as to provide the material with semiconductive properties, i.e. to obtain a volumetric resistivity value, at room temperature, of less than 500 Ω- m, preferably less than 20 Ω-m. Typically, the amount of carbon black can vary between 1 and 50% by weight, preferably between 3 and 30% by weight, relative to the weight of the polymer.
    [65] The use of the same base polymer composition for both the insulating layer and the semiconductive layers is particularly advantageous in the production of cables for medium or high voltages, as this ensures excellent adhesion between adjacent layers and consequently good electrical behavior, particularly at the interface between the insulating layer and the internal semiconductive layer, where the electric field and consequently the risk of partial discharges are highest.
    [66] Polymeric compositions for the cable according to the present invention can be produced by mixing thermoplastic polymer material, the nano-sized charge and possibly the dielectric fluid and any other optional additive, using known methods in the technique. The mixing can be carried out for example by an internal mixer of the type with tangential rotors (Banbury) or with interpenetrating rotors; in a Ko-Kneader type continuous mixer (Buss), co-or counter-rotating double screw type extruder; or in a single screw.
    [67] According to a preferred embodiment, the dielectric fluid can be added to the thermoplastic polymer material during the extrusion step by direct injection into the extruder cylinder as described,
    Petition 870190096583, of 9/26/2019, p. 24/37 / 22 for example, in International Patent Application WO 02/47092 in the name of the Applicant.
    [68] Although the present description is mainly focused on cables for carrying or distributing medium or high voltage energy, the polymer composition of the invention can be used to coat electrical devices in general and in particular cable of a different type, for example low voltage (ie cables carrying a voltage lower than 1 kV), telecommunications cables or combined power / telecommunications cables, or accessories used in electrical lines, such as terminals, seals, connectors and the like.
    Brief description of the drawing [69] Other characteristics will be evident from the detailed description given below with reference to the attached drawings, in which:
    Figure 1 is a perspective view of a power cable, particularly suitable for medium or high voltages, according to the invention.
    Detailed description of the preferred embodiments [70] In Figure 1, 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 wire mesh layer (6), and a sheath (7).
    [71] The conductor (2) generally consists of metallic wires, preferably copper or aluminum or alloys thereof, braided together by conventional methods, or a solid rod of aluminum or copper.
    [72] The insulating layer (4) can be produced by extruding, around the conductor (2), a composition according to the present invention.
    Petition 870190096583, of 9/26/2019, p. 25/37 / 22 [73] The semiconductive layers (3) and (5) are also manufactured by the extrusion of polymeric material usually based on polyolefins, preferably a composition according to the present invention. The composition is made to be semiconductive by adding at least one conductive charge, usually carbon black.
    [74] Around the outer semiconductive layer (5), a layer of wire mesh (6) is usually placed, made of electrically conductive wires or strips helically wound around the cable core or of an electrically conductive tape longitudinally wrapped and overlapped (preferably glued) over the underlying layer. The electrically conductive material of said wires, strips or tapes is usually copper or aluminum or alloys thereof.
    [75] The canvas layer (6) can be covered by a sheath (7), generally made of a polyolefin, usually polyethylene.
    [76] The cable can also be provided with a protective structure (not shown in Figure 1) the main purpose of which is to mechanically protect the cable from impact or compression. This protective structure can be, for example, a metallic reinforcement or an expanded polymer layer as described in WO 98/52197 in the name of the Applicant.
    [77] The cable according to the present invention can be manufactured according to known methods, for example by extruding the various layers around the central conductor. The extrusion of two or more layers is advantageously carried out in a single pass, for example by the tandem method in which individual extruders are arranged in series, or by coextrusion with a multiple extrusion head. The screen layer is then applied around the cable core thus produced. Finally, the sheath according to the present invention is applied, usually by another extrusion step.
    [78] The cable of the present invention can be used for
    Petition 870190096583, of 9/26/2019, p. 26/37 / 22 alternating current (AC) or direct current (DC) energy transmission.
    [79] Figure 1 shows only one embodiment of a cable according to the invention. Suitable modifications can be made to this embodiment according to the technical needs and specific application requirements without departing from the scope of the invention.
    [80] The following examples illustrate the invention.
    EXAMPLES 1 to 3.
    [81] The following compositions were prepared with the amounts reported in Table 1 (expressed as% by weight with respect to the total weight of the composition).
    [82] In all examples, the propylene copolymer was fed directly into the extruder feeder silo. Subsequently, the dielectric fluid, previously mixed with antioxidants, was injected at high pressure into the extruder. An extruder having a diameter of 80 mm and an L / D ratio of 25 was used. The injection was made during the extrusion about 20 D from the beginning of the extruder thread through three injection points in the same cross section at 120 ° from each other. The dielectric fluid was injected at a temperature of 70 ° C and a pressure of 250 bar. The nano-load was fed into the polymer mixture by a side dosimeter and dispersed by a twin screw extruder (alternatively a Buss-bas can be used) with a thermal profile for the polymer mixture from 140 ° C to 200 ° C.
    TABLE 1
    EXAMPLE 1 (*) 2 3 Adflex® Q200F 93.7 91.2 92.7 Jarilec® Exp3 6 6 6 Nyasil® 5 - 2.5 1 Irgastab® KV10 0.3 0.3 0.3
    (*) comparative [83] Adflex® Q200F: propylene heterophase copolymer having a melting point of 165 ° C, melting enthalpy of 30 J / g, and a flexural modulus of 150 MPa (Basell);
    Petition 870190096583, of 9/26/2019, p. 27/37 / 22
    Jarilec® Exp3: dibenzyltoluene (DBT) (Elf Atochem);
    Nyasil® 5: nano-sized amorphous silica with an average particle size of 1.8 pm (Nyacol Inc.).
    [84] Irgastab® KV10: 4,6-bis (octylmethyl) -ocresol antioxidant (Ciba Specialty Chemicals, Inc.).
    [85] The dielectric strength (DS) of the polymeric compositions obtained was evaluated on the 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). In this method, the cable is simulated with test pieces in the form of a lens made of insulating material having its base coated on both sides with a coating of semiconductive material. The test pieces in the form of a lens were formed by molding discs of insulating material from 160 to 170 ° C from a 10 mm thick plate obtained by compressing each mixture of Example 1 to 3 at about 190 ° Ç.
    [86] The inner and outer surfaces of the base, which had a thickness of about 0.40 to 0.45 mm, were coated with a semiconductive coating. The measurement of DS 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 the test piece drilling has occurred. Each measurement was repeated on 10 test pieces. The values given in Table 2 are the arithmetic mean of the individual measured values. Two series of experiments were carried out: the first for the disposal of the samples having a DS lower than 25 kV / mm, the second for the disposal of the samples having a DS lower than 75 kV / mm. Screening above specimens is necessary to exclude those that are defective because of the molding process.
    [87] In the last row of Table 2, the percentage of specimens
    Petition 870190096583, of 9/26/2019, p. 28/37 / 22 having a DS higher than 100 kV / mm is reported. An increase in DS is observed for the specimens according to the present invention.
    TABLE 2
    EXAMPLE 1 (*) 2 3 DS> 25 kV / mm 98 109 94 DS> 75 kV / mm 98 109 117 Specimens with DS> 100 kV / mm (%) 33 83 33
    (*) comparative
    EXAMPLES 4 to 5.
    [88] The following compositions were prepared with the amounts reported in Table 3 (expressed as% by weight with respect to the total weight of the composition), following the same conditions reported for examples 1 to 3.
    TABLE 3
    EXAMPLE 4 (*) 5 Hifax® CA 7441 A 97 95 Jarilec® Exp3 2.8 2.8 MgO - 2 Irganox® B225 0.2 0.2
    (*) comparative [89] Hifax® CA7441A: heterophasic propylene copolymer having melting point of 165 ° C, melting enthalpy of 30 J / g, and flexural modulus of 100 MPa (Basell);
    Jarilec ® Exp3: dibenzyltoluene (DBT) (Elf Atochem);
    MgO: magnesium oxide with an average particle size of 35 nm (Cometex S.r.l.)
    Irganox ® B225: phenolic / phosphate antioxidant (Ciba Specialty Chemicals, Inc.).
    [90] From the above compositions, specimens were obtained in the form of 1 mm thick plates. The plates were molded at 195 ° C with 15 min of preheating. The specimens thus obtained were tested to determine the tensile properties according to the CEI EN 60811-1 (2006-06) standard, with a tension speed of 50 mm / min. The results are reported in Table 4:
    TABLE 4
    Petition 870190096583, of 9/26/2019, p. 29/37 / 22
    EXAMPLE 4 (*) 5 Tensile strength (MPa) 17.4 18.0 Elongation at break (%) 778.0 788.6 100% modulus (MPa) 4.6 5.4 200% modulus (MPa) 5.9 6.3 Module at 300% (MPa) 7.1 7.4
    (*) comparative [91] The mechanical strength of the sample with the composition according to the invention has been shown to be improved despite the absence of a nano-charge compatibilizer.
    [92] The above compositions were also used for Electro Acoustic Pulse (PEA) measurements to assess the formation of space charge in insulating materials.
    [93] For each composition, disks were prepared having a thickness of 0.3 mm and a diameter of 50 mm, placed between semicon electrodes having a thickness of 0.1 mm and a diameter of 30 mm. A DC voltage of 30 kV / mm was applied for 10,000 seconds, and the spatial load was measured by the PEA with no voltage applied. The sample was electrically grounded with no voltage applied for 2,000 seconds, and then a DC voltage of -30 kV / mm was applied for 10,000 seconds. The spatial load without applied voltage was measured again by the PEA. The sample was electrically grounded with no voltage applied for 1,000 seconds, then the percentage of residual charge was measured. All measurements were made at room temperature. The results are reported in Table 5.
    TABLE 5
    EXAMPLE 4 (*) 5 Q (+) (C / m 3 ) 0.50 0.25 Q (-) (C / m 3 ) 0.45 0.35 Q res. @ 1,000 seconds (%) 40 25
    (*) comparative [94] The above results show a significantly lower spatial charge content in Volt Off (Q (+) or Q (-) depending on the type of charge) for the insulating compositions according to the present invention (Ex . 5), with respect to the corresponding compositions devoid of any nanocharge (Ex. 4). In addition, the discharge rate of the accumulated charge after
    Petition 870190096583, of 9/26/2019, p. 30/37 / 22 Volt Off is much lower for the composition of Example 5 than for the composition of Example 4, as shown by the values of Q res. @ 1,000 seconds (the lower the amount of residual charge after 1,000 seconds of Volt Off, the higher the discharge rate of the accumulated charge). EXAMPLES 6 to 8.
    [95] The following compositions were prepared with the amounts reported in Table 6 (expressed as% by weight relative to the total weight of the composition), following the same conditions reported for examples 1 to 3.
    TABLE 6
    EXAMPLE 6 (*) 7 8 Hifax® CA 7441A 99.7 97.7 94.7 Jarilec® Exp3 - - 3 ZnO - 2 2 Irgastab® KV10 0.3 0.3 0.3
    (*) comparative [96] Hifax® CA7441A: heterophasic propylene copolymer having melting point of 165 ° C, melting enthalpy of 30 J / g, and flexural modulus of 100 MPa (Basell);
    Jarilec ® Exp3: dibenzyltoluene (DBT) (Elf Atochem);
    ZnO: nanopowder with an average particle size lower than 100 nm (Sigma Aldrich)
    Irgastab ® KV10: 4,6-bis (octylmethyl) -ocresol antioxidant (Ciba Specialty Chemicals, Inc.).
    [97] From the above compositions, specimens were obtained in the form of 1 mm thick plates. The plates were molded at 195 ° C with 15 min preheating. The specimens thus obtained were tested to determine the tensile properties according to the CEI EN 60811-1 (2006-06) standard, with a tension speed of 50 mm / min. The results are reported in Table 7:
    TABLE 7
    Petition 870190096583, of 9/26/2019, p. 31/37 / 22
    EXAMPLE 6 (*) 7 8 Tensile strength (MPa) 18.2 21.5 17.2 Elongation at break (%) 781.9 816.4 791.1 100% modulus (MPa) 4.8 5.9 4.9 200% modulus (MPa) 6.0 6.8 5.9 Module at 300% (MPa) 7.2 7.9 7.1
    (*) comparative [98] The mechanical strength of the sample with the composition according to the invention has been shown to be unaffected if not improved despite the absence of a nano-charge compatibilizer.
    [99] The addition of a nano-charge in the absence of an adjuvant for compatibility between the nano-charge and a polypropylene material provides an insulating layer for the power cable with improved electrical performance while maintaining, or even improving mechanical strength. .
    权利要求:
    Claims (24)
    [1]
    1. Cable comprising at least one electrical conductor and at least one electrically insulating layer surrounding said electrical conductor, characterized by the fact that the at least one electrically insulating layer comprises:
    (a) a thermoplastic polymer material selected from:
    - at least one propylene copolymer (i) with at least one olefin comonomer selected from ethylene and an α-olefin other than propylene, said copolymer having a melting point greater than or equal to 130 ° C and an enthalpy melting range 20 J / g to 90 J / g;
    - a mixture of at least one copolymer (i) with at least one copolymer (ii) of ethylene with at least one α-olefin, said copolymer (ii) having a melting enthalpy of 0 J / g to 70 J / g;
    - a mixture of at least one propylene homopolymer with at least one copolymer (i) or copolymer (ii);
    (b) at least one nano-sized charge;
    wherein at least one of copolymer (i) and copolymer (ii) is a heterophasic copolymer;
    wherein the at least one electrically insulating layer is substantially devoid of any compatibilizer.
    [2]
    2. Cable according to claim 1, characterized by the fact that the at least one nano-sized load (b) is not treated.
    [3]
    Cable according to claim 1, characterized in that the copolymer (i) is a propylene / ethylene copolymer.
    [4]
    4. Cable according to claim 1, characterized by the fact that the olefin comonomer in the copolymer (i) is present in an amount equal to or less than 15 mol%, preferably equal to or less than 10 mol%
    [5]
    5. Cable according to claim 1, characterized by
    Petition 870190096583, of 9/26/2019, p. 33/37
    2/4 the fact that copolymer (i) or copolymer (ii) is a random copolymer.
    [6]
    6. Cable according to claim 1, characterized by the fact that in copolymer (i) or copolymer (ii) or both, when heterophasic, an elastomeric phase is present in an amount equal to or greater than 45% by weight with relative to the total weight of the copolymer.
    [7]
    7. Cable according to claim 6, characterized in that the elastomeric phase consists of an elastomeric copolymer of ethylene and propylene comprising 15% by weight to 50% by weight of ethylene and 50% by weight to 85% by weight of propylene in relation to the weight of the elastomeric phase.
    [8]
    8. Cable according to claim 1, characterized by the fact that the olefin comonomer in the copolymer (ii) is propylene, 1hexene or 1-octene.
    [9]
    9. Cable according to claim 1, characterized in that the copolymer (i), copolymer (ii) or both have a melting point of 140 ° C to 180 ° C.
    [10]
    10. Cable according to claim 1, characterized in that the copolymer (i) has a melting enthalpy of 25 J / g to 80 J / g.
    [11]
    11. Cable according to claim 1, characterized in that the copolymer (ii) has a melting enthalpy of 10 J / g to 30 J / g.
    [12]
    Cable according to claim 1, characterized in that when the thermoplastic material of the insulating layer comprises a mixture of copolymer (i) and copolymer (ii), the latter has a lower melting enthalpy than that of the former .
    [13]
    13. Cable according to claim 1, characterized in that when the thermoplastic material of the insulating layer comprises a mixture of copolymer (i) and copolymer (ii), the ratio between copolymer (i) and copolymer (ii) is from 1: 9 to 8: 2.
    [14]
    14. Cable according to claim 1, characterized by the
    Petition 870190096583, of 9/26/2019, p. 34/37
    3/4 the fact that when the thermoplastic material of the insulating layer comprises a mixture of a propylene homopolymer and at least one of copolymer (i) and copolymer (ii), the ratio between the propylene homopolymer and copolymer (i) or copolymer (ii) or both is 0.5: 9.5 to 5: 5.
    [15]
    Cable according to claim 1, characterized in that the at least one electrically insulating layer additionally comprises at least one dielectric fluid (c), intimately mixed with the thermoplastic material.
    [16]
    16. Cable according to claim 1, characterized in that the weight concentration of said at least one dielectric fluid in said thermoplastic polymer material is lower than the saturation concentration of said dielectric fluid in said polymer material thermoplastic.
    [17]
    17. Cable according to claim 1, characterized in that the weight ratio between the at least one dielectric fluid (c) and the thermoplastic polymer material (a) is from 1:99 to 25:75, preferably from 2:98 to 15:85.
    [18]
    18. Cable according to claim 1, characterized in that the at least one dielectric fluid (c) has a melting point or a spill point from -130 ° C to + 80 ° C.
    [19]
    19. Cable according to claim 1, characterized by the fact that at least one dielectric fluid (c) is selected from mineral oils, optionally containing at least one heteroatom selected from oxygen, nitrogen or sulfur; liquid paraffins; vegetable oils; oligomeric aromatic polyolefins; paraffinic waxes; synthetic oils.
    [20]
    20. Cable according to claim 1, characterized in that the at least one nano size charge (b) has an average particle size (at least in one dimension) equal to or less than 2000 nm, preferably from 1 to 500 nm.
    Petition 870190096583, of 9/26/2019, p. 35/37
    4/4
    [21]
    21. Cable according to claim 1, characterized by the fact that the at least one nano-sized load (b) is selected from metal oxides, titanates, silicates.
    [22]
    22. Cable according to claim 21, characterized by the fact that the at least one nano-sized charge (b) is selected from: ZnO, MgO, TiO 2 , SiO 2 , Al 2 O 3 , BaTiO 3 , SnO, MnO 2 , BiO 3 , CuO, In 2 O 3 , La2O 3 , NiO, Sb2O3, SnO2, SrTiO3, Y2O3, W2O3.
    [23]
    23. Cable according to claim 1, characterized by the fact that at least one nano-sized load (b) is present in an amount of 0.2% by weight to 5% by weight, preferably 0.5% by weight at 2% by weight, with respect to the weight of the thermoplastic polymer material (a).
    [24]
    24. Cable according to claim 1, characterized by the fact that it includes at least one semiconductive layer that comprises, in addition to components (a) and (b):
    (d) at least one conductive charge, preferably a carbon black charge.
    类似技术:
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    同族专利:
    公开号 | 公开日
    RU2547011C2|2015-04-10|
    US20130025909A1|2013-01-31|
    AR080049A1|2012-03-07|
    AU2010344307A1|2012-08-23|
    BR112012018898A2|2016-04-12|
    US10811163B2|2020-10-20|
    CN102822257B|2014-03-12|
    CN102822257A|2012-12-12|
    RU2012135514A|2014-03-10|
    WO2011092533A1|2011-08-04|
    EP2528968B1|2017-03-22|
    CA2788403C|2017-08-08|
    CA2788403A1|2011-08-04|
    AU2010344307B2|2014-06-05|
    EP2528968A1|2012-12-05|
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    法律状态:
    2018-04-17| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-02| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-10-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-11-26| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/01/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/01/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/IB2010/000155|WO2011092533A1|2010-01-29|2010-01-29|Energy cable|
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