WO2016097249A1 - Composition polymère pour câble d'alimentation, à propriétés électriques avantageuses - Google Patents

Composition polymère pour câble d'alimentation, à propriétés électriques avantageuses Download PDF

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Publication number
WO2016097249A1
WO2016097249A1 PCT/EP2015/080407 EP2015080407W WO2016097249A1 WO 2016097249 A1 WO2016097249 A1 WO 2016097249A1 EP 2015080407 W EP2015080407 W EP 2015080407W WO 2016097249 A1 WO2016097249 A1 WO 2016097249A1
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Prior art keywords
power cable
polymer composition
direct current
crpe
high voltage
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PCT/EP2015/080407
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English (en)
Inventor
Villgot Englund
Per-Ola Hagstrand
Virginie Eriksson
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Borealis Ag
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Publication of WO2016097249A1 publication Critical patent/WO2016097249A1/fr

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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
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the invention relates to a power cable polymer composition which comprises a chromium catalyst polyethylene (CrPE), a power cable, for example, a high voltage direct current
  • a power cable polymer composition which comprises a chromium catalyst polyethylene (CrPE), a power cable, for example, a high voltage direct current
  • PV DC high vacuum DC
  • a power cable polymer insulation use of a polymer composition for producing a layer of a power cable, and a process for producing a power cable.
  • Polyolefms produced in a high pressure (HP) process are widely used in demanding polymer applications wherein the polymers must meet high mechanical and/or electrical requirements. For instance in power cable applications, particularly in medium voltage (MV) and especially in high voltage (HV) and extra high voltage (EHV) cable
  • the electrical properties of the polymer composition have a significant importance. Furthermore, the electrical properties of importance may differ in different cable applications, as is the case between alternating current (AC) and direct current (DC) cable applications.
  • AC alternating current
  • DC direct current
  • a typical power cable comprises a conductor surrounded, at least, by an inner
  • the cables are commonly produced by extruding the layers on a conductor.
  • the polymer material in one or more of said layers is often crosslinked to improve, e.g., heat and deformation resistance, creep properties, mechanical strength, chemical resistance and abrasion resistance of the polymer in the layer(s) of the cable.
  • crosslinking reaction of a polymer interpolymer crosslinks (bridges) are primarily formed.
  • Crosslinking can be achieved using e.g. a free radical generating compound, such as a peroxide. Free radical generating agent is typically incorporated to the layer material prior to, or during, the extrusion of the layer(s) on a conductor.
  • the cable is then subjected to a crosslinking step to initiate the radical formation and thereby crosslinking reaction.
  • Peroxides are very common free radical generating compounds used e.g. in the polymer industry for said polymer modifications.
  • the resulting decomposition products of peroxides may include volatile by-products which are undesired, since they may have a negative influence on the electrical properties of the cable. Therefore the volatile decomposition products such as methane e.g. where, for example, dicumylperoxide is used, are conventionally reduced to a minimum or removed after crosslinking and cooling step.
  • Such removal step is generally known as a degassing step.
  • the degassing step is time and energy consuming and is thus a costly operation in a cable manufacturing process. Also the used cable production line and desired production speed can bring limitations to the cable materials especially when producing power cables of a larger size.
  • the DC electrical conductivity is an important material property for, e.g., insulating materials for high voltage direct current (HV DC) cables.
  • HV DC high voltage direct current
  • the temperature and electric field dependence of this property will influence the electric field.
  • the second issue is the fact that heat will be generated inside the insulation by the electric leakage current flowing between the inner and outer semiconductive layers. This leakage current depends on the electric field and the DC electrical conductivity of the insulation.
  • High DC conductivity of the insulating material can even lead to thermal runaway under high stress/high temperature conditions and subsequently breakdown of the insulation system. The DC conductivity must therefore be sufficiently low to avoid thermal runaway.
  • the insulation is heated by the leakage current.
  • the heating is proportional to the insulation DC conductivity x (electrical field) 2 .
  • EP2548208 discloses polymer compositions for producing layers of a direct current (DC) power cable wherein the polymer composition comprises a polyolefm being a polyethylene or polypropylene.
  • An object of the present invention is to provide a power cable polymer composition with advantageous electrical properties, e.g. low direct current (DC) electrical conductivity.
  • advantageous electrical properties e.g. low direct current (DC) electrical conductivity.
  • the present invention provides a power cable polymer composition, which power cable polymer composition comprises a chromium catalyst polyethylene (CrPE).
  • CrPE chromium catalyst polyethylene
  • the power cable polymer composition of the present invention has advantageous electrical properties, i.e. the DC electrical conductivity of the power cable polymer composition is reduced, i.e. lowered or low.
  • the DC electrical conductivity of the power cable polymer composition of the present invention is reduced in comparison to the DC electrical conductivity of conventional polymer material suitable for power cables, while desired mechanical properties are maintained.
  • “Reduced”, “lowered” or “low” DC electrical conductivity may herein be used interchangeably, and it means that it is the value obtained from the DC conductivity measurement as described herein under “Determination methods” that is reduced.
  • the low DC electrical conductivity is beneficial for minimising the undesired heat formation in, e.g., an insulation layer of a power cable.
  • the power cable polymer composition has, unexpectedly, a low DC electrical conductivity and is produced without any crosslinking by means of a crosslinking agent, such as peroxide.
  • a crosslinking agent such as peroxide.
  • the non-crosslinked power cable polymer composition can still meet e.g. the mechanical properties desired for, for example, an insulation layer of a power cable.
  • the power cable polymer composition comprising a chromium catalyst polyethylene (CrPE) typically contains very low levels of chlorine compared to Ziegler Natta
  • the chromium catalyst polyethylene which is a low pressure PE, may be selected from homopolymers of ethylene and copolymers of ethylene with, for example, minor amounts of at least one C 3 to C20 alpha-olefm, e.g. C 3 to Cs alpha-olefm.
  • a polymer composition has a low amount of undesired particles/contaminants, i.e. solid material that is not a part of the composition.
  • a power cable polymer composition in accordance with the present invention, has a high level of "physical cleanliness".
  • a low amount of undesired particles/contaminants are a prerequisite for a power cable polymer composition as otherwise the power cable will be prone to electric breakdown.
  • a general polymer composition without a low and controlled level of undesired particles/contaminants may not work in a power cable.
  • power cable polymer compositions are generally produced with highly optimised processes and delivered in special packages suited for power cable polymer compositions to withhold the level of contaminants.
  • concentration of molecular species contributing to the DC electrical conductivity must also be kept on a very low level, i.e. the "chemical cleanliness" must be high. Otherwise, as described above, there is a risk for thermal breakdown of the power cable.
  • the absence of acid scavenger can be seen as an improvement of the chemical cleanliness of the power cable polymer composition of the present invention.
  • a chromium catalyst polyethylene means that the polyethylene is polymerised in the presence of a chromium catalyst which is a
  • the chromium catalysts are previously well known, and for detailed description, see M. P. McDaniel, Advances in Catalysis, Vol. 33 (1985), pp 47-98 and M. P. McDaniel, Ind. Eng. Chem. Res., Vol. 27 (1988), pp 1559-1569.
  • the chromium catalyst is supported by a carrier, preferably silica.
  • the so-called Phillips catalyst which is based on chromium trioxide on a silica carrier, is a chromium catalyst suitably used in the invention.
  • the Phillips catalyst is generally produced by activating silica together with a so-called master batch of chromium trioxide or chromic acetate.
  • chromic acetate When chromic acetate is used it is oxidised to chromium trioxide, so that the end product is the same no matter whether chromium trioxide or chromic acetate is uses.
  • the chromium trioxide forms volatile chromic acid, which is evenly distributed on the silica particles.
  • the 6-valent chromium deposited on the silica particles should then be reduced in order to become catalytically active, and this happens when the chromium comes into contact with the ethylene in the polymerisation reactor.
  • chromium catalyst that can be used in the present invention is the so-called chromate-type catalyst.
  • a chromate compound such as silyl chromate
  • an activated silica carrier When producing such a catalyst, a chromate compound, such as silyl chromate, is deposited on an activated silica carrier. The deposited chromate is reduced by means of an alkoxide, such as an aluminium alkoxide, e.g. diethyl aluminium ethoxide.
  • the chromium catalyst in accordance with the present invention, can be modified by titanation and fluoridation, which is in accordance with the prior art (see, for instance, the Preparation of Catalysts, V. G. Oncelet et al, Elsevier Science Publishers, Amsterdam, 1991, pp 215-227, an article by C. 30 E. Marsden).
  • the power cable polymer composition as described herein, is a power cable insulation polymer composition.
  • the power cable polymer composition is in this embodiment especially suitable for insulation in a power cable, as described herein.
  • the power cable polymer composition of the present invention is a power cable insulation polymer composition
  • the power cable polymer composition has special properties typical for a power cable insulation polymer composition.
  • Special properties of a power cable insulation may be, for example, high level of "physical cleanliness” i.e. low level of undesired particles/contaminants, specialised packaging that facilitates a low risk of contamination from production of the polymer composition until it is extruded onto the conductor when the cable is formed.
  • concentration of species contributing to the DC electrical conductivity must be kept on a very low level, i.e. the "chemical cleanliness” must be high. Otherwise, as described above, there is a risk for thermal breakdown of the power cable.
  • a power cable polymer composition as described herein, is provided, wherein the power cable polymer composition is a non- crosslinked power cable polymer composition.
  • An embodiment of the present invention provides a power cable polymer composition, as described herein, wherein the power cable polymer composition is a thermoplastic power cable po lymer composition.
  • the present invention provides a power cable polymer composition, as described herein, which is suitable for a low voltage (LV), medium voltage (MV), high voltage (HV) and/or extra-high voltage (EHV) power cable.
  • LV low voltage
  • MV medium voltage
  • HV high voltage
  • EHV extra-high voltage
  • High voltage direct current (HV DC) is usually considered to be operating at voltages higher than 36 kV and up to 320 kV DC
  • extra high voltage direct current (EHV DC) is usually considered to be above 320 kV DC
  • high voltage alternating current (HV AC) is usually considered to be up to 220 kV AC
  • extra high voltage alternating current (EHV AC) is usually considered to be above 220 kV AC.
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • a power cable operating at very high voltages is known in the art as extra high voltage direct current (EHV DC) power cable which in practice can operate as high as 900 kV, or possibly even higher.
  • a power cable polymer composition as described herein, is provided being a high voltage (HV) and/or extra-high voltage (EHV) power cable polymer composition.
  • An embodiment of the present invention provides a power cable polymer composition, as described herein, being an extra-high voltage (EHV) power cable polymer composition.
  • a power cable polymer composition as described herein, is provided being high voltage (HV) power cable polymer composition.
  • HV high voltage
  • composition as described herein, being a medium voltage (MV) power cable polymer composition.
  • MV medium voltage
  • LV low voltage
  • the present invention further provides a power cable polymer composition, as described herein, which is a direct current (DC) power cable polymer composition.
  • a power cable polymer composition as described herein, which is a direct current (DC) power cable polymer composition.
  • the present invention provides a power cable polymer composition, as described herein, being a high voltage direct current (HV DC) and/or an extra high voltage direct current (EHV DC) power cable polymer composition.
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • the present invention provides a power cable polymer composition, as described herein, direct current (DC) power cable, e.g., for a direct current (DC) power cable operating at voltages higher than 320 kV, for example, up to 525 kV, such as a high voltage direct current (HV DC) or extra high voltage direct current (EHV DC) power cable, as described herein.
  • DC direct current
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • the present invention provides a power cable polymer composition, as described herein, being a medium voltage direct current (MV DC) power cable polymer composition. Still further, the present invention provides a power cable polymer composition, as described herein, which is a low voltage direct current (LV DC) power cable polymer composition. Accordingly, the low DC electrical conductivity makes the power cable polymer composition of the present invention desirable for power cable applications. Furthermore, the low DC electrical conductivity makes the power cable polymer composition of the present invention very desirable for DC power cable applications. In DC power cable applications, the voltage applied to the power cable is direct current (DC).
  • a DC power cable is defined to be a DC cable transferring energy operating at any DC voltage level, typically operating at DC voltages higher than 1 kV.
  • the power cable polymer composition is advantageous in insulation layer material for a power cable, which can be, e.g., a low voltage (LV), a medium voltage (MV), a high voltage (HV) or an extra high voltage (EHV) power cable, which terms, as well known, indicate the level of operating voltage.
  • a power cable which can be, e.g., a low voltage (LV), a medium voltage (MV), a high voltage (HV) or an extra high voltage (EHV) power cable, which terms, as well known, indicate the level of operating voltage.
  • the power cable polymer composition may be comprised in an exemplified insulation layer material for a DC power cable operating at voltages higher than 36 kV, such as a HV DC cable.
  • a DC power cable operating at voltages higher than 36 kV such as a HV DC cable.
  • the operating voltage is defined herein as the electric voltage between ground and the conductor of the high voltage cable.
  • the present invention is further directed to a power cable as described herein, for example, a direct current (DC) power cable, comprising a conductor surrounded by at least an inner semiconductive layer, an insulation layer and an outer semiconductive layer, in that order, wherein at least one layer, for example, at least an insulation layer, comprises the power cable polymer composition of the present invention, as described herein.
  • a direct current (DC) power cable comprising a conductor surrounded by at least an inner semiconductive layer, an insulation layer and an outer semiconductive layer, in that order, wherein at least one layer, for example, at least an insulation layer, comprises the power cable polymer composition of the present invention, as described herein.
  • the inner semiconductive layer comprises a first semiconductive composition
  • the insulation layer comprises an insulation composition
  • an outer semiconductive layer comprises a second semiconductive composition, in that order, and wherein the insulation composition of the insulation layer comprises, for example, consists, of said power cable polymer composition of the present invention, as described herein.
  • the outer semiconductive layer comprises, for example, consists of, a non-crosslinked second semiconductive composition.
  • the inner semiconductive layer for example, comprises, e.g., consists of, a non-crosslinked first semiconductive composition.
  • a power cable as described herein for example, a direct current (DC) power cable
  • the first semiconductive composition of the inner semiconductive layer and the power cable polymer composition of the invention of the insulation layer are non- crosslinked
  • the second semiconductive composition of the outer semiconductive layer is non-crosslinked.
  • DC conductivity properties of the final power cable of such embodiments are advantageous for the power cable applications as described herein, and are very advantageous for DC power cable applications, even for HV DC power cable applications and also for EHV DC power cable applications. Further, at the same time desired mechanical properties are maintained with such embodiments for the power cable applications as described herein.
  • the power cable polymer composition of the present invention is, for example, used in an insulation layer of a high voltage direct current (HV DC) power cable operating at voltages of 40 kV or higher, even at voltages of 50 kV or higher.
  • HV DC high voltage direct current
  • the power cable polymer composition of the present invention, as described herein is, for example, used in an insulation layer of a HV DC power cable operating at voltages of 60 kV or higher.
  • the power cable polymer composition of the present invention, as described herein is also highly feasible in very demanding cable applications and can be used in an insulation layer of a HV DC power cable operating at voltages higher than 70 kV.
  • the upper limit may be as high as 1000 kV, or possibly even higher.
  • the power cable polymer composition of the present invention is advantageous for use in a high voltage direct current (HV DC) power cable and extra high voltage direct current (EHV DC) power cable applications operating from 75 to 400 kV, for example, 75 to 350 kV. Moreover, the power cable polymer composition of the present invention, as described herein, invention is also found to be advantageous even in demanding extra high voltage direct current (EHV DC) power cable applications operating from 400 to 850 kV.
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • HV DC power cable as used herein means either HV DC power cable, for example, with operating at voltages as defined herein, or extra HV DC power cable, for example, with operating at voltages as defined herein.
  • the term covers independently the operating areas for both HV DC power cable applications and also the EHV DC power cable applications.
  • the power cable polymer composition of the present invention has, for example, a DC electrical conductivity of 45 fS/m or less, for example, 40 fS/m or less, e.g., 35 fS/m or less, for example, 30 fS/m or less, e.g., 25 fS/m or less, for example, 20 fS/m or less, e.g., 17 fS/m or less, for example, 15 fS/m or less, e.g., 0.01 to 45 fS/m, for example, 0.01 to 40 fS/m, e.g., 0.05 to 45 fS/m, for example, 0.05 to 40 fS/m, e.g., 0.05 to 35 fS/m, for example, 0.05 to 30 fS/m, e.g., 0.05 to 20 fS/m, for example, 0.05 to 10.0 fS/m, e.g., 0.05
  • the power cable polymer composition has, for example, a DC electrical conductivity of 10.0 fS/m or less, for example, 8.0 fS/m or less, e.g., 7.0 fS/m or less, for example, 6.0 fS/m or less, or, e.g., 5.0 fS/m or less, when measured according to the DC conductivity method as described under "Determination Methods".
  • composition as described herein, has, for example, a DC electrical conductivity 0.05 to 10.0 fS/m, e.g., 0.05 to 6.0 fS/m, for example, 0.01 to 7.0 fS/m, or, e.g., 0.01 to 5.0 fS/m, when measured according to the DC conductivity method as described under
  • the chromium catalyst polyethylene (CrPE), in accordance with the present invention, may be selected from an ethylene homopolymer or a copolymer of ethylene with one or more comonomer(s). Further, the chromium catalyst polyethylene (CrPE) belongs to the group of "poly ethylenes polymerised in the presence of an olefin polymerisation catalyst", which group is also often called “low pressure polyethylenes” or “low pressure PEs” to distinguish it clearly from HPPEs, "high pressure polyethylenes”.
  • the chromium catalyst polyethylene which is a low pressure PE
  • can be unimodal or multimodal with respect to molecular weight distribution (MWD Mw/Mn).
  • Mw molecular weight distribution
  • a polymer comprising at least two polymer fractions, which have been produced under different polymerisation conditions resulting in different (weight average) molecular weights and molecular weight distributions for the fractions is referred to as "multimodal".
  • multi relates to the number of different polymer fractions present in the polymer.
  • multimodal polymer includes so called "bimodal" polymer consisting of two fractions.
  • the form of the molecular weight distribution curve i.e.
  • the appearance of the graph of the polymer weight fraction as a function of its molecular weight, of a multimodal polymer will show two or more maxima or is typically distinctly broadened in comparison with the curves for the individual fractions.
  • the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight.
  • the individual curves from these fractions form typically together a broadened molecular weight distribution curve for the total resulting polymer product.
  • the chromium catalyst polyethylene (CrPE) being the low pressure PE can be a copolymer of ethylene with one or more comonomer(s).
  • Comonomer as used herein means monomer units other than ethylene, which are copolymerisable with ethylene.
  • the chromium catalyst polyethylene (CrPE) being the low pressure PE copolymer is, for example, a copolymer of ethylene with one or more olefin comonomer(s), for example, with at least C 3 _ 2 o alpha-olefm, e.g., with at least one C 4 _i 2 alpha-olefm, for example, with at least one C 4 _8 alpha-olefm, e.g. with 1-butene, 1-hexene or 1-octene.
  • the amount of comonomer(s) present in such a PE copolymer is from 0.1 to 15 mol%, typically 0.25 to 10 mol-%.
  • the chromium catalyst polyethylene is selected from homopolymers of ethylene and copolymers of ethylene with, for example, minor amounts of at least one C 3 to C 2 o alpha-olefm, e.g. C 3 to Cs alpha-olefm.
  • the chromium catalyst polyethylene (CrPE) being homopolymers or copolymers of ethylene generally have a density of 935 to 970 kg/m 3 , for example, of 940 to 960 kg/m 3 and the C 3 to C 2 o alpha-olefm, e.g. C 3 to Cs alpha-olefm, content in the copolymers of ethylene can be about from 0.01% to 5% by weight.
  • the chromium catalyst polyethylene is selected from medium density polyethylene (MDPE) copolymers or high density polyethylene (HDPE) homopolymers or copolymers. These well known types are named according to their density area.
  • the MDPE has a density of from 930 to 945 kg/m 3 , for example, 931 to 945 kg/m 3 .
  • the HDPE has a density of more than 945 kg/m 3 , for example, more than 946 kg/m 3 , e.g., 946 to 977 kg/m 3 , for example, 946 to 965 kg/m 3 .
  • a power cable polymer composition as described herein, is provided, wherein the power cable polymer composition comprises a chromium catalyst polyethylene with a density of 930 to 949 kg/m 3 .
  • the chromium catalyst polyethylene (CrPE) being a low pressure PE has, for example, an MFR 2 i of up to 120 g/10 min, e.g., up to 100 g/10 min, for example, up to 80 g/10 min, e.g., up to 70 g/10 min, for example, up to 65 g/10 min, e.g., 0.01 to 100, for example, 0.01 to 80 g/10 min, e.g., 0.01 to 70.0 g/10 min, or, for example, from 0.05 to 65.0 g/10 min.
  • MFR 2 i of up to 120 g/10 min, e.g., up to 100 g/10 min, for example, up to 80 g/10 min, e.g., up to 70 g/10 min, for example, up to 65 g/10 min, e.g., 0.01 to 100, for example, 0.01 to 80 g/10 min, e.g., 0.01 to 70.0 g/10 min, or, for example,
  • the chromium catalyst polyethylene has, for example, an MFR 2 of, for example up to 20 g/10 min, e.g., up to 10 g/10 min, for example, up to 5.0 g/10 min, e.g., up to 4.0 g/10 min, for example, up to 3.0 g/10 min, e.g., up to 2.0 g/10 min, for example, up to 1.5 g/10 min, e.g., 0.01 to 10, for example, 0.01 to 5.0 g/10 min, e.g., 0.01 to 4.0 g/10 min, for example, from 0.05 to 3.0 g/10 min, e.g., from 0.1 to 2.0 g/10 min or, e.g., from 0.2 to 1.5 g/10 min.
  • MFR 2 of, for example up to 20 g/10 min, e.g., up to 10 g/10 min, for example, up to 5.0 g/10 min, e.g., up to 4.0 g/10 min, for example,
  • Suitable chromium catalyst polyethylenes (CrPEs) being low pressure PEs as comprised in the power cable polymer composition of the present invention are as such well known and can be e.g. commercially available or, alternatively, can be produced according to or analogously to conventional polymerisation processes which are well documented in the literature.
  • the chromium catalyst polyethylene (CrPE) can be unimodal or multimodal with respect to molecular weight distribution. Further, the chromium catalyst polyethylene (CrPE) is selected from a MDPE copolymer or a HDPE polymer, for example, the chromium catalyst polyethylene (CrPE) is selected from a MDPE copolymer or a HDPE polymer which is unimodal or multimodal with respect to molecular weight distribution. Further, such MDPE or HDPE polymer is multimodal with respect to molecular weight distribution.
  • the power cable polymer composition comprises a medium or high density chromium catalyst polyethylene (MD or HD CrPE).
  • MD or HD CrPE medium or high density chromium catalyst polyethylene
  • An exemplified power cable polymer composition consists of the chromium catalyst polyethylene (CrPE) as the only polymer component.
  • the expression means, in this specific embodiment, that the power cable polymer composition does not contain further polymer components but the chromium catalyst polyethylene (CrPE) as the sole polymer component.
  • the power cable polymer composition also in this specific embodiment, may comprise further components other than the chromium catalyst polyethylene (CrPE), such as additives which may optionally be added in a mixture with a carrier polymer, i.e. in so called master batch.
  • the DC electrical conductivity of the power cable polymer composition of the present invention is surprisingly low.
  • the power cable polymer composition of the present invention may in an embodiment be non-crosslinked, and thus then it comprises no crosslinking agent.
  • the power cable polymer composition of the present invention, which is non-crosslinked, has a very advantageous low DC electrical conductivity.
  • the prior art drawbacks relating to the use of a crosslinking agent in cable layer can be avoided. Naturally, this embodiment enables to simplify the cable production process.
  • the power cable polymer composition of the present invention may contain, in addition to the chromium catalyst polyethylene (CrPE), further component(s) such as polymer component(s) and/or additive(s), for example, additive(s), such as any of antioxidant(s), stabiliser(s), processing aid(s), flame retardant additive(s), water tree retardant additive(s), acid or ion scavenger(s), inorganic filler(s) and voltage stabilizer(s), as known in the polymer field.
  • the power cable polymer composition of the present invention comprises, for example, conventionally used additive(s) for W&C applications, such as one or more antioxidant(s).
  • the used amounts of additives are conventional and well known to a skilled person.
  • the power cable polymer composition of the present invention is used for producing an insulation layer.
  • the power cable polymer composition of the present invention may be without, i.e. does not comprise, a carbon black.
  • the power cable polymer composition of the present invention may be without, i.e. does not comprise, flame retarding additive(s) in such amounts conventionally used for acting as "flame retardants", e.g. a metal hydroxide containing additives in flame retarding amounts.
  • the exemplified embodiments, properties and subgroups herein of the power cable polymer composition of the present invention are independently generalisable so that they can be used in any order or combination to further define the exemplified embodiments of the power cable polymer composition and the power cable produced using the power cable polymer composition.
  • the chromium catalyst polyethylene (CrPE) being the low pressure PE copolymer can be a binary copolymer, i.e. such PE copolymer may contain ethylene and one comonomer, or a terpolymer, i.e such PE copolymer may contain ethylene and two or three comonomers.
  • LLDPE, MDPE or HDPE are exemplified types of a chromium catalyst polyethylene (CrPE) being a low pressure PE for use as the power cable polymer composition of the present invention.
  • CrPE chromium catalyst polyethylene
  • Such LLDPE, MDPE or HDPE can be unimodal or multimodal.
  • the catalyst may be selected from, well known, chromium catalysts, or any mixtures of chromium catalysts. Moreover the catalyst system is supported on a carrier, usually silica- based or Mg-based carrier.
  • the chromium catalyst polyethylene (CrPE) being a unimodal low pressure PE can be produced by a single stage polymerisation in a single reactor in a well known and documented manner.
  • the chromium catalyst polyethylene (CrPE) being a multimodal (e.g. bimodal) low pressure PE can be produced e.g. by blending mechanically together two or more separate polymer components or, for example, by in-situ blending during the polymerisation process of the components. Both mechanical and in-situ blending are well known in the field.
  • the exemplified in-situ blending means the polymerisation of the polymer components under different polymerisation conditions, e.g. in a multistage polymerisation reactor system, i.e. two or more stage, or by the use of two or more different chromium polymerisation catalysts, including multi- or dual site catalysts, in a one stage
  • the polymer is polymerised in a process comprising at least two polymerisation stages.
  • Each polymerisation stage may be conducted in at least two distinct polymerisation zones in one reactor or in at least two separate reactors.
  • the multistage polymerisation process may be conducted in at least two cascaded polymerisation zones. Polymerisation zones may be connected in parallel, or, for example, the polymerisation zones operate in cascaded mode.
  • the polymerisation zones may operate in bulk, slurry, solution, or gas phase conditions or in any combinations thereof.
  • a first polymerisation step is carried out in at least one slurry, e.g. loop, reactor and the second polymerisation step in one or more gas phase reactors.
  • One exemplified multistage process is described in EP517868.
  • the temperature in the chromium catalyst polyethylene (CrPE) polymerisation is typically from 50 to 115 °C, e.g., 60 to 110 °C.
  • the pressure is from 1 to 150 bar, for example, 10 to 100 bar.
  • the precise control of polymerisation conditions can be performed by using different types of catalyst and using different comonomer and/or hydrogen feeds.
  • Prepolymerisation may precede the actual polymerisation step(s), as well known in the field.
  • polymerisation product may be compounded in a known manner and optionally with additive(s) and pelletised for further use.
  • the present invention discloses a power cable, for example, a high voltage direct current (HV DC) and/or an extra high voltage direct current (EHV DC) power cable, which power cable comprises a chromium catalyst polyethylene (CrPE), or which power cable comprises a polymer composition being, or comprising, the power cable polymer composition as described herein.
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • CrPE chromium catalyst polyethylene
  • a further embodiment of the present invention discloses a power cable, for example, a high voltage direct current (HV DC) and/or an extra high voltage direct current (EHV DC) power cable, which power cable comprises a polymer composition being, or comprising, the power cable polymer composition as described herein.
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • Still a further embodiment of the present invention discloses a power cable polymer insulation, for example, a high voltage direct current (HV DC) and/or an extra high voltage direct current (EHV DC) power cable insulation, which power cable insulation comprises a chromium catalyst polyethylene (CrPE), or which power cable insulation comprises a polymer composition being, or comprising, the power cable polymer composition as described herein.
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • CrPE chromium catalyst polyethylene
  • a further embodiment of the present invention discloses a power cable polymer insulation, for example, a high voltage direct current (HV DC) and/or an extra high voltage direct current (EHV DC) power cable insulation, which power cable insulation comprises a polymer composition being, or comprising, the power cable polymer composition as described herein.
  • HV DC high voltage direct current
  • EHV DC extra high voltage direct current
  • the power cable polymer composition of the present invention may be used for producing an insulation, e.g. an insulation layer, of a power cable as described herein, e.g. a direct current (DC) power cable, as described herein.
  • an insulation e.g. an insulation layer
  • DC direct current
  • the invention further provides a power cable, e.g. a direct current (DC) power cable, comprising a conductor which is surrounded at least by an inner semiconductive layer, an insulation layer and an outer semiconductive layer, in that order, wherein at least one layer, for example, at least the insulation layer, comprises, for example, consists of, a power cable polymer composition of the present invention as described herein, or a polymer composition comprising the power cable polymer composition as described herein.
  • the inner semiconductive layer of the power cable comprises, for example, consists of, a first semiconductive composition
  • the insulation layer comprises, for example, consists of, an insulation composition
  • the outer semiconductive layer comprises, e.g., consists of, a second semiconductive composition.
  • the insulation composition comprises, e.g., consists of the power cable polymer composition of the present invention, or of a polymer composition comprising the power cable polymer composition as described herein.
  • the first and the second semiconductive compositions can be different or identical and comprise a polymer(s) which is, for example, a polyolefm or a mixture of polyolefms and a conductive filler, e.g., carbon black.
  • Suitable polyolefm(s) are e.g. polyethylene produced in a low pressure process or a polyethylene produced in a HP process (LDPE).
  • LDPE low pressure process
  • LDPE low pressure process
  • the carbon black can be any conventional carbon black used in the semiconductive layers of a power cable as described herein, e.g. a DC power cable, for example, in the semiconductive layer of a DC power cable.
  • the carbon black may have one or more of the following properties: a) a primary particle size of at least 5 nm which is defined as the number average particle diameter according ASTM D3849-95a, dispersion procedure D b) iodine number of at least 30 mg/g according to ASTM D1510, c) oil absorption number of at least 30 ml/lOOg which is measured according to ASTM D2414.
  • Non-limiting examples of carbon blacks are e.g.
  • the power cable polymer composition may comprise 10 to 50 wt% carbon black, based on the weight of the semiconductive composition.
  • the inner semiconductive layer comprises a first semiconductive composition
  • the insulation layer comprises an insulation composition
  • an outer semiconductive layer comprises a second semiconductive composition, in that order, and wherein the insulation composition of the insulation layer comprises, for example, consists, of said power cable polymer composition of the present invention, as described herein.
  • the outer semiconductive layer comprises, for example, consists of, a non-crosslinked second semiconductive
  • the inner semiconductive layer may, comprise, for example, consists of, a non-crosslinked first semiconductive composition.
  • the term "conductor” means herein that the conductor comprises one or more wires. Moreover, the cable may comprise one or more such conductors. Further, the conductor may be a DC electrical conductor and comprise one or more metal wires. It is exemplified that the power cable polymer composition of the insulation layer of the present invention, consists of the chromium catalyst polyethylene (CrPE), in accordance with the present invention, as the only polymer component. Accordingly, in this embodiment the power cable polymer composition of the present invention comprises no other polymer component(s).
  • CrPE chromium catalyst polyethylene
  • the cable can optionally comprise further layers, e.g. layers surrounding the insulation layer or, if present, the outer semiconductive layers, such as screen(s), a jacketing layer(s), other protective layer(s) or any combinations thereof.
  • the present invention provides a process for producing a power cable, e.g. a direct current (DC) power cable, which process comprises use of a chromium catalyst polyethylene (CrPE), or of a polymer composition being, or comprising, the power cable polymer composition as described herein.
  • the invention also provides a process for producing a power cable, e.g. a direct current (DC) power cable, wherein the process comprises the steps of
  • an inner semiconductive layer comprising a first semiconductive composition
  • an insulation layer comprising an insulation composition
  • an outer semiconductive layer comprising a second
  • the insulation composition of the insulation layer comprises, e.g., consists of, a power cable polymer composition of the present invention, as described herein.
  • a power cable e.g. a direct current (DC) power cable, may be produced, wherein the process comprises the steps of
  • a first semiconductive composition comprising a polymer, a carbon black and optionally further component(s) for the inner semiconductive layer
  • a second semiconductive composition which comprises a polymer, a carbon black and optionally further
  • step (a) a meltmix of the second semiconductive composition obtained from step (a) to form the outer semiconductive layer.
  • Melt mixing means mixing above the melting point of at least the major polymer component(s) of the obtained mixture and is carried out for example, without limiting to, in a temperature of at least 15°C above the melting or softening point of polymer
  • (co)extrusion means herein that in case of two or more layers, said layers can be extruded in separate steps, or at least two or all of said layers can be coextruded in a same extrusion step, as well known in the art.
  • (co)extrusion” means herein also that all or part of the layer(s) are formed simultaneously using one or more extrusion heads. For instance a triple extrusion head can be used for forming three layers.
  • the layers can be extruded using two extrusion heads, the first one for forming the inner semiconductive layer and the inner part of the insulation layer, and the second head for forming the outer insulation layer and the outer semiconductive layer.
  • the power cable polymer composition of the present invention and the optional and exemplified first and second semiconductive compositions can be produced before or during the cable production process.
  • the power cable polymer composition of the present invention and the optional and exemplified first and second semiconductive composition can each independently comprise part or all of the
  • the power cable polymer composition of the present invention and, optionally, the optional first and second semiconductive composition are suitably provided to the cable production process in form of powder, grain or pellets.
  • Pellets mean herein generally any polymer product which is formed from reactor-made polymer (obtained directly from the reactor) by post-reactor modification to solid polymer particles.
  • a well-known post-reactor modification is pelletising a meltmix of a polymer product and optional additive(s) in a pelletising equipment to solid pellets.
  • Pellets can be of any size and shape.
  • the power cable polymer composition of the present invention can be combined in a powder, grain or pellet product, which thus contains a solid polymer mixture of said power cable polymer composition.
  • the (melt)mixing step (a) of the provided power cable polymer composition of the invention and of the exemplified first and second semiconductive compositions is, for example, carried out in a cable extruder.
  • the step (a) of the cable production process may optionally comprise a separate mixing step, e.g. in a mixer arranged in connection and preceding the cable extruder of the cable production line. Mixing in the preceding separate mixer can be carried out by mixing with or without external heating (heating with an external source) of the component(s).
  • any optional exemplified additive(s) can be added to any power cable polymer
  • composition as such or as a mixture with a carrier polymer, i.e. in a form of so-called master batch.
  • a power cable e.g. a direct current (DC) power cable
  • the insulation layer comprises, e.g., consists of, a power cable polymer composition of the present invention.
  • processing temperatures and devices are well known in the art, e.g. conventional mixers and extruders, such as single or twin screw extruders, are suitable for the process of the invention.
  • connection of cables may be facilitated due to non-crosslinked thermoplastic power cable insulation polymer composition and thermoplastic power cable.
  • Exemplified DC power cables are high voltage direct current (HV DC) power cable or extra high voltage direct current (EHV DC) power cable. Further, said high voltage direct current (HV DC) power cable, or extra high voltage direct current (EHV DC) power cable, may operate at voltages as defined herein.
  • the thickness of the insulation layer of the power cable e.g. the direct current (DC) power cable, for example, the HV DC power cable
  • the thickness of the insulation layer of the power cable is typically 2 mm or more, for example, at least 3 mm, for example, at least 5 to 100 mm, for example, from 5 to 50 mm, and conventionally 5 to 40 mm, e.g. 5 to 35 mm, when measured from a cross section of the insulation layer of the cable.
  • the thickness of the inner and outer semiconductive layers is typically less than that of the insulation layer, and in, for example, HV DC power cables can be e.g. more than 0.1 mm, such as from 0.3 up to 20 mm, 0.3 to 10 of inner
  • the thickness of the inner semiconductive layer is for example, 0.3 - 5.0 mm, e.g., 0.5 - 3.0 mm, for example, 0.8 - 2.0 mm.
  • the thickness of the outer semiconductive layer is, for example, 0.3 to 10 mm, such as 0.3 to 5 mm, e.g., 0.5 to 3.0 mm, for example, 0.8 - 3.0 mm. It is evident for and within the skills of a skilled person that the thickness of the layers of the power cable, e.g. the direct current (DC) power cable, depends on the intended voltage level of the end application cable and can be chosen accordingly.
  • DC direct current
  • the present invention does also relate to use of a chromium catalyst polyethylene (CrPE); or of a polymer composition being, or comprising, the power cable polymer composition as described herein; for producing at least one layer, for example, an insulation layer, of a power cable comprising a conductor surrounded by at least an inner semiconductive layer, an insulation layer and an outer semiconductive layer, in that order.
  • CrPE chromium catalyst polyethylene
  • the present invention does also further relate to use of a polymer composition being, or comprising, the power cable polymer composition as described herein, for producing at least one layer, for example, an insulation layer, of a power cable comprising a conductor surrounded by at least an inner semiconductive layer, an insulation layer and an outer semiconductive layer, in that order.
  • the present invention does also relate to use of a chromium catalyst polyethylene (CrPE); or of a polymer composition being, or comprising, the power cable polymer composition as described herein; for producing at least one layer, for example, an insulation layer, of a power cable which is a direct current (DC) power cable.
  • CrPE chromium catalyst polyethylene
  • the present invention does also relate to use of a polymer composition being, or comprising, the power cable polymer composition as described herein, for producing at least one layer, for example, an insulation layer, of a power cable which is a direct current (DC) power cable.
  • a polymer composition being, or comprising, the power cable polymer composition as described herein, for producing at least one layer, for example, an insulation layer, of a power cable which is a direct current (DC) power cable.
  • DC direct current
  • a use of the power cable polymer composition, as described herein, for producing an insulation layer of a power cable is disclosed, wherein the insulation layer comprises, for example, consists of, a chromium catalyst polyethylene (CrPE), or comprises, for example, consists of, a power cable polymer composition, as described herein.
  • the insulation layer comprises, for example, consists of, a chromium catalyst polyethylene (CrPE), or comprises, for example, consists of, a power cable polymer composition, as described herein.
  • Figure 1 shows a schematic picture of the measurement setup used in the DC conductivity method as described under “Determination methods”.
  • Explanation of the numbered parts “1-6” “1" Connection to high voltage; “2" Measuring electrode; “3” Electrometer/Pico Ammeter; “4" Brass electrode; “5" Test sample, i.e. polymer composition; “6” Si-rubber.
  • the melt flow rate is determined according to ISO 1133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
  • the MFR is determined at 190 °C for polyethylene. MFR may be determined at different loadings such as 2.16 kg (MFR 2 ) or 21.6 kg (MFR 2 i). Density
  • Low density polyethylene The density was measured according to ISO 1183-2. The sample preparation was executed according to ISO 1872-2 Table 3 Q (compression moulding).
  • Example 2 The chromium catalyst polyethylene (CrPE) in Example 2, 3 and 4 (low pressure process polyethylene): Density of the Example 2, 3 and 4 was measured according to ISO 1183 / 1872-2B.
  • CrPE chromium catalyst polyethylene
  • the plaques are compression moulded from pellets of the test polymer composition.
  • the final plaques have a thickness of 1 mm and a diameter of 260 mm.
  • the plaques are compression moulded at 130°C for 600 s at a pressure of 2.6 MPa.
  • the temperature is increased and reaches 180°C after 5 min.
  • the temperature is then kept constant at 180°C for 1000 s.
  • the temperature is decreased at a cooling rate 15 °C/min until room temperature is reached when the pressure is released.
  • a high voltage source is connected to the upper electrode in order to apply voltage over the test sample.
  • the resulting current through the sample is measured with an
  • the measurement cell is a three electrodes system with brass electrodes placed in a heated oven circulated with dried compressed air to maintain constant humidity level.
  • the diameter of the measurement electrode is 100 mm.
  • the applied voltage is 30 kV DC meaning a mean electric field of 30 kV/mm.
  • the temperature is 70°C and the whole experiments last for 24 hours including heating to the test temperature.
  • the current through the plaque is logged.
  • the current after 24 hours is used to calculate the conductivity of the test sample i.e. the plaque consisting of the polymer composition to be tested.
  • LDPE low density polyethylene having a density of 922 kg/m 3 .
  • Example 2 (inventive), example 3 (inventive) and example 4 (inventive)
  • Chromium catalyst polyethylene (CrPE)
  • Chromium catalyst polyethylene (CrPE): The chromium catalyst polyethylene (1- hexene as the comonomer) for example 2, the chromium catalyst polyethylene (1-butene as comonomer) for example 3 and the chromium catalyst polyethylene (homopolymer ) for example 4 was prepared with the above chromium catalysts and as described below. Fluid Bed Gas Phase Example
  • Example 2 inventive
  • example 3 inventive
  • example 4 Inventive
  • a fluid bed gas phase reactor an olefin is polymerised in the presence of a polymerisation catalyst in an upwards moving gas stream.
  • the reactor typically contains a fluidized bed comprising the growing polymer particles containing the active catalyst located above a fluidization grid.
  • the polymer bed is fluidized with the help of the fluidization gas comprising the olefin monomer, eventual comonomer(s), eventual chain growth controllers or chain transfer agents, such as hydrogen, and eventual inert gas.
  • the fluidization gas is introduced into an inlet chamber at the bottom of the reactor.
  • One or more of the above- mentioned components may be continuously added into the fluidization gas to compensate for losses caused, among other, by reaction or product withdrawal.
  • From the inlet chamber the gas flow is passed upwards through a fluidization grid into the fluidized bed.
  • the fluidization gas passes through the fluidized bed.
  • the superficial velocity of the fluidization gas must be higher than the minimum fluidization velocity of the particles contained in the fluidized bed, as otherwise no fluidization would occur.
  • the velocity of the gas should be lower than the onset velocity of pneumatic transport, as otherwise the whole bed would be entrained with the fluidization gas.
  • the reactive components of the gas react in the presence of the catalyst to produce the polymer product, i.e. the chromium catalyst polyethylene.
  • the gas is heated by the reaction heat.
  • the unreacted fluidization gas is removed from the top of the reactor and cooled in a heat exchanger to remove the heat of reaction.
  • the gas is cooled to a temperature which is lower than that of the bed to prevent the bed from heating because of the reaction. It is possible to cool the gas to a temperature where a part of it condenses.
  • the liquid droplets enter the reaction zone they are vaporised. The vaporisation heat then contributes to the removal of the reaction heat.
  • the condensing agents are non-polymerisable components, such as n- pentane, isopentane, n-butane or isobutane, which are at least partially condensed in the cooler.
  • the gas is then compressed and recycled into the inlet chamber of the reactor. Prior to the entry into the reactor fresh reactants are introduced into the fluidization gas stream to compensate for the losses caused by the reaction and product withdrawal. It is generally known how to analyse the composition of the fluidization gas and to introduce the gas components to keep the composition constant. The actual composition is determined by the desired properties of the product and the catalyst used in the polymerisation.
  • the catalyst may be introduced into the reactor in various ways, either continuously or intermittently.
  • the polymeric product may be withdrawn from the gas phase reactor either continuously or intermittently. Combinations of these methods may also be used.
  • the fluidized bed polymerisation reactor is operated at a temperature within the range of from 50 to 110 °C, preferably from 65 to 110 °C.
  • the pressure is suitably from 10 to 40 bar, preferably from 15 to 30 bar.
  • Ref contained crosslinking agent and was crosslinked as disclosed in DC conductivity method under "Determination methods" and the conductivity was measured from the crosslinked plaques.
  • the amounts of polymer composition components in table 2 are based on the combined amount of the used polymer composition components.
  • the amount 100 wt% of polymer in table 2 means that this polymer is the sole polymer component.
  • the chromium catalyst polyethylene (CrPE) of inventive example 2 , inventive example 3 and inventive example 4 shows excellent low DC conductivity.
  • the chromium catalyst polyethylenes (CrPEs), in accordance with the present invention, are suitable in the power cable polymer compositions of the invention, e.g. in DC power cables, for example, in HV DC power cables.

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Abstract

L'invention concerne une composition polymère pour câble d'alimentation, comprenant un polyéthylène à catalyseur au chrome (CrPE), un câble d'alimentation, par exemple, un courant continu haute tension (CC HT), une isolation polymère du câble d'alimentation, l'utilisation d'une composition polymère aux fins de réalisation d'une couche d'un câble d'alimentation, ainsi qu'un procédé de fabrication d'un câble d'alimentation.
PCT/EP2015/080407 2014-12-19 2015-12-18 Composition polymère pour câble d'alimentation, à propriétés électriques avantageuses WO2016097249A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674915A (en) * 1971-06-01 1972-07-04 Phillips Petroleum Co Electrical cable having an ethylene-1-olefin copolymer as the dielectric material
JP2006045273A (ja) * 2004-07-30 2006-02-16 Nippon Polyethylene Kk 電線用直鎖状低密度ポリエチレン・その組成物ならびにその電線用直鎖状低密度ポリエチレンの製造方法
US7238765B2 (en) * 2003-02-06 2007-07-03 Equistar Chemicals, Lp High density polyethylene and insulation compositions for wire and cable
WO2011113685A1 (fr) * 2010-03-17 2011-09-22 Borealis Ag Composition polymère pour application w&c à propriétés électriques avantageuses

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674915A (en) * 1971-06-01 1972-07-04 Phillips Petroleum Co Electrical cable having an ethylene-1-olefin copolymer as the dielectric material
US7238765B2 (en) * 2003-02-06 2007-07-03 Equistar Chemicals, Lp High density polyethylene and insulation compositions for wire and cable
JP2006045273A (ja) * 2004-07-30 2006-02-16 Nippon Polyethylene Kk 電線用直鎖状低密度ポリエチレン・その組成物ならびにその電線用直鎖状低密度ポリエチレンの製造方法
WO2011113685A1 (fr) * 2010-03-17 2011-09-22 Borealis Ag Composition polymère pour application w&c à propriétés électriques avantageuses

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200617, Derwent World Patents Index; AN 2006-160091, XP002740376 *

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